Catalyst for synthesis of carboxylic esters, preparation method thereof and method for synthesis of carboxylic esters

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for synthesis of carboxylic esters. Described is a catalyst for synthesis of a carboxylic ester through reaction of (a) an aldehyde and alcohol, or (b) one or more types of alcohols in the presence of oxygen, the catalyst containing: nickel oxide; and X, where X is at least one element selected from a group comprising palladium, platinum, ruthenium, gold, silver and copper, deposited on a carrier in atomic ratio Ni/(Ni+X) from 0.20 to 0.99. Described is a method of preparing a catalyst for synthesis of a carboxylic ester, involving a first step for producing a catalyst precursor by depositing nickel and component X, where X is at least one element selected from a group comprising palladium, platinum, ruthenium, gold, silver and copper on a carrier through neutralisation of an acidic solution of a soluble metal salt containing nickel and X; and a second step for oxidising nickel via thermal treatment of the obtained catalyst precursor, where the atomic ratio Ni/(Ni+X) ranges from 0.20 to 0.99. Described also is a method for synthesis of a carboxylic ester, involving a step for reaction of the described catalyst with (a) an aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen.

EFFECT: active catalyst for synthesis of a carboxylic ester is obtained.

17 cl, 5 tbl, 5 dwg, 48 ex

 

The technical field

The present invention relates to a catalyst for obtaining esters of carboxylic acids by reacting the aldehyde and alcohol, or one or more types of alcohols, in the presence of oxygen, to a method for producing the catalyst and to a process for the preparation of esters of carboxylic acids using a catalyst.

Prior art

The method of obtaining esters of carboxylic acids on an industrial scale, in the case of methyl methacrylate, for example, may include the way in which methacrylic acid is obtained by oxidation of methacrolein oxygen with the subsequent interaction of methacrylic acid with methanol to obtain methyl methacrylate. However heterophilically the catalyst used in the process of getting methacrylic acid by the oxidation of methacrolein, has problems with thermal stability, and gradually decomposes at temperature conditions of the reaction. In addition, the output also remains insufficient, giving thus the opportunity to improve industrial catalyst.

On the other hand, direct Metaprocess receipt of methyl methacrylate or methyl acrylate in one stage by reacting methacrolein or acrolein with methanol and molecular oxygen is the simple way is which does not require separation easily polymerized methacrylic acid or acrylic acid, and currently attracts attention due to higher yield of methyl methacrylate in comparison with the above method.

In this way, as the catalyst used, the catalyst mainly containing palladium. However, in the process of producing methyl methacrylate or methyl acrylate in one stage by reacting methacrolein or acrolein with methanol and molecular oxygen as methacrolein or acrolein is unsaturated aldehyde, numerous acetals of unsaturated aldehyde, alkoxy-shape formed by the addition of alcohol to the unsaturated linkages, formed as a by-product, which also leads to the problem associated with the formation of gaseous carbon dioxide, which is the final oxidation product (see patent document 1).

In this regard, created modifications of the catalyst to overcome these problems. For example, it was reported that the above-mentioned problems relating to the formation of by-products, solved, and an ester of carboxylic acid can be obtained with high yield resulting from the use of a catalyst containing intermetallic compound, composed of palladium and at least one element selected from the group consisting of lead, mercury, bismuth and thallium, or a catalyst containing a compound of an alkali metal or a compound of alkaline earth metal (see patent document 2).

On the other hand, though, as Polak is whether for a long time, for catalysts used in this way requires the presence of a catalyst containing palladium, recently reported on the use of catalysts which contain a noble metal such as ruthenium or gold, deposited on the carrier. Specific examples of such methods include the use of a catalyst in which gold is deposited on the carrier (see patent document 3), or the use of a catalyst containing ruthenium (see patent document 4), in the process of obtaining a complex ester of carboxylic acid by reacting the aldehyde and alcohol in the presence of oxygen-containing gas.

Patent document 1: publication of the Japan patent No. S45-34368

Patent document 2: publication of the Japan patent No. S62-7902

Patent document 3: published patent application of Japan No. 2000-154164

Patent document 4: lined patent application of Japan No. 2001-220367.

Description of the invention

The problems solved by the present invention

Whatever the case, each of the known methods described above, the selectivity of the obtained esters of carboxylic acids and the activity of the catalyst is insufficient, and because the expensive noble metals such as palladium, ruthenium and gold, used by applying to the media in large quantities, economic burden, emerged the abuser from the increased cost of production of the catalyst, great, that makes it difficult, therefore, consider these methods as advantageous on an industrial scale.

In addition, since palladium, ruthenium and gold, which are used in the above production methods, are representatives of noble metals, they are expensive, and as a component of the catalyst is often used by dispersing and applying media, making, thus, in such cases it is extremely important choice of media.

With the aim of practical application of industrial methods, as a result of extensive research catalysts coated composite nanoparticles containing oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper), the authors present invention are made obvious conclusion that the catalyst is satisfactory from the point of view of its useful life, not necessarily obtained in the case of using activated charcoal, calcium carbonate, aluminum oxide, silicon oxide, or silicon oxide with titanium dioxide as the carrier. Namely, in the case of a reaction catalyst in suspension in the commonly used industrial reactor vessel with stirring or bubbling Rea the Torah in the form of towers and the like, mechanical strength was insufficient and peeling of the Nickel component and X, which are components of the catalyst was observed in the case of activated carbon. In addition, although the aluminum oxide has a high mechanical strength, the strength of the carrier is reduced due to corrosion under the action of acidic substances, examples of which are typical side reaction products of methacrylic acid and acrylic acid, which leads to a disadvantage in more light flaking of the Nickel component and X, which are components of the catalyst. The use of calcium carbonate for the media leads to greater sensitivity to corrosion under the influence of acidic substances, than in the case of aluminum oxide, making it, thus, unsuitable for industrial applications. In the case of silicon oxide or silicon oxide with titanium dioxide, a portion of the silicon oxide gradually plagued by water, entered during the process, or water obtained as a by-product of the reaction that leads to the leaching of silicon oxide, while at the same time is also observed peeling and leaching of Nickel and X component, which are components of the catalyst. Therefore, there are problems associated with the fact whether these substances to remain stable over a long PE the iodine use. In addition, there are also problems with mechanical strength, which is lower than that of the above-mentioned aluminum oxide.

On the other hand, it was reported about the research methods of obtaining silica gel and research on the application of high temperature sintering for the modification of silica gel with the aim of improving the mechanical strength and the corrosion resistance of silicon oxide. However, it was not reported about successful examples of improving the mechanical strength and stability to hydrolysis without affecting the functional properties of the catalyst. For example, it is known that quartz, which is a type of matter on the basis of silicon oxide, is solid, has a high mechanical strength and is highly resistant to hydrolysis. However, in the case of using silica as a carrier, although the mechanical strength and corrosion resistance are improved noticeably, it also leads to a decrease of the specific surface (1 m2/g or less), and because it prevents the metal catalyst was loaded in the form of fine particles in a highly dispersed state, there is a problem with the extremely low reactivity of the resulting catalyst.

With this in mind, the technical level, as described above, in the present time, there is a need for the media to produce the RA, which has a high mechanical strength and is physically stable and has a large surface area suitable for use as a catalyst carrier, exhibits sufficient corrosion resistance compared to typical liquid-phase reaction in the form of a synthesis reaction of ester of carboxylic acid in the presence of oxygen and is capable of stable deposition of a Nickel component and X, which are the active components of the catalyst over a long period of time.

Considering the above, the present invention is the creation of a catalyst to obtain a complex ester of carboxylic acid by reacting the aldehyde and alcohol, or one or more types of alcohols, in the presence of oxygen, in which a high level of reactivity is supported through the use of the main components of the catalyst stable metal elements having excellent reactivity, instead of the usual expensive noble metals, creating a method of producing such a catalyst and to provide a method for obtaining esters of carboxylic acids using a catalyst.

Tools for problem solving

As a result of extensive research for the development of the solutions to the above problems by the authors of the present invention found, that the above problems can be solved by using a catalyst to produce complex ether carboxylic acids, in which the oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper) is applied to the carrier in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99.

Namely, this invention is described below.

[1] the Catalyst to obtain a complex ester of carboxylic acid by reacting (a) aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen containing:

oxidized Nickel; and

X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper)deposited on the carrier in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99.

[2] the Catalyst to obtain a complex ester of carboxylic acid on p.[1]containing the composite nanoparticles consisting of oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper).

[3] the Catalyst to obtain a complex ester of carboxylic acid on p.[2], in which the composite nanoparticle is a particle having X in their Serdtsev is not, and the surface of the core is covered with oxidized Nickel.

[4] the Catalyst to obtain a complex ester of carboxylic acid on p.[2] or [3], in which in addition to the composite nanoparticles on the carrier is applied independently oxidized Nickel.

[5] the Catalyst to obtain a complex ester of carboxylic acid according to any one of paragraphs.[1]-[4], in which the oxidized Nickel is a Nickel oxide and/or a complex oxide containing Nickel.

[6] the Catalyst to obtain a complex ester of carboxylic acid according to any one of paragraphs.[1]-[5], in which the carrier is aluminium-containing composition on the basis of silicon oxide that contains silicon oxide and aluminum oxide, and the amount of aluminum is in the range from 1 to 30 mol.%, in the calculation of the total molar amount of silicon and aluminum.

[7] the Catalyst to obtain a complex ester of carboxylic acid on p.[6], in which the medium further comprises at least one kind of the main metal component selected from the group consisting of alkali metal, alkaline earth metal and rare earth metal.

[8] the Catalyst to obtain a complex ester of carboxylic acid on p.[6] or [7], in which the ratio of Nickel and aluminum oxide is from 0.01 to 1.0, based on the atomic ratio of Ni/Al.

[9] the Catalyst to produce complex ether carboxylic acid p is p.[7] or [8], in which the ratio of Nickel and base metal component is from 0.01 to 1.2, based on the atomic ratio of Ni/(alkali metal + earth + metal rare earth metal).

[10] the Catalyst to obtain a complex ester of carboxylic acid according to any of the PP[1]-[9], in which the carrier is a composition comprising silicon oxide, aluminum oxide and magnesium oxide, and contains from 42 to 90 mol.% silicon, from 5.5 to 38 mol.% aluminum and from 4 to 38 mol.% magnesium, based on the total molar amount of silicon, aluminum and magnesium.

[11] the Catalyst to obtain a complex ester of carboxylic acid on p.[10], in which the ratio of Nickel and aluminum oxide is from 0.01 to 1.0, based on the atomic ratio of Ni/Al, and the balance Nickel and magnesium oxide is from 0.01 to 1.2, based on the atomic ratio of Ni/Mg.

[12] the Catalyst to obtain a complex ester of carboxylic acid according to any one of paragraphs.[1]-[11], in which the specific surface area is from 20 to 350 m2/g, the diameter of pores with a maximum frequency of occurrence is 3 to 50 nm, the pore volume is from 0.1 to 1.0 ml/g and a particle diameter is from 10 to 200 microns.

[13] the Method of producing catalyst to produce complex ether carboxylic acids, including:

the first stage of obtaining a catalyst precursor deposition of the Nickel component and X (where X made the focus of an at least one element, selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper) on the medium by neutralization of the acidic solution of a soluble metal salt containing Nickel and X; and

the second stage of oxidation of Nickel by heat treatment of the obtained catalyst precursor.

[14] the Method of obtaining complex ether carboxylic acids, including the stage of interaction of the catalyst to produce complex ether carboxylic acid according to any one of paragraphs.[1]-[12] (a) aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen.

[15] a method of obtaining a complex ester of carboxylic acid on p.[14], in which the aldehyde is a compound selected from acrolein, methacrolein and mixtures thereof.

[16] a method of obtaining a complex ester of carboxylic acid on p.[14], in which the aldehyde is a compound selected from acrolein, methacrolein and mixtures thereof, and the alcohol is methanol.

[17] a method of obtaining a complex ester of carboxylic acid on p.[14], in which one type of alcohol is ethylene glycol, and other types of alcohol is methanol.

The advantages of this invention

In accordance with this invention can be a catalyst to obtain a complex ester of carboxylic acid, which maintains a high level of reactivity due to the COI is whether the main component of the catalyst is stable compounds of Nickel, having excellent reactivity, instead of the usual expensive noble metals, the method of obtaining such a catalyst and method for producing a complex ester of carboxylic acid using such a catalyst.

Brief description of drawings

Figure 1 shows a micrograph obtained with a transmission electron microscope (TEM, svetlopoli image), catalyst to obtain a complex ester of carboxylic acid of example 4;

Figure 2 shows an enlarged micrograph presented in figure 1, and the image part thereof, obtained using the fast Fourier transform (FFT);

Figure 3 shows a micrograph obtained by scanning transmission electron microscope (STEM, svetlopoli image), catalyst to obtain a complex ester of carboxylic acid of example 4 together with the results of the composition analysis at specified points by the method of energy dispersive x-ray spectroscopy;

Figure 4 shows a micrograph obtained by scanning transmission electron microscope (STEM, svetlopoli image), catalyst to obtain a complex ester of carboxylic acid of example 4, together with a linear profile of its composition obtained by the method of energy dispersive x-ray spectroscopy; the

Figure 5 shows a graph illustrating the results of analysis by spectroscopy in the UV and visible regions of the catalyst to obtain a complex ester of carboxylic acid of example 4.

The best option is the implementation of the present invention

The following description gives a detailed explanation of the best alternative implementation of the present invention (the link to which is given as "this option exercise"). In addition, the invention is not limited to implementation options below and can be implemented with a change in various ways within the scope of this invention.

Catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment is a catalyst to obtain a complex ester of carboxylic acid by reacting (a) aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen, in which the oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper) deposited on the carrier in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99.

Catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment preference is sustained fashion further comprises a composite nanoparticles, consisting of oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper).

Oxidized Nickel is preferably a Nickel oxide formed by the binding of Nickel and oxygen (for example, Ni2O, NiO, NiO2, Ni3O4or Ni2O3), or a complex oxide containing Nickel, for example, a compound of Nickel oxide, a solid solution or their mixture, and formed by the binding of Nickel and X and/or one or more of the other metal element and oxygen.

The term "Nickel oxide", as used herein, refers to a compound containing Nickel and oxygen. Nickel oxide includes Ni2O, NiO, NiO2, Ni3O4or Ni2O3or hydrates of the above compounds, hydroperoxides Nickel containing group OOH, or peroxides Nickel containing group O2or a mixture of the above compounds, etc.

In addition, the term "complex oxide", as used herein, refers to an oxide containing two or more kinds of metals. The term "complex oxide" refers to the oxide, in which two or more kinds of metal oxides form a connection, and although it includes a dual oxides, in which ions exocyclic not present as the structures of the s units (such as oxides of Nickel-type perovskite or spinel), it also includes all oxides in a broader sense than double oxides, which combine two or more kinds of metals. Oxides in which two or more kinds of metal oxides form a solid solution, also come in a range of complex oxides.

Below is an explanation of the action, which is manifested extremely high effectiveness of the catalyst due to the deposition of oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper) to the medium in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99.

The authors of the present invention found that the catalytic activity characteristic of oxides of Nickel, with activity against oxidative esterification is achieved by combining Nickel oxide and X, and which shows an unusually high efficiency of the catalyst, not shown catalysts consisting of each individual component. This can be attributed to the unique effect manifested as a result of a combination of Nickel oxide and X, and is believed to be the result of the formation of a new catalytic activity, which is completely different from the action of catalysts consisting of each individual component, as a result, voltage is emer, education binary functional catalyst or new active ingredients between the two metal components. Based on this new concept, in the case of deposition of oxidized Nickel and X in the carrier in a highly dispersed state, could be, in particular, the implemented characteristics of the catalyst are radically different from those obtained for the catalysts in accordance with the prior art.

In past years the nanoparticles, which have attracted considerable attention due to achievements in the technology of synthesis of ultra fine particles, has been recognized as the main material in the field of nanotechnology and the study of their progress throughout the world. Nanoparticles having a particle diameter of 100 nm or less, different from large particles in that they have a high proportion of the surface of the metal element among the metal elements that constitute the nanoparticles, which in result leads to the fact that the surface area of the metal element per unit mass increases rapidly with decreasing particle size. Examples of nanoparticles known in the field of catalytic materials may include metal nanoparticles, such as nanoparticles of platinum, palladium, ruthenium, rhodium, gold, silver and copper, or nanoparticles of a metal oxide, that is their nanoparticles of iron oxide, of cobalt oxide, Nickel oxide, zinc oxide, titanium oxide, zirconium oxide, indium oxide, aluminum oxide and silicon oxide, and these nanoparticles are attracting attention as a heterogeneous catalytic materials. Namely, one of the reasons for the increasing attention paid to the use of nanoparticles in catalytic materials is that, as a factor that contributes to the catalytic action, is limited to a metallic element present on the surface of the particles, in the case of applications at the nanoscale, the surface area per unit mass of the metal element involved in the reaction (specific surface area)increases by increasing the activity of the catalyst based on the weight of the metal element. Changes in the catalytic activity is attributed to the size of the nanoparticles, thus, widely known as "the effects of particle size".

On the other hand, there are also cases in which several new effects, in addition to these effects of particle size. For example, the effect of binary metal nanoparticles is known as one of the factors that have a significant influence on the catalytic activity of the nanoparticles. This effect refers to the effect, which may not be manifested only metal component and manifests l is nil as a result of the merger. Alloys, as they are referred to in accordance with the prior art, are a well known example of this (binary metal nanoparticles are related not only to the case of elementary components, which are metals, but also include cases in which the United metal compounds or metals and metal compounds. Although the size and shape of particles are the main parameters controlled in the case of nanoparticles, consisting of a single element, in the case of nanoparticles, consisting of two or more basic components, additional parameters to be monitored include composition, crystal structure and phase structure (for example, the structure of the alloy or solid solution in which the crystal position is randomly occupied the chemical components, the structure of the core and the cladding, in which each chemical component is separated in the form of concentric spheres, anisotropic phase structure in which the phase separated anisotropic manner, and the structure with heterophile relationships in which both chemical component there are next to each other on the surface of the particles). Namely, as a result of the use of the structure of binary compounds, changes in weight of the metal component, leading to the development of the chemical and electronic properties, which is tchelio differ from single nanoparticles. Thus, it is found that the binary metal nanoparticles exhibit novel catalytic, magnetic and optical properties that are not found in the nanoparticles, consisting of a single metal element, and the methods of their application, in addition to catalysts, in various fields, such as materials for electronic engineering, medicine and biotechnology.

The authors of the present invention conducted extensive search of materials to create catalysts with high selectivity and activity upon receipt of ester carboxylic acids, as well as having as their main component budget metallic element with high reactivity to replace their expensive noble metals in accordance with the prior art. Attention was focused on the Nickel as an element that has properties that are similar to the properties of noble metals, and have conducted extensive research on the correlation between its chemical state and reactivity, which has led to completion of this invention. Namely, as described above, the catalyst according to this variant implementation contains oxidized Nickel and X as a binary metallokhimicheskie component (where X represents at least od the n element, selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper)deposited on the carrier in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99. The catalyst for this variant implementation preferably further comprises nanoparticles consisting of oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper). Below is a more detailed explanation of such a catalyst.

When the authors of the present invention used as a catalyst oxides of Nickel, now attracting attention as a catalyst for the oxidation of alcohol, was first found that, despite the low level of activity, even one Nickel oxide (NiO) shows activity against the formation of ester carboxylic acid. Moreover, as a result of additional research, the authors present invention clearly showed that this highly oxidised peroxide Nickel (NiO2shows higher performance compared to Nickel oxide. On the other hand, the activity was not observed when using only one metal of Nickel (Ni).

Based on this information, an assumption was made that a cheap metal element is, Nickel can be used as a main component of the catalyst. Then the authors of this invention have investigated the addition of various metal elements to Nickel oxide by changing the oxidized state of Nickel, hoping to find opportunities for improving the characteristics of the catalyst by adjusting the oxidized state of Nickel and deposition of the active component on the carrier in a highly dispersed state. As a result, the authors of the present invention found that by applying the oxidized Nickel and at least one metal component selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper on the carrier in a highly dispersed state in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99 is the conversion of Nickel oxide from the normal oxidized state in this highly oxidised Nickel oxide, whereby substantially increases the activity and selectivity compared with catalysts consisting only of each item, or catalysts, in which the atomic ratio of Ni/(Ni + X) is outside the above interval.

For example, when gold is selected as X and an oxide of Nickel and gold are deposited on the carrier in a highly dispersed state, is shown very high activity of the catalyst. There is ALOS, this catalyst shows higher selectivity upon receipt of ester carboxylic acids, as compared with catalysts in which only one oxide of Nickel or only gold supported on a carrier, and a significant increase in activity was observed for a specific ratio of Ni/(Ni + Au). In terms of catalyst activity per metal atom, activity (Ni + Au) in the formation of ester carboxylic acids higher than the activity of catalysts consisting of each component separately, and the functioning of the catalyst attributable to their Association, largely depends on the actual composition of Nickel and gold. It is assumed, due to the presence of correlation, optimal for the formation of the oxidized state of Nickel, which is optimal for the reaction. Thus, by applying to the media two components, oxide of Nickel and gold, in dispersed condition manifested significant effects associations that could not be predicted by a simple summation of the effects created by each component separately.

In the above catalyst oxidized Nickel and gold are deposited on the carrier in a highly dispersed state, and both components are combined at the nanoscale. Based on the results of observations using transmission electrical wiring in the traditional microscope/scanning transmission electron microscope (TEM/STEM) almost spherical nanoparticles, having a distribution of particle diameter of from 2 to 3 nm, were deposited uniformly dispergirovannykh to the media. On the basis of elemental analysis of nanoparticles by the method of energy dispersive x-ray spectroscopy (EDS) as Nickel and gold are present in all particles and, as observed, are in the form of nanoparticles of gold, the surface of which is coated with Nickel. In addition, a separate component of Nickel was found deposited on the carrier, in addition to the nanoparticles containing Nickel and gold.

According to the results of x-ray photoelectron spectroscopy (XPS) and powder x-ray diffraction (powder XRD), although the gold is present as crystalline metal, Nickel, assumed to be present in the form of amorphous oxide with a valence of 2.

Based on the results of spectroscopy in the UV and visible region of the spectrum, providing the possibility of observing changes in the electronic excited States, it was found that the Association of oxidized Nickel oxide and gold causes the disappearance of the peak absorption of surface plasmons (about 530 nm), due to the gold nanoparticles and observed in gold nanoparticles, consisting only of gold as a component. The disappearance of this peak absorption of surface plasmons was not observed in the combinations of the Olot and component metal oxide, other than Nickel oxide, such as chromium oxide, manganese oxide, iron oxide, cobalt oxide, copper oxide or zinc oxide, a combination which, as has been observed, do not affect the reaction. The disappearance of this peak absorption of surface plasmons is believed to be the result of mixing of electronic States at the interface between the oxidized Nickel and gold, or, in other words, the hybridization of two species metallogenically components.

Conversion in this highly oxidised Nickel oxide can be observed by the color change in the catalyst and using spectroscopy in the UV and visible part of the spectrum. By adding gold to the oxide Nickel color Nickel oxide varies from grayish-green to brown, and the UV-spectrum shows absorption throughout the visible spectrum. View UV spectrum and the color of the catalyst is similar to the form of the spectrum and color this highly oxidised peroxide Nickel (NiO2used as a comparative sample. Based on this conclusion suggests that the Nickel oxide converted in this highly oxidised Nickel oxide by adding gold.

On the basis of these results suggest that the structure of the composite nanoparticles such that the nanoparticles of gold are located in the core, the surface of gold nanoparticles covered Vysokomol is authorized oxide of Nickel and gold atoms are not present on the surface of the composite nanoparticles.

The proposed principle

Below is an explanation of the alleged principle of action of the catalysts in accordance with this embodiment, using the example of the modification and improvement of Nickel compounds, for which studies have been conducted in relation to their use as catalysts and materials for electronic devices.

Examples of the application of heterogeneous compounds Nickel for oxidative reactions in accordance with the prior art may include (1) the oxidation of alcohol using peroxide Nickel (NiO2as the stoichiometric oxidant (J. Org. Chem. 27 (1962) 1597), (2) the oxidation reaction of the alcohol-based oxygen using Ni-Al hydrotalcite as catalyst (Angew. Chem. Int. Ed. 40 (2001) 763), (3) the oxidation reaction of the alcohol-based oxygen using Mg-Al hydrotalcite containing Ni(II)as a catalyst (J. Mol. Catal. A 236 (2005) 206), (4) the oxidation reaction of the alcohol-based oxygen using nanoparticles peroxide Nickel (NiO2) as a catalyst (Appl. Catal. A 290 (2005) 25) etc.

Although this highly oxidised peroxide Nickel has a higher oxidative capacity than conventional Nickel oxide, and it has long been known that it is able to oxidize various alcohols stoichiometric manner, as a result of various modify the Nations and improvements of Nickel catalysts in the past years carried out the reaction of catalytic oxidation of alcohol by molecular oxygen. Catalysts containing Nickel hydrotalcite allow Nickel to function as places of activation of oxygen by combining Nickel and another metal element (such as Al or Mg), and it is believed, leads to the formation of peroxide component as a reaction component in the Nickel. In addition, it was reported that methods using nanoparticles of Nickel peroxide reactions proceed catalytically due to the formation of peroxide Nickel nanoparticles.

Nickel oxide is used as the electrochromic material, for example, in the field of materials for electronic equipment, other than catalysts. In order to increase the reaction rate of the films of Nickel oxide upon photoabsorption, studies (5) film chemical compounds NiO-Me (where Me represents Au, Ag, Cu, Ni, Pd or Pt), in which the metal (Me) is alloyed with Nickel oxide (J. Phys. D: Appl. Phys. 36 (2003) 2386). Metals, doped Nickel oxide, act as p-type material, and the rate of dyeing the oxidation is considered to increase when Nickel oxide is converted in this highly oxidised Nickel oxide.

Such examples of the application of Nickel compounds provide important guidance regarding the understanding of the manifestations of the catalytic ability, demonstrated Katalizator is by this option implementation. Although the authors of the present invention found that the Nickel peroxide is active in reactions of synthesis of ester carboxylic acids, the level of catalyst activity was low. Pure Nickel peroxide and its anhydrides are yet to be obtained, in this respect, there are many aspects of their structure, which remain unclear, and it is also considered a form of Nickel oxide (divalent), which has adsorbed oxygen. However, since the Nickel peroxide is widely applicable as agent for the stoichiometric oxidation, if it was possible the formation of catalytically active oxidizing the active component through the use of molecular oxygen for the oxidizer peroxide Nickel could be used for oxidation of organic substrates by molecular oxygen. Pioneering research in this area is described in (2) above, and these studies have led for the first time in the world to conduct oxidation using heterogeneous Nickel catalyst, implemented by highly efficient activation of molecular oxygen by combining Nickel and another metal element. In addition, as described in (4) above, a message indicating that the Nickel peroxide functions as a catalyst due to the conversion to nanoparticles, indicates the importance of monitoring geometrician the cooling structure for the catalytically active component.

In addition, examples of the method of regulation of the oxidized state of Nickel oxide, is used as the electrochromic material may include a combination of metal of the group 8 metal of group 1B, as indicated in (5) above, by increasing the degree of conversion in this highly oxidised Nickel oxide. This suggests that also in the catalytic reactions, the regulation of electronic States of oxidized Nickel is possible by combining with specific metal, and this applies also to the basic concept of the catalyst according to this variant implementation.

As described above, it is assumed that the structure of the composite nanoparticles according to this variant implementation contains particles X, serving as a core, the surface of which is covered by this highly oxidised Nickel oxide. On the basis of (1)to(5) above, in the composite nanoparticles according to this variant implementation, since the oxidized Nickel and X interact at the atomic level, the electronic state of Nickel oxide is converted in this highly oxidised state, and changes in the geometric structure of the active sites, as well as changes in the electronic properties can be considered as the factors affecting its catalytic action. In addition, it is assumed that through the mediation of oxygen atoms formed a new asset is th component at the interface between the Nickel oxide and X, and it is believed, leads to the formation of new functional ability of the catalyst that is completely different from what takes place in case of application of each of the components separately.

Namely, the catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment is explicitly different from the usual metal catalysts, consisting of a single metal component, binary metal catalysts, such as alloys or intermetallic compounds, and binary catalysts, consisting of a combination of metal oxides, other than Nickel, and metal elements, and is thought to change the state of an active places, specifically due to the Association of oxidized Nickel and X, leads to a completely new characteristics of the catalyst, which cannot be obtained in the case of catalysts in accordance with the prior art.

Detailed description of the catalyst to produce complex ether carboxylic acid

Catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment is a catalyst in which the oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, Rute the Oia, gold, silver and copper) deposited on the carrier in the range of the atomic ratio Ni/(Ni + X) from 0.20 to 0.99.

The catalyst in accordance with this embodiment preferably further comprises a composite nanoparticles consisting of oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper).

The oxidized Nickel and X is preferably supported on a carrier in a highly dispersed state. The oxidized Nickel and X is more preferably applied when the dispersion in the form of fine particles or thin film, and the average diameter of each particle is preferably from 2 to 15 nm, more preferably from 2 to 10 nm and even more preferably from 2 to 6 nm. The average particle diameter as referred to in this embodiment, refers to srednekamennogo the particle diameter when measuring transmission electron microscope (TEM).

Applied composition of Nickel and X is such that the atomic ratio of Ni/(Ni + X) is in the range from 0.20 to 0.99, preferably in the range from 0.30 to 0.90, and more preferably in the range from 0.50 to 0.90. The atomic ratio of Ni/(Ni + X), as referred to herein, is the ratio of the number of atoms of Nickel supported on a carrier, to the total is the number of Ni atoms and atoms X. If the atomic ratio of Ni/(Ni + X) is within the above ranges, you form a certain structure of the active component composed of Nickel and X, and the oxidized state of Nickel, suitable for the reaction, resulting in the activity and selectivity tend to be higher than that of catalysts in which this atomic ratio is outside these intervals.

In case of composite nanoparticles consisting of oxidized Nickel and X, are contained in the catalyst, this catalyst is not limited to such form, in which the nanoparticles are only supported on a carrier, but also includes catalysts, in addition to the composite nanoparticles on the carrier applied separately oxidized Nickel.

Composite nanoparticles refers to the nanoparticles containing the oxidized Nickel and X (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper).

Although there are no particular restrictions on the structure of the composite nanoparticles containing both components, preferably both components are present in the nanoparticles, and the structure preferably is a phase structure, such as the structure of the solid solution in which the crystal position arbitrarily C the adopted chemical components, the structure of the core and the cladding, in which each chemical component is separated in the form of concentric spheres, anisotropic phase structure in which the phase separated anisotropic manner, and the structure with heterophile relationships in which both chemical component are present next to each other on the surface of the particles. More preferably, X is used as a core, and oxidized Nickel covers its surface. There are no special restrictions with regard to form composite nanoparticles, provided that they contain both components, and they can be of any shape, such as spheres or hemispheres.

The content of Nickel and X in the composite nanoparticles is such that the atomic ratio of Ni/X preferably ranges from 0.1 to 10, more preferably in the range from 0.2 to 5.0, and more preferably in the range from 0.3 to 3.0.

Interval average particle diameter of the composite nanoparticles is preferably from 2 to 15 nm, more preferably from 2 to 10 nm and even more preferably from 2 to 6 nm.

In the case where a composite nanoparticles have a shape in which X is in the core and oxidized Nickel covers its surface, the average particle diameter preferably X is in the range from 1.5 to 12 nm, more preferably in the range from 2 to 10 nm, and even more prefer is Ino in the range of from 2 to 6 nm, taking into account the balance between activity and stability. The thickness of the surface layer of Nickel is determined by one or more layers of molecules of oxidized Nickel and varies according to such factors as the composition of the deposited Nickel and X, the atomic ratio and the diameter of the particles of Nickel and X in the composite nanoparticles, and method, according to which the catalyst. The thickness of the layer of Nickel per molecule oxidized Nickel, preferably approximately from 1 to 5 layers, and more preferably about 1 to 3 layers. In addition, the complex oxide may be formed inside the composite nanoparticles that are chemically associated component, such as Ni-O-X on the boundary surface, which are in contact components of Nickel and X.

The reason for the existence of preferred intervals for composition applied composition of Nickel and X and the atomic ratio of Nickel and X in the composite nanoparticles and the reason for admission is that the proportion of surface atoms varies in accordance with the particle diameter X. for Example, bringing gold as an example, when the diameter of the gold particles of 10 nm the total number of atoms is approximately 2.1×104and the ratio of the number of surface atoms becomes equal to approximately 15%. If the particle diameter is 2 nm, obiechina atoms is approximately 150, and the ratio of the number of surface atoms becomes equal to approximately 63%. Thus, if we take into account the way in which the surface X is covered with Nickel, it is easy to assume that the atomic ratio of Nickel and X varies depending on the particle diameter X.

As described previously, using a transmission electron microscope/scanning transmission electron microscope (TEM/STEM) is an effective analytical method to study the morphology of the composite nanoparticles, and images of nanoparticles obtained TEM/STEM when the electron beam irradiation, make possible the analysis of the elements inside the nanoparticles and extracting information on the distribution of these elements. As will be shown in examples described below, it was confirmed that the composite nanoparticles according to this embodiment have a structure in which the Nickel and X contains all the particles, and the surface X is covered with Nickel. In the case of this structure, the atomic ratio of Nickel and X varies in accordance with the analysis of the composition of the nanoparticles, and a higher amount of Nickel found on the edges of the particles compared to the center of the particles. Therefore, allowance must be made for the atomic ratio of Nickel and X, depending on the location of the analysis, even for individual nanoca the TIC, and this tolerance interval is included in the intervals of the atomic ratio of Ni/X, as described previously.

If selected as X gold, silver or copper, spectroscopy in the UV and visible part of the spectrum (UV-Vis) is an effective means of identifying their patterns. In the case of nanoparticles containing only gold, silver or copper, the PV field in the band of visible light and near IR binds with the free electrons on the metal surface, which leads to absorption of surface plasmons. For example, if the catalyst coated gold nanoparticles irradiated visible light, the observed absorption spectrum due to a plasmon resonance that is generated by gold nanoparticles, at a wavelength of approximately 530 nm. However, in the case of the catalyst caused by the oxide of Nickel and gold in accordance with this embodiment the absorption of surface plasmons disappears, suggesting the absence of gold on the surface of the catalyst in accordance with this embodiment.

Preferred examples of the oxidized Nickel may include oxides of Nickel formed by the binding of Nickel and oxygen (for example, Ni2O, NiO, NiO2, Ni3O4or Ni2O3), and complex oxides containing Nickel, for example compounds of Nickel oxide, solid rastvoriteli mixtures thereof, and formed by the binding of Nickel and X and/or one or more other metal elements and oxygen.

There are no particular restrictions on solid forms of Nickel, provided that it allows you to get a given activity of the catalyst, and preferably Nickel is in an amorphous state in which no diffraction peaks observed by x-ray diffraction. The use of such form, since the interaction with oxygen, as expected, more and a surface boundary between the mutually associated oxidized Nickel and X is increased, there can be obtained an even higher activity of the catalyst.

X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper, and more preferably selected from the group consisting of Nickel, palladium, ruthenium, gold and silver.

Although the chemical state X may be a metal, an oxide, a hydroxide, a complex compound containing X and Nickel or one or more types of other metal elements, or any mixtures thereof, the preferred chemical state is the metal or the oxide, and more preferred is the metal. In addition, there are no particular restrictions on hard X-shaped, with the moustache is ovii, what it allows you to get a given activity of the catalyst, and it can be crystalline or amorphous.

Another metallic element, as referred to herein, means a composite media item, described below, the third element contained in the catalyst in addition to the oxidized Nickel and X, or a metal component, such as alkali metal, alkaline earth metal or rare earth metal.

The catalyst in accordance with this embodiment contains an oxidized Nickel and X, supported on a carrier, as described previously, and preferably exhibits an excellent effect due to the formation of composite nanoparticles consisting of oxidized Nickel and x in Addition, composite nanoparticles, as it is referred to in this embodiment, relates to a nano-particle containing various binary metal components within a single particle. Although examples of various binary metal components can include binary metal particles, which as a component of Nickel and X component are metal, and metal particles, in which is formed an alloy or intermetallic compound of Nickel and X in case of their use as catalysts for production of ester carboxylic acids, selectively the path and the catalytic activity of the target product are low compared with the catalyst in accordance with this invention, that makes them unsuitable.

The catalyst in accordance with this embodiment preferably contains oxidized Nickel on the media independent way, in addition to the composite nanoparticles consisting of oxidized Nickel and x the Presence of oxidized Nickel, not combined with X, serves to further increase the structural stability of the catalyst particles and inhibits the increase of the diameter of pores caused by long-term reactions, and the accompanying increase of the composite nanoparticles. This effect is noticeable in the case of applications for aluminium-containing media composition based on silicon oxide containing silicon oxide and aluminum, or of a composition containing silicon oxide, aluminum oxide and magnesium oxide, as will be described below.

Below is the explanation of action, in which the structural stability of the catalyst particles is increased, and the increase in the diameter of the pores caused by prolonged reaction, with concomitant growth of the composite nanoparticles is constrained due to the presence of free oxidized Nickel on the media.

As will be described later, the formation of acetals and the like under the action of acidic substances, examples of which include methacrylic acid or acrylic acid, which are by-products of typical reactions produce complex e is IRow carboxylic acid, you can keep maintaining the pH of the reaction system in the range of 6 to 9, and more preferably under neutral conditions (for example, at a pH of from 6.5 to 7.5) or, in other words, maintaining the pH value as closely as possible to pH 7 by addition to the reaction system connection alkali metal or alkaline earth metal.

According to research conducted by the authors of the present invention, in the case of a continuous reaction in accordance with the methodology described above, using a catalyst in which a single gold nanoparticles supported on a carrier in this variant implementation, it was found that the catalyst particles gradually undergo structural changes. This phenomenon is believed due to the fact that the catalyst particles repeatedly locally open to the effects of acids and bases due to the reaction procedure described above, resulting in part of Al in the carrier dissolves and precipitates, which leads to the transformation of cross-linked structures based on silicon oxide and aluminium oxide, which, in turn, causes an increase in the diameter of the pores of the catalyst particles. In addition, simultaneously with the increase of the diameter of pores stimulates the growth of particles due to sintering of the gold particles, which, as it reduces the activity of the catalyst.

On the other hand, when OUTSTA composite nanoparticles and oxidized Nickel separately on the media serves to increase the structural stability of the catalyst particles due to the procedure, as described above, it is also constrained by the increase in the diameter of pores and the growth of the composite nanoparticles. As described earlier, the reason for this, as I believe, lies in the fact that the reaction between the oxidized Nickel and elements of the media lead to the formation of oxide compounds of Nickel or complex oxides containing Nickel, such as solid solutions, and due to the fact that these compounds act in a stabilizing manner on a cross-linked structure based on silicon oxide and aluminium oxide, the structural stability of the catalyst particles is significantly increased. Performance of such a catalyst with the effects of structural stabilization, as suggested by the authors of the present invention, due to the oxidized Nickel present in the media. Therefore, these effects take place naturally when oxidized Nickel contained in the composite nanoparticles, is in contact with the carrier, and the maximum stabilizing effects, considered to be achieved if the free oxidized Nickel is present on the media.

Media

In respect to the catalyst carrier to obtain a complex ester of carboxylic acid in accordance with this embodiment there are no particular restrictions, provided that it is capable of supporting oxidized the initial Nickel and X, and can be used catalyst carrier in accordance with known prior art for the synthesis of ester of carboxylic acid.

Examples of this media can include various types of media, such as activated carbon, silica, alumina, silica-alumina, titanium dioxide, silicon oxide-titanium dioxide, zirconium dioxide, magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-aluminum oxide-magnesium oxide, calcium carbonate, zinc oxide, zeolite and crystalline metroselect. Its preferred examples may include activated carbon, silica, alumina, system silica-alumina system, the silicon oxide-magnesium oxide, system of a silicon oxide-aluminum oxide-magnesium oxide, titanium dioxide, system of a silicon oxide-titanium dioxide and zirconium dioxide. More preferred examples may include a system for the silicon oxide-aluminum oxide and silicon oxide-aluminum oxide-magnesium oxide.

In addition, the medium may also contain one or more kinds of metal selected from the group consisting of alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Be, Mg, Ca, Sr, Ba) and rare earth metals (La, Ce, Pr). Supported metal component is preferably oxide, is perceived by the NYM firing, for example, nitrate or acetate.

It is preferable for the carrier used aluminium-containing composition based on silicon oxide containing silicon oxide and aluminum, or a composition comprising silicon oxide, aluminum oxide and magnesium oxide. This type of media has a higher resistance as compared with silicon oxide and a higher acid resistance compared to aluminum oxide. In addition, it also provides superior physical properties compared to the native usually applied in accordance with the prior art, including, has a higher hardness and a higher mechanical strength than the activated carbon, while it also provides a more stable deposition of oxidized Nickel and X, which are the active components of the catalyst (where X represents at least one element selected from the group consisting of Nickel, palladium, platinum, ruthenium, gold, silver and copper). As a result, the catalyst is able to maintain a high level of reactivity over a long period of time.

Catalyst to produce complex ether carboxylic acids, in which the oxidized Nickel and X are determined by atomic ratio, and aluminium-containing composition based on silicon oxide or a composition comprising a hydroxy is silicon, aluminum oxide and magnesium oxide, is used for media that exhibits high mechanical strength and physical stability, having a large surface area suitable for use as a catalyst carrier, also exhibits sufficient corrosion resistance compared to typical liquid-phase reactions, reactions for the synthesis of ester of carboxylic acid in the presence of oxygen.

Below is an explanation of the properties of the media in this variant implementation, which provides a significant increase in service life of the catalyst. The reason that it will considerably increase the mechanical strength and chemical resistance of the medium is assumed to be the following.

In aluminium-containing medium on the basis of silicon oxide due to Si-O-Al-O-Si bonds are formed again by adding aluminum (Al) to seamless chains of silicon oxide (Si-O) in the silica gel. Because of the structure made of Al, formed without loss of stability inherent in the chains of Si-O in relation to acidic substances, due to Si-O strengthened and resistance to hydrolysis (which hereafter in this document referred to as "resistance"), as I believe, this greatly increases. In addition, when the formation of crosslinked structure of Si-O-Al-O-Si, the number of unstitched chains of Si-O is reduced compared to silica the LEM separately, what is believed, leads to the increase in mechanical strength. Namely, it is assumed that the number of educated structures of Si-O-Al-O-Si correlates with increased mechanical strength and water resistance of the obtained silica gel.

In the media system based on a silicon oxide-aluminum-magnesium oxide, in the presence of magnesium oxide in addition to silicon oxide and aluminum oxide, supported the stabilization of the charge in the compensating neutralization by Mg (divalent) differences in charge, due to differences in valence between the Si (IV) and Al (trivalent), which is caused by the formation of cross-linked structures of Si-O-Al-O-Si. Moreover, since through the use of three-component system made the charge balance, it is assumed that structural stability is further enhanced. Therefore, in contrast to the media on the basis only of the system silica-alumina exhibiting acidity, medium containing silicon oxide, aluminum oxide and magnesium oxide, is almost neutral, and it is believed, provides the containment of appreciable formation of the acetal under acidic conditions.

One of the reasons for the sustainable support of oxidized Nickel and X in the carrier for a long period of time is that the Electromechanical what I strength and chemical resistance of the carrier is substantially improved, as described above, thereby providing the carrier with excellent physical properties in comparison with commonly used media in accordance with the prior art. As a result, the Nickel and X, which are the active components of the catalyst that is resistant to peeling, which, accordingly, provides stable support on the media for a long period of time.

It was found that the Nickel component commonly used substrates, such as silicon oxide or silicon oxide-aluminum oxide, washed out gradually during prolonged reactions. In contrast, in the case of using the above media, the authors of the present invention found that the leaching of the Nickel component is restrained for a long period of time. Based on the results of x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM/EDX) and rentgenolyuminestsentnye high resolution (HRXRF), in the case of media based on silica or on the basis of the silicon oxide-titanium dioxide, it was confirmed that the discharge of the Nickel component is an oxide of Nickel present separately on the media. Since the Nickel oxide is a compound, soluble in acid, it is assumed that it is ivalsa typical byproducts of this reaction in the form of acidic substances, presents methacrylic acid and acrylic acid.

Based on the analysis of the chemical state of Nickel by the method of rentgenolyuminestsentnye high resolution (HRXRF) Nickel catalyst, in accordance with this embodiment, as expected, is not only the oxide of Nickel, which is the only connection, but is also present in the result of the formation of complex oxides containing Nickel, such as compounds of Nickel oxide, solid solutions or mixtures thereof, formed by the binding of Nickel and a constituent element of the media.

The analysis method rentgenolyuminestsentnye high resolution (HRXRF) gives the opportunity to analyze the chemical state on the basis of the energy positions (chemical shifts) and the obtained form of the spectrum due to its extremely high resolution in energy. In particular, in the case of K-spectra of 3d transition metal elements changes occur in the chemical shift and shape due to changes in valence and electronic state, and the chemical state can be analyzed in detail. The catalyst in accordance with this embodiment changes have taken place in the Ni K-spectrum, confirming thereby that the chemical state of Nickel is different from Nickel oxide, which is the only one with whom the Association.

For example, Nickel aluminate, which is formed of Nickel oxide and aluminum oxide, is a compound which is insoluble in acid. As a result of formation of such compounds of Nickel on the carrier leaching component of Nickel is expected to be significantly reduced.

The following is a clarification with respect to two preferred carriers for a significant increase in service life of the catalyst in accordance with this embodiment, namely the media containing silicon oxide and aluminum oxide, and media on the basis of the silicon oxide-aluminum oxide-magnesium oxide.

The elemental composition of a carrier containing silicon oxide and aluminum oxide, is such that the amount of aluminum is from 1 to 30 mol.%, preferably from 5 to 30 mol.% and more preferably from 5 to 25 mol.%, in the calculation of the total molar amount of silicon and aluminum. If the amount of aluminum is within this interval, the acid resistance and mechanical strength tend to compliance with the appropriate values.

In addition, silicon oxide and aluminum oxide, the additional inclusion of at least one kind of the main metal component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, in the media produce the RA in accordance with this embodiment is preferred from the viewpoint of further increasing the mechanical strength and chemical resistance. Examples of alkali metals of this basic metal component may include Li, Na, K, Rb and Cs, examples of the alkaline earth metals include Be, Mg, Ca, Sr and Ba, and examples of rare earth metals may include La, Ce and Pr.

The elemental composition of a carrier containing silicon oxide, aluminum oxide and at least one kind of the main metal component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, is such that the amount of aluminum is in the range from 1 to 30 mol.%, preferably from 5 to 30 mol.% and more preferably from 5 to 25 mol.%, in the calculation of the total molar amount of silicon and aluminum. In addition, the ratio of the main metal component and aluminum oxide, based on the atomic ratio of (alkali metal + 1/2 × alkaline earth metal + 1/3 × rare earth metal)/Al is preferably in the range from 0.5 to 10, more preferably from 0.5 to 5.0 and more preferably from 0.5 to 2.0. If the elemental composition of silicon oxide, aluminum oxide and base metal component is in the above range, silicon, aluminum, and the main metal element form a certain stably associated structure, and the mechanical strength and water resistance of the carrier tend to appropriate estview appropriate values.

Moreover, the medium containing silicon oxide, aluminum oxide and magnesium oxide, preferably comprises from 42 to 90 mol.% silicon, from 5.5 to 38 mol.% aluminum and from 4 to 38 mol.% magnesium, and more preferably from 75 to 90 mol.% silicon, from 5.5 to 15 mol.% of aluminum oxide and from 4 to 10 mol.% of magnesium oxide, based on the total molar amount of silicon, aluminum and magnesium, from the viewpoint of mechanical strength and water resistance of the carrier. This is believed to be due to the fact that silicon, aluminum and magnesium content in these intervals form a certain stably associated structure.

The following description provides an explanation of the method of obtaining two preferred forms of media used in this embodiment and having the composition described above.

There are no particular restrictions on the method of receiving media containing silicon oxide and aluminium oxide, and aluminium-containing composition based on silicon oxide, obtained, for example, in accordance with the methods 1)to(5) below can be obtained by firing under the conditions described below.

(1) the Use of commercially available compositions of the silica-alumina.

(2) the Interaction Zola silicon oxide with a solution of aluminum compounds.

(3) the Interaction Zola silicon oxide with a compound of aluminum, insoluble in water.

(4) the Interaction of silica gel with an aqueous solution of aluminum compounds, soluble in water.

(5) Solid-phase interaction of silica gel with a compound of aluminum.

The following description provides a detailed explanation of ways to get media marked with (2) through (5) above.

In the methods (2) through (5) above Sol of silicon oxide or silica gel is used as a source of silicon oxide. There are no special restrictions with regard to the length of the chain Si-O silica gel, provided that it has nodes Si, without cross-linking, which react with Al. Although preferred examples of the aluminum compounds may include water-soluble compounds such as sodium aluminate, uranyl chloride of aluminum, hexahydro perchlorate aluminum, aluminum sulfate, nonahydrate of aluminum nitrate or aluminum diacetate, insoluble compounds such as aluminum hydroxide or aluminum oxide, can also be used, provided that they are compounds that react with Si without cross-linking, in the ashes of silicon oxide or silica gel.

In the case of methods (2) and (3)using the Sol of silicon oxide as a starting material, a Sol of silicon oxide is mixed with the compound of aluminium, receiving mixed Sol containing a colloidal solution of silicon oxide and a compound of aluminum, then Westlaw hydrothermal reaction for 1 to 48 hours at a temperature of from 20 to 100°C and drying to obtain a gel, and then calcined at a temperature, time and atmospheric conditions, which are described next. Alternatively, the alkaline aqueous solution is added to the above mixed solu to jointly precipitated silica and a compound of aluminum, followed by drying and subsequent calcination under the conditions described below. In addition, the above mixed Sol may be subjected to conversion into fine particles by direct use of the device for spray drying, or a mixed Sol can be dried with the formation of the gel, and then granulated with the receipt of a carrier containing silicon oxide and aluminum and having the desired particle diameters.

In the case of method (3), in particular, although the Sol of silicon oxide interacts with the compound of aluminium, which is insoluble in water, connection of aluminum can be pre-crushed to obtain particles of a given size or roughly chopped. After mixing and interaction Zola oxide of silicon and aluminum compounds, insoluble in water, the mixture is dried, followed by firing under the conditions described below. The composition of the silica-alumina can be crushed to obtain particles of a given size after firing without prior grinding aluminum compounds.

In the case of method (4)where is lycogel used as a starting material, an aqueous solution of a water-soluble aluminum compounds react in the silica gel, and silica gel can either be pre-crushed to obtain particles of a given size, or roughly chopped. After mixing and interaction of silica gel and an aqueous solution of water-soluble aluminum compounds, for from 1 to 48 hours at a temperature of from 20 to 100°C, the mixture is dried, followed by firing for 1 to 48 hours under the conditions described below. The composition of the silica-alumina can be crushed to obtain particles of a given size after firing without prior grinding of the silica gel.

Similarly, in the method (5), which also use silica gel as the starting material, the mixture is produced by reacting silica gel with a compound of aluminum in the solid phase. Al interacts in the solid phase with Si without cross-linking. Silica gel and the connection of aluminum can be pre-crushed to obtain particles of a given size or can be roughly chopped. Grinding can be performed separately for each substance or both substances can be ground after mixing. The firing is performed at a temperature, time and atmospheric conditions, which are described next. The mixture of silica gel and aluminum compounds can be used in ismalic the Institute to the desired particle size after the reaction without prior grinding.

As for the method of receiving media containing silicon oxide, aluminum oxide and at least one kind of the main metal component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, the carrier can be obtained by drying a slurry containing a mixture of silicon oxide, aluminum oxide, and compounds of alkali metals, compounds of alkaline earth metal and/or compounds of rare-earth metal, in accordance with the method of receiving media containing silicon oxide and aluminum oxide, as described above, followed by firing under the conditions described below.

Typical commercially available compounds, similar containing aluminum source material, can be used as a starting compound of the alkali metal, alkaline earth metal and rare earth metal. The source material is preferably a water-soluble compound, and more preferably is a hydroxide, carbonate, sulfate or acetate.

Another example of the production method, which can be used may include the adsorption of the primary metal component selected from the group consisting of alkali metals, alkaline earth metals and rare-earth metals on a medium containing about what led silicon and aluminum oxide. For example, can be used with immersion, in which a carrier is added to the solution in which the dissolved compound of the base metal, followed by heat treatment, or an application in which the main compound in the amount equal to the pore volume, is included in the carrier, followed by drying. However, the way in which the connection of the alkali metal is then adsorbed, requires caution, namely, that the processing liquid drying is performed in mild conditions, taking into account the high degree of dispersion of the primary metal component on the carrier.

Below is an explanation of the method of receiving media containing silicon oxide, aluminum oxide and magnesium oxide. The media system based on a silicon oxide-aluminum oxide-magnesium oxide obtained in accordance with methods (1)to(5) below, may be, for example, obtained by firing under conditions that are described below.

(1) Preliminary gel formation of the silicon oxide-aluminum oxide followed by the addition of magnesium oxide.

(2) the Interaction Zola oxide of silicon, aluminum compounds and compounds of magnesium.

(3) the Interaction Zola silicon oxide, aluminum compounds, insoluble in water, and compounds of magnesium, insoluble in water.

(4) the Interaction of silica gel, water-soluble compounds the Oia aluminum and water-soluble magnesium.

(5) Solid-phase interaction of silica gel, aluminum compounds and compounds of magnesium.

In the methods (1) through (5) above Sol of silica, water glass or silica gel is used as a source of silicon oxide. There are no special restrictions with regard to the length of the chain Si-O silica gel, provided that it has nodes Si, without cross-linking, which react with Al. Although preferred examples of the aluminum compounds may include water-soluble compounds such as sodium aluminate, the uranyl aluminium chloride, uranyl perchlorate aluminum, aluminum sulfate, nonahydrate of aluminum nitrate or aluminum diacetate, insoluble compounds such as aluminum hydroxide or aluminum oxide, can also be used, provided that they are compounds that react with Si without cross-linking, in the ashes of silicon oxide or silica gel. Examples of magnesium compounds which may be used may include magnesium oxide, magnesium hydroxide, magnesium acetate, magnesium nitrate, magnesium chloride and magnesium sulfate.

In the case of method (1), in which the gel of silica-alumina is used as the source material, initially to liquid glass add sulfuric acid, obtaining a hydrogel of silica having a pH from 8 to 10.5, followed by the addition thereto of a solution Alsub> 2(SO4)3(pH 2 or less) and adding sodium aluminate (pH 5 to 5.5) to obtain the hydrogel of silica-alumina. After that, the moisture content of the gel is adjusted to a value from 10 to 40% by spray drying and the like, followed by addition of magnesium oxide, conducting a hydrothermal reaction for 1 to 5 hours at a temperature of from 50 to 90°C, drying and then firing under the conditions described below, to obtain the media.

In the case of methods (2) and (3)using the Sol of silicon oxide as a starting material, a Sol of silicon oxide, a compound of aluminum and magnesium compound are mixed, receiving mixed Sol containing a colloidal solution of silicon oxide, a compound of aluminum and magnesium compound, and carry out the hydrothermal reaction for 1 to 48 hours at a temperature of from 20 to 100°C and subsequent drying to obtain a gel, then the gel is calcined at a temperature, time and atmospheric conditions, which are described next. Alternatively, the alkaline aqueous solution is added to the above mixed solu for co-deposition of silicon oxide, aluminum compounds and a compound of magnesium, followed by drying and subsequent calcination under the conditions described below. In addition, the above mixed Sol may be subjected to conversion into fine particles with the direct use of the selected authentication device for spray drying, or mixed Sol can be dried with the formation of the gel and then granulated with the receipt of a carrier containing silicon oxide, aluminum oxide and magnesium oxide and having the desired particle diameters.

In the case of method (3), in particular, although the Sol of silicon oxide interacts with the compound of aluminium and magnesium compound, which is insoluble in water, a compound of aluminum and magnesium compound can be pre-crushed to obtain particles of a given size or roughly chopped. After mixing and interaction Zola silicon oxide, aluminum compounds, insoluble in water, and compounds of magnesium, insoluble in water, the mixture is dried, followed by firing under the conditions described below. The composition of the silicon oxide-aluminum oxide-magnesium oxide may be pulverized to obtain particles of a given size after firing without prior grinding of aluminum compounds and compounds of magnesium.

In method (4) using silica gel as the starting material an aqueous solution of a water-soluble aluminum compounds and water-soluble magnesium reacts in the silica gel, and silica gel can either be pre-crushed to obtain particles of a given size, or roughly chopped. After mixing and interaction of silica gel and water rest the RA water-soluble aluminum compounds and water-soluble magnesium within 1 to 48 hours, at a temperature of from 20 to 100°C, the mixture is dried, followed by firing for 1 to 48 hours under the conditions described below. The composition of the silicon oxide-aluminum oxide-magnesium oxide may be pulverized to obtain particles of a given size after firing without prior grinding of the silica gel.

Similarly, in the method (5), which also use silica gel as the starting material, the mixture is produced by reacting silica gel with a compound of aluminum and a magnesium compound in the solid phase. Silica gel, a compound of aluminum and magnesium compound can be pre-crushed to obtain particles of a given size or can be roughly chopped. Grinding can be performed separately for each substance, or all three substances can be shredded after mixing. Firing is performed at a temperature, time and atmospheric conditions, which are described next. The mixture of silica gel, aluminum compounds and magnesium compounds can be used during grinding to the desired particle size after the reaction without prior grinding.

In addition, inorganic and organic substances can be added to a mixed suspension of each of the above raw materials in order to adjust the properties of the suspension or fine-tune the properties of the product, for example, is the structure of the pores, or properties of the resulting media.

Specific examples of inorganic substances may include inorganic acids such as nitric acid, hydrochloric acid or sulfuric acid, metal salts of alkaline metals such as Li, Na, K, Rb or Cs, or alkaline earth metals such as Mg, Ca, Sr or Ba, a water-soluble compounds such as ammonia or ammonium sulfate, and clay minerals, which form a suspension by dispersing in water. In addition, specific examples of organic substances may include polymers, such as polyethylene glycol, methylcellulose, polyvinyl alcohol, polyacrylic acid or polyacrylamide.

Although there are a variety of effects adding inorganic and organic substances, these effects can basically enable the formation of spherical media, as well as regulation of pore size and pore volume, and more specifically, fluid properties in relation to the mixed suspension is an important factor in obtaining spherical media. Fluid properties can be changed to such values that contribute to obtaining a spherical carrier by adjusting the viscosity and concentration of solid particles with inorganic and organic substances. In addition, the regulation of pore size and pore volume can be fulfilled you is by EO optimal organic compounds, which remains inside media at the stage of education and may be removed by roasting and leaching after education.

The media can be obtained by spray drying the mixed slurry of each of the above raw materials and additives. Known spray devices, such as devices with rotating disk devices with the dual fluid nozzle or nozzle of high pressure, can be used for grinding the mixed slurry to drip condition.

It is necessary that the spray was used in the well-mixed condition. If the liquid is poorly mixed, the liquid affects the characteristics of the media, for example, causes a decrease in durability due to uneven distribution of the composition. In particular, in the preparation of the mixture of starting materials, because there are cases in which there is an increase in the viscosity of the suspension or partial gilotinirovaniya (hardening of the colloid), you should pay attention to prevent the formation of an inhomogeneous particles. Accordingly, there are cases in which it is preferable to adjust the pH of the Sol of silicon oxide values near 2, polystable interval, for example, using a method such as adding acid or base, at the same time, also taking other measures, the same is a gradual mixing of source materials with stirring.

It is necessary that the spray had a certain degree of viscosity and concentration of solid substances. If the viscosity and the concentration of solid substances excessively low, many of porous bodies obtained by spray drying, have the form of deformed spheres, not perfect spheres. In addition, if the viscosity and concentration of solid substances excessively high, then, in addition to the negative impact on the dispersion of porous bodies, depending on the liquid properties, it is impossible the formation of a stable drops. Therefore, the viscosity is preferably in the range from 5 to 10000 CPS, provided that the liquid can be sprayed at this viscosity, and a higher viscosity that sputtering is more preferable in respect of shape, and taking into account the balance between viscosity and ease of handling, the viscosity is preferably selected from the range of 10 to 1000 CP. In addition, the concentration of solid substances in the range from 10 to 50 wt.% is preferable from the viewpoint of the shape and diameter of the particles. In addition, the temperature of hot air at the inlet of the drying column device for spray drying from 200 to 280°C and the outlet temperature of the drying column in the range from 110 to 140°C are preferred as generally accepted indicators of the conditions of spray drying.

The firing temperature of the carrier is usually chosen in the range from 200 to 800°C. Sintering at temperatures above 800°C causes a marked decrease in specific surface area, which makes such a temperature is undesirable. In addition, although there are no particular restrictions on the atmosphere for firing, the firing is usually carried out in air or in nitrogen atmosphere. In addition, although the firing time may be determined depending on the specific surface, after calcination, it usually takes from 1 to 48 hours. Due to changes in the physical properties of the medium, such as porosity, it is necessary to choose the appropriate temperature and heating conditions as conditions of firing. If the firing temperature is excessively low, it becomes difficult to maintain the durability in the form of a complex oxide, while if the firing temperature is excessively high, it leads to the reduction of pore volume. In addition, the conditions of heating preferably may include a gradual increase in temperature by a programmable heating, etc. In the case of firing under these conditions, when the temperature is rising quickly, gasification and combustion of inorganic and organic substances become intense, causing exposure to temperatures above a predetermined temperature or by grinding, which makes these undesirable conditions.

The specific surface is here media in the measurement method of nitrogen adsorption according to BET, is preferably 10 m2/g or more, more preferably 20 m2/g or more and more preferably 50 m2/g or more, from the viewpoint of ease of application and composite nanoparticles, catalytic activity and resistance to peeling. In addition, although it is not particularly required from the viewpoint of catalytic activity, the specific surface of the carrier is preferably 700 m2/g or less, more preferably 350 m2/g or less and more preferably 300 m2/g or less, from the viewpoint of mechanical strength and durability.

The pore structure of the media is an extremely important physical property in relation to the characteristics of the coating metal components, except for strength, long-term stability, including resistance to flaking, and characteristics of the reaction, and the diameter of pores is a physical quantity that is required for the manifestation of these characteristics. If the pore diameter of less than 3 nm, while the characteristics of exfoliation of the deposited metal are suitable, in the case of the use of the catalyst for liquid-phase reactions and the like, the diameter of pores is preferably 3 nm or more, from the viewpoint of maintaining high reactivity without excessive weather resistance is of diffusion inside the pores, so phase diffusion source of the reaction materials is not limiting stage. On the other hand, the pore size is preferably 50 nm or less, from the viewpoint of stability of the catalyst to cracking and resistance to flaking of deposited material. Thus, the diameter of pores is preferably from 3 to 50 nm and more preferably from 3 to 30 nm. Pore volume is required to ensure the presence of pores for the application of composite nanoparticles. However, if the pore volume becomes excessively large, the strength tends to rapidly decrease. Therefore, it is preferable pore volume in the range from 0.1 to 1.0 ml/g, along with the fact that from the point of view of strength is more preferable and its value in the interval from 0.1 to 0.5 ml/g Media in this variant implementation preferably satisfies the above intervals for pore size and pore volume.

The form of the medium is selected from a hollow cylindrical shape or a honeycomb shape, which is the structure that exhibits a low pressure drop in a fixed bed, in accordance with the type of reaction, and in suspension in the liquid phase of the suspension particles are usually spherical, and is selected in such form of media that allows the use of the media by selecting the optimum pore diameter of at osnovaniyakh ability and method of separation. For example, in the case of complete separation of the catalyst, using a typical simple way of separating by settling, the particle diameter is preferably selected from 10 to 200 μm, more preferably from 20 to 150 μm and even more preferably from 30 to 150 μm, considering the balance with the characteristics of the reaction. In the case of using the method with transverse preferred filter small particles having a diameter of from 0.1 to 20 μm or less, due to their high reactivity. Catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment can thus be used to change the appearance and shape of the carrier in accordance with the intended application.

Although there are no particular restrictions on the amount of oxidized Nickel, supported on a carrier, it usually ranges from 0.1 to 20 wt.%, preferably from 0.2 to 10 wt.%, more preferably from 0.2 to 5 wt.% and even more preferably from 0.5 to 2 wt.% in the calculation of the Nickel from the mass media. The number of X supported on a carrier, is usually from 0.1 to 10 wt.%, preferably from 0.2 to 5 wt.%, more preferably from 0.2 to 2 wt.%, even more preferably from 0.3 to 1.5 wt.% and particularly preferably from 0.5 to 1.0 wt.% in the calculation of the metal from the mass media.

Moreover, in this embodiment, the implementation of the population has a preferred spacing for the atomic ratio between Nickel and elemental composition of the media. In the case of the use of media in this variant implementation containing silicon oxide and aluminum oxide, the ratio of Nickel and aluminium oxide in the catalyst, based on the atomic ratio of Ni/Al, is preferably from 0.01 to 1.0, more preferably from 0.02 to 0.8 and even more preferably from 0.04 to 0.6. In addition, in the case of the use of media containing silicon oxide, aluminum oxide and at least one kind of the main metal component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals, the ratio of Nickel and aluminium oxide in the catalyst, based on the atomic ratio of Ni/Al, is preferably from 0.01 to 1.0, more preferably from 0.02 to 0.8 and even more preferably from 0.04 to 0.6, along with the fact that the ratio of Nickel and base metal component, calculated on an atomic ratio of Ni/(alkali metal + alkaline earth metal + rare earth metal)is preferably from 0.01 to 1.2, more preferably from 0.02 to 1.0, and more preferably from 0.04 to 0.6.

Moreover, the preferred intervals are also available for the atomic ratio between Nickel and components of the media elements of aluminum and magnesium in the case of a media system based on a silicon oxide-aluminum oxide-magnesium oxide. Ratio neither the El and alumina in the catalyst, in the calculation of the atomic ratio of Ni/Al, is preferably from 0.01 to 1.0, more preferably from 0.02 to 0.8 and even more preferably from 0.04 to 0.6. In addition, the ratio of Nickel and magnesium, based on the atomic ratio of Ni/Mg, preferably ranges from 0.01 to 1.2, more preferably from 0.02 to 1.0, and more preferably from 0.04 to 0.6.

If the atomic ratio of Nickel and aluminum, which are a constituent element of the carrier, the main metal element or magnesium are within the above interval, there is a tendency to increase the effects, leading to curb the leaching of Nickel and structural changes in the catalyst particles. It is believed to be the result of the formation of a specific complex oxide of Nickel, aluminium, primary metal component and magnesium when they are within these intervals, whereby is formed stably associated structure.

Catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment may also contain a third element as the active component of the catalyst, in addition to the oxidized Nickel and x Examples of items that might be found may include titanium, vanadium, chromium, manganese, iron, cobalt, zinc, Galli is, zirconium, niobium, molybdenum, rhodium, cadmium, indium, tin, antimony, tellurium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, mercury, thallium, lead, bismuth, aluminum, boron, silicon and phosphorus. The content of these third compound is from 0.01 to 20 wt.% and preferably from 0.05 to 10 wt.% in the calculation of the catalyst. In addition, the catalyst may also contain at least one kind of metal component selected from the group consisting of alkali metals, alkaline earth metals and rare earth metals. The content of these alkali metals, alkaline earth metals or rare earth metals is selected in the range of from 15 wt.% or less based on the catalyst.

It should be noted that these third elements or alkali metals, alkaline earth metals and rare earth metals may be contained in the catalyst at the time of receipt and the reaction catalyst, or may be used a method in accordance with which they advance contained in the carrier.

The shape of the catalyst

The specific surface of the catalyst in accordance with this embodiment, as measured using nitrogen adsorption according to BET, is preferably in the range from 20 to 350 m2/g, more preferably from 50 to 300 m2/g and even more preferably from 100 to 250 m2/g point the of view of catalytic activity and resistance to peeling of the active components.

The pore structure of the catalyst is extremely important physical property in relation to the characteristics of the coating metal components, long-term stability, including resistance to flaking, and characteristics of the reaction, and the diameter of pores is a physical quantity that is required for the manifestation of these characteristics. If the pore diameter of less than 3 nm, while the characteristics of exfoliation of the deposited metal are suitable, in the case of the use of the catalyst for liquid-phase reactions and the like, the diameter of pores is preferably 3 nm or more, from the viewpoint of maintaining high reactivity without excessive resistance diffusion inside the pores, so that the phase diffusion source of the reaction materials is not limiting stage. On the other hand, the pore size is preferably 50 nm or less, from the viewpoint of stability of the catalyst to cracking and resistance to flaking of deposited material. Accordingly, the diameter of pores is preferably from 3 to 50 nm, more preferably from 3 to 30 nm and even more preferably from 3 to 10 nm. The pore volume is preferably in the range from 0.1 to 1.0 ml/g, more preferably from 0.1 to 0.5 ml/g and even more preferably from 0.1 to 0.3 ml/g, from the viewpoint of the characteristics of the application and characteristics of the reaction. Rolled the ATOR in accordance with this embodiment preferably satisfies the above intervals for pore size and pore volume.

The diameter of pores of the catalyst may be selected appropriately depending on the type of reaction. For example, when used in a state of suspension in the liquid phase, the diameter of the pores varies in accordance with the method used to separate the catalyst, and in the case of a branch of the spontaneous deposition is preferably from 10 to 200 μm, more preferably from 20 to 150 μm and even more preferably from 20 to 100 microns.

The method of preparation of the catalyst used to produce complex ether carboxylic acid

There are no particular restrictions on the method of preparation of the catalyst in accordance with this embodiment, provided that the catalyst was prepared as described above, and can be applied commonly used methods of obtaining the catalyst on the carrier, examples of which may include methods with application (such as adsorption, the pores are filled, drying by evaporation or sputtering), methods of deposition (such as co-precipitation, deposition or mixing), ion exchange, and precipitation from the vapor phase. In this embodiment, the methods of application and deposition are preferred, more preferred are methods of deposition.

The following description provides an explanation of a typical pic is BA the preparation of the catalyst in accordance with this embodiment, using the example of deposition. In the first stage, for example, the catalyst precursor is produced by deposition of Nickel and X component on the carrier by neutralizing the acidic aqueous solution of a soluble metal salt containing Nickel and X. At this stage, the components of Nickel and X (such as the hydroxide) are precipitated and fixed on the carrier by means of a neutralization reaction between Nickel ions and X in aqueous solution. The Association of Nickel and X component preferably make more appropriate due to the simultaneous deposition of a mixed aqueous solution of both components.

Then, in the second stage, the catalyst in accordance with this embodiment can be obtained by washing and drying the catalyst precursor obtained in the first stage, in accordance with need, followed by heat treatment.

Examples of soluble metal salts containing Nickel, which is used for catalyst may include Nickel nitrate, Nickel acetate and Nickel chloride. In addition, examples of soluble metal salts containing X may include palladium chloride and palladium acetate in the case where palladium is selected as X, ruthenium chloride and ruthenium nitrate in the case where ruthenium is selected as X, soloconsolidation acid, tetrachloroaurate sodium, dicyanoaurate potassium, gold, diethylamine is lurid and cyanide gold in case when gold is selected as X, and silver chloride and silver nitrate when silver is selected as X.

Examples of the bases used for the preparation of the catalyst may include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia. In addition, the medium may also contain one or more kinds of main metal component selected from the group consisting of alkali metals (such as Li, Na, K, Rb or Cs), alkaline earth metals such as Be, Mg, Ca, Sr or Ba) and rare earth metals such as La, Ce or Pr).

In the first stage, the acidic aqueous solution of a soluble metal salt containing Nickel and X, is mixed with a carrier and then neutralized with base under stirring to precipitate a precipitate of Nickel and X component on the carrier. During the deposition of the Nickel component and X are selected suitable conditions, such as concentration of an aqueous solution containing Nickel and X, the base, the pH of the aqueous solution and the temperature.

The concentration of each component in an aqueous solution containing Nickel and X is typically in the range of from 0.0001 to 1.0 mol/l, preferably from 0.001 to 0.5 mol/l and more preferably 0.005 to 0.2 mol/L. the Ratio of Nickel and X in aqueous solution, based on the atomic ratio of Ni/X preferably ranges from 0.1 to 10, more preferred the equipment from 0.2 to 5.0 and more preferably from 0.5 to 3.0.

In addition, the pH of the aqueous solution of regulate above the base so that the pH generally ranged from 5 to 10 and preferably in the range from 6 to 8. The temperature of the aqueous solution is usually in the range from 0 to 100°C, preferably from 30 to 90°C and more preferably from 60 to 90°C.

In addition, there are no special restrictions with regard to the time of deposition of the Nickel component and X, although this time varies depending on factors such as damage to components, the number of deposited Nickel and X and the ratio of Nickel and X, it is usually in the range from 1 minute to 5 hours, preferably from 5 minutes to 3 hours and more preferably from 5 minutes to 1 hour.

The temperature during heat treatment of the catalyst precursor in the second stage is usually from 40 to 900°C, preferably from 80 to 800°C, more preferably from 200 to 700°C and even more preferably from 300 to 600°C. Heat treatment is performed on the air (or ambient air), in an oxidizing atmosphere (such as oxygen, ozone, nitrous oxide, carbon dioxide, hydrogen peroxide, hypochlorous acid, or inorganic/organic peroxide) or in the atmosphere of inert gas (such as helium, argon or nitrogen). The duration of heat treatment is chosen appropriately in accordance with the temperature the first heat treatment and the amount of catalyst precursor.

Following this second stage, if necessary, can be performed restorative treatment in a reducing atmosphere (such as hydrogen, hydrazine, formaldehyde or formic acid). In this case, the recovery is performed when the selection processing method, in which the oxidized Nickel is not restored completely to metallic state. The temperature and duration of the recovery processing is chosen appropriately in accordance with the type of reducing agent, the type of X and the number of catalyst.

Moreover, if necessary, can be performed oxidation treatment in air (or in the atmospheric air or in an oxidizing atmosphere (such as oxygen, ozone, nitrous oxide, carbon dioxide, hydrogen peroxide, hypochlorous acid, or inorganic/organic peroxide), followed by heat treatment or recovery processing, as described above.

The third constituent element in addition to Nickel and X, may be added during preparation of the catalyst or reaction conditions. Alkali metal, alkaline earth metal or rare earth metal can also be added during preparation of the catalyst or in the reaction system. In addition, the raw materials of the third constituent element, alkali metal, alkaline earth metal and redkozemelnye metal selected from salts of organic acids, salts of inorganic acids, hydroxides, etc.

The method of obtaining complex ether carboxylic acid

Ester carboxylic acids can be obtained from (a) aldehyde and alcohol, or (b) one or more kinds of alcohols in the presence of oxygen using a catalyst to produce complex ether carboxylic acids in accordance with this embodiment.

Although there are no particular restrictions on the number of used catalyst, and it can vary in a wide range according, for example, with the input of the reaction materials, the catalyst composition and method of its production, the reaction conditions or the type of reaction, in the case of participating in the reaction, the catalyst in suspension, the catalyst may be preferably used so that the concentration of solid matter in suspension ranged from 1 to 50 wt./vol.%, preferably from 3 to 30 wt./vol.% and more preferably from 10 to 25 wt./vol.%.

Examples of aldehydes that can be used as starting materials may include C1-C10aliphatic saturated aldehydes, such as formaldehyde, acetaldehyde, Propionaldehyde, Isobutyraldehyde or glyoxal; C3-C10aliphatic α-β-unsaturated aldehydes, such as acrolein, methacrolein or CROTONALDEHYDE; C6-C20aromatic aldehydes such as benzaldehyde, tolylaldehyde, Benzylalcohol or phthalaldehyde; and derivatives of these aldehydes. These aldehydes may be used singly or as a mixture of any two or more types.

Examples of alcohols which can be used may include C1-C10aliphatic saturated alcohols, such as methanol, ethanol, isopropanol, butanol, 2-ethylhexanol or octanol; C5-C10alicyclic alcohols, such as Cyclopentanol or cyclohexanol; C2-C10diols, such as ethylene glycol, propylene glycol or butanediol; C3-C10aliphatic unsaturated alcohols such as allyl alcohol or metalloy alcohol; C6-C20aromatic alcohols such as benzyl alcohol; and hydroxyacetone, such as 3-alkyl-3-hydroxyethyloxy. These alcohols can be used individually or as mixtures of any two or more kinds of them.

In the method of obtaining, in accordance with this embodiment (a) the corresponding ester of carboxylic acid can be obtained by reacting the aldehyde and alcohol, or (b) the corresponding ester of carboxylic acid can be obtained by reacting one or more kinds of alcohols.

If p is the receipt of a complex ester of carboxylic acid from aldehyde and alcohol there are no special restrictions with respect to mass ratio of the aldehyde and alcohol, although obtaining may be performed in a wide range of mass ratios, for example, when the molar ratio of aldehyde to alcohol is from 10 to 1/1000, getting typically carried out at a molar ratio in the range from 1/2 to 1/50.

In case of receipt of ester carboxylic acids of the two types of alcohols are also no specific limitations with respect to mass ratios kinds of alcohols, and the receiving may be performed at a molar ratio of one type of alcohol for a different kind of alcohol from 10 to 1/1000 and preferably from 1/2 to 1/50.

Obtaining a complex ester of carboxylic acid can be performed either periodic or continuous manner using any arbitrary method, such as the reaction in the vapor phase, the reaction in the liquid phase or reaction under irrigation.

Although the reaction can be carried out in the absence of solvent, it can also be carried out using a solvent which is inert towards the reaction components, such as hexane, decane, benzene or dioxane.

Although the reaction can be carried out using a type of reaction known from the prior art, such as reaction in a fixed bed, the reaction in the fluidized bed or the reaction vessel with stirring in the course of reaction, for example, in the liquid phase, the reaction can be conducted and the use of any of the reaction tank, such as the reactor in the form of a bubble column reactor in the form of a suction pipe or reactor in the form of a tank with stirring.

Oxygen is used to produce complex ether carboxylic acids, may be in the form of molecular oxygen, namely gaseous oxygen by itself or mixed gas, in which gaseous oxygen is diluted with a diluent which is inert to the reaction, for example, gaseous nitrogen or carbon dioxide, and preferably as the source of oxygen is air because of the simplicity of the implementation process, saving etc.

Although the partial pressure of oxygen varies according to the type of aldehyde, type of alcohol and other reactive materials, reaction conditions, or the type of the reaction vessel and the like, whereas the practical application, the partial pressure of oxygen at the outlet of the reaction vessel is in the interval that is less than the lower limit value of explosive interval of its concentration, and preferably regulated so that is, for example, from 20 to 80 kPa. Although the reaction can be conducted in a wide range of arbitrary values of the reaction pressure from low pressure to high pressure, the reaction is usually carried out at Yes the tion from 0.05 to 2 MPa. From a security perspective, it is preferable to set the total pressure so that oxygen concentration in the gas leaving the reaction vessel does not exceed the lower explosive limit (oxygen concentration, for example, 8%).

When conducting the reaction receipt of ester carboxylic acid in the liquid phase and the like, the pH of the reaction system is preferably supported at size 6 to 9 by adding to the reaction system connection alkali metal or alkaline earth metal (such as oxide, hydroxide, carbonate or carboxylate). These compounds are alkali metal or alkaline earth metal can be used alone or two types or more may be used in combination.

Although obtaining a complex ester of carboxylic acid can be performed at a high temperature of 200°C and above as the reaction temperature, the reaction temperature is preferably from 30 to 200°C, more preferably from 40 to 150°C and even more preferably from 60 to 120°C. there are No particular restrictions on the reaction time, and although it cannot be unconditionally determined because it varies in accordance with specified conditions, it usually takes from 1 to 20 hours.

Examples

Although the following description provides a more detailed R is yasnenie this variant implementation through examples this alternative implementation is not limited to these examples. An ordinary person skilled in the art can perform the examples below, as well as their various ways, and such variations are also included in the scope of claims for patent.

In addition, in the examples and comparative examples, the determination of the amounts of Ni and X, supported on a carrier, and the atomic ratio Ni/(Ni + X), determination of the constituent elements (Si, Al, base metal, Mg)supported on a carrier, the determination of the proportions of Nickel and components supported on a carrier, the analysis of the crystal structure of the nanoparticles, the analysis of the chemical state of the metal catalyst components, morphological control and elemental analysis of nanoparticles, the measurement of the spectra of the catalysts in the UV and visible region, the analysis of the chemical state of Nickel, measuring the physical properties of the carrier and catalyst (specific surface, pore diameter, pore volume), visual examination of the forms of media and catalyst and measuring the average diameter of the particles was performed in accordance with the methods described below.

The determination of the amounts of Ni and X, supported on a carrier, and the atomic ratio Ni/(Ni + X)

Concentrations of Nickel and X in the catalyst was quantitatively determined using atomic emission spectrometer with inductively related is Anna plasma IRIS Intrepid II Model XDL (ICP-AES, MS) manufactured by Thermo Fisher Scientific K.K.

Samples were prepared, when the catalyst in a Teflon vessel for the decomposition of added sulfuric acid and hydrogen fluoride was dissolved by heating using a microwave device sample preparation ETHOS TC manufactured by Milestone General K.K. and evaporated to dryness heater followed by the addition of nitric acid and hydrochloric acid to the precipitated residue was dissolved by heating using a microwave device sample preparation and was used for sample clean fluid with a fixed volume, obtained by decomposition.

This method of quantitative determination was performed using its own standard method by ICP-AES, and subtract the value of the test blank sample to determine the content of Nickel and X in the catalyst and to calculate their deposited amount and the atomic ratio.

The determination of the content of the constituent elements (Si, Al, base metal, Mg), applied to the media

To prepare the samples, obtained by dissolution of the carrier sodium silicate, and samples obtained by dissolving the molten alkali salt. The content of the base metal and/or Mg were measured in samples obtained by dissolving sodium silicate, while the content of Al and Si were measured in samples obtained solution is of the molten alkali salt, using atomic emission spectrometer with inductively coupled plasma (ICP-AES) JY-38P2 manufactured by Seiko Electronics Industry Co., Ltd., with the subsequent calculation of the atomic ratios of the values obtained metal content.

Determination of the proportions of Nickel and composite media elements

The atomic ratio was calculated from the values of Ni, Al, Mg and base metal, measured as specified above.

Analysis of the crystal structure of the nanoparticles

Analysis of the crystal structure of the nanoparticles was performed using a system of powder x-ray diffraction (XRD) Rint2500 production Rigaku Corp., using a copper tube as an x-ray source (40 kV, 200 mA), the measurement interval from 5 to 65 degrees (0.02 deg./step), the speed of measurement of 0.2 deg./min and the width of the slits (scattering, divergence, reception) 1 C, 1 C and 0.15 mm

The catalyst samples were evenly dispersible on non-reflective plate for sample and recorded neoprene wrap.

The analysis of the chemical state of the metal catalyst components

The analysis of the chemical state of the metal catalyst components was performed using system x-ray photoelectron spectroscopy (XPS) ESCALAB 250 Thermo Electron Corp., using Al Kα (15 kV × 10 mA) for the excitation source, with review of the dummy surface area of about 1 mm (shape: oval), using the overview scan (from 0 to 1, 100 eV) and a narrow scan (Ni2p) for absorption fields.

Samples for measurement of XPS were prepared by grinding the catalyst particles by using an agate mortar and pestle and sampling the received powder.

Morphological control and elemental analysis of nanoparticles

Received svetlopoli image TEM dark-field STEM image and the analyses of the composition of the STEM-EDS analysis at points, mapping, linear distribution) was performed using a transmission electron microscope/scanning transmission electron microscope (TEM/STEM) model 3100FEF, production JEOL (accelerating voltage: 300 kV, equipped with energy dispersive x-ray detector (EDX)).

Software for data analysis consisted of Digital Micrograph™ Ver. 1.70.16 (Gatan) for analytical TEM images and STEM (length measurement, analysis with Fourier transform) and NORAN System SIX Ver. 2.0 (Thermo Fisher Scientific) for data analysis, EDS (processing mapped image, quantitative estimates of the composition).

Samples for measurements were prepared by grinding the catalyst particles using a mortar and pestle, was dispersible in ethanol and subjected to ultrasonic cleaning for about 1 minute, and then fed dropwise to microedu from molybdenum (Mo) and were subjected to the hcpa the ha with obtaining samples for observation of TEM/STEM.

The dimension spectrum of the catalyst in the UV and visible region

The dimension spectrum of the catalyst in the UV and visible region was performed using a spectrophotometer V-550 UV and visible region production company JASCO Corporation (the integrating sphere, with the holder of the powder sample), during the measurement interval from 800 to 200 nm and scan speed of 400 nm/min

Samples for measurements were prepared by grinding the catalyst particles using a mortar and pestle, placed in the holder of the powder sample and used for measurements in the UV and visible region.

Analysis of the chemical state of Nickel

Ni Kα spectra were measured using x-ray spectrometer high resolution (HRXRF) XFRA-190 production Techno Corp., and each of the obtained types of parameters were compared with parameters for standard substances (Nickel metal, Nickel oxide)to assess the chemical valence state of Nickel, etc. in the catalysts.

Samples for measurements were used for measurements without modification. Measurement of the Ni Kα spectra was performed in partial spectrum. For crystal structure analysis used the gap Ge (220)having a vertical divergence angle of 1°, and the excitation voltage and current were set at 35 kV and 80 mA, respectively. Filter paper was used DL the absorber in the standard samples, time accounts were chosen for each sample of the sample catalyst and the measurements were performed so that the intensity of the Kα peak in spectrum was 3000 account/s or less, and the time the account was 10000 or more accounts. The measurements were repeated five times for each sample and the sample of the metal was measured before each repeated measurement and after him. After smoothing (method of stochastic gradient (S-G), 7 points, 5 cycles) of the measured spectra was calculated peak position, full width at half maximum (FWHM) and the asymmetry factor (Al), and the position of the peak is considered as a bias, or chemical shift (ΔE), relative to measured values for a sample of metal before and after measurement of the sample.

The physical properties of the carrier and catalyst: specific surface area, pore size, pore volume

The measurements were performed using a device Autosoap 3MP production Yuasa Ionics Inc., using nitrogen as the adsorbed gas method with nitrogen adsorption). Specific surface area was measured by the method according to BET, the diameter of pores and the pore size was measured by the method of bjh's (Barrett-Joyner-Halenda) and pore volume were measured by using the adsorbed amount at the maximum ratio P/P0.

Visual examination of the forms of media and catalyst

Visual examination of the particles of the medium and produce the RA was performed using scanning electron microscope (SEM), X-650 production Hitachi, Ltd.

The measurement of average particle diameter of the carrier and catalyst

The average particle diameter (volume-based) was measured by using a particle size analyzer by laser diffraction LS230 production Beckman-Coulter, Inc.

Reference example 1

Using 0.5 g of commercially available Nickel oxide (Wako Pure Chemical Industries, Ltd.) as a catalyst, 1.0 g of methacrolein and 10 ml of methanol were loaded into the reaction vessel in the form of a high pressure autoclave (total volume: 120 ml)made of SUS316 and equipped with a magnetic stirrer. After the autoclave was closed and the atmosphere inside the system was replaced with nitrogen gas, the gas mixture-based nitrogen containing 7 vol.% oxygen was injected into the headspace of the site and the total pressure inside the system was increased to 3.0 MPa. Then the reaction vessel was placed in an oil bath and reaction was performed for 2 hours at the reaction temperature of 80°C under stirring. After cooling down the residual pressure and opening the autoclave, after which the catalyst was filtered and the filtrate analyzed by gas chromatography. As a result, the amount formed of methyl methacrylate was 1.0 μmol.

Reference example 2

The reaction was conducted in the same manner as in reference example 1, except for the catalyst guide the ATA peroxide Nickel (Aldrich Corp.) instead of Nickel oxide. As a result, the amount formed of methyl methacrylate was 5.3 mmol.

Reference example 3

The reaction was conducted in the same manner as in reference example 1, except for metallic Nickel catalyst (Wako Pure Chemical Industries, Ltd.) instead of Nickel oxide. The result was confirmed by the inability of the education of methyl methacrylate.

Example 1

(1)Obtaining catalyst

30 g of commercially available γ-alumina (Neobead, Mizusawa Industrial Chemicals, Ltd.) added to a glass container containing 100 ml of distilled water, and then added dropwise in the specified quantities of an aqueous solution of Nickel nitrate and an aqueous solution of palladium chloride, stirring at 60°C, was added to 0.5 N. aqueous sodium hydroxide solution to bring the pH of aqueous solutions up to 8, continued stirring for 1 hour, gave calmly to settle, removing the supernatant, washed with distilled water until until Cl ions was no longer found, were dried for 16 hours at 105°C and annealed in air for 5 hours at 600°C. Then the catalyst was subjected to reduction treatment for 1 hour at room temperature in hydrogen atmosphere, receiving the catalyst coated with 1.5 wt.% Nickel and 0.5 wt.% palladium (NiOPd/γ-alumina). The atomic ratio of Ni/(Ni + Pd) obtained in the second catalyst was 0,84. Based on the results of x-ray diffraction (XRD) diffraction pattern characteristic of Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. On the other hand, although he could not be defined as a distinct peak, was attended by a broad peak corresponding to the crystal palladium. Although the magnitude of this peak was close to the detection limit of the powder x-ray diffraction (2 nm), the calculations of the average crystallite size using the sherrer formula gave a value of about 3 nm. Regarding the chemical state of Ni was confirmed by the valence equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS).

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 3 to 4 nm (srednesemennyh particle diameter: 3,8 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles by the method of auxiliary energy dispersive x-ray spectroscopy (EDX) and confirmed the presence of Nickel and palladium all particles. The atomic ratio of Nickel to palladium in these composite particles (average value) was $ 1,24.

(2)The synthesis is false ether carboxylic acid

0.2 g of the catalyst obtained in (1) above, 1.0 g of methacrolein and 10 ml of methanol were loaded into the reaction vessel in the form of a high pressure autoclave (total volume: 120 ml)made of SUS316 and equipped with a magnetic stirrer. After the autoclave was closed and the atmosphere inside the system was replaced with nitrogen gas mixture-based nitrogen containing 7 vol.% oxygen was injected into the headspace of the site and increased the pressure inside the system to 3.0 MPa.

Then the reaction vessel was placed in an oil bath and reaction was performed for 1 hour at the reaction temperature of 80°C and under stirring. After cooling down the residual pressure and opening the autoclave, after which the catalyst was filtered and the filtrate analyzed by gas chromatography. As a result, the degree of conversion of methacrolein was 18.2% and the selectivity of the formation of methyl methacrylate amounted to 74.5%.

Example 2

The catalyst was obtained in the same manner as in (1) of example 1, except for using an aqueous silver nitrate solution instead of an aqueous solution of palladium chloride. Deposited Nickel and silver obtained catalyst was 1.6 wt.% and 1.3 wt.%, respectively (NiOAg/γ-alumina). In addition, the atomic ratio of Ni/(Ni + Ag) amounted to 0.69. Based on the results of powder x-ray di is racchi (XRD) was attended by a broad peak, suitable crystals of silver. Calculations of the average size of the crystallites in accordance with the formula sherrer gave a value of about 4 nm. On the other hand, a diffraction pattern characteristic of Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. Regarding the chemical state of Ni was confirmed by the valence equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS).

Visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 4 to 5 nm (srednesemennyh particle diameter: 4,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles by the method of auxiliary energy dispersive x-ray spectroscopy (EDX) and confirmed the presence of Nickel and silver in all the particles. The atomic ratio of Nickel to silver in these composite particles (average value) was 0.81.

In addition, the study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to silver nanoparticles, not nablyudalis the near 405 nm, while there was wide scope absorption characteristic of NiO2over the range of wavelengths from 200 to 800 nm.

The reaction was conducted in the same manner as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein amounted to 6.2% and the selectivity of the formation of methyl methacrylate was 55.1 per cent.

Example 3

The catalyst was obtained in the same manner as in (1) of example 1, except for using an aqueous solution soloconsolidation acid instead of an aqueous solution of palladium chloride. Deposited Nickel and gold obtained catalyst amounted to 1.4 wt.% and 0.4 wt.%, respectively (NiOAu/γ-alumina). In addition, the atomic ratio of Ni/(Ni + Au) amounted to 0.92. Based on the results of powder x-ray diffraction (XRD) diffraction pattern characteristic of Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. On the other hand, although he could not be defined as a distinct peak, was attended by a broad peak corresponding to the gold crystals. Although the magnitude of this peak was close to the detection limit of the powder x-ray diffraction (2 nm), the calculations of the average crystallite size using the sherrer formula gave a value of about 3 nm. Regarding the chemical state of Ni was under the approved valency, equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS).

Visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles by the method of auxiliary energy dispersive x-ray spectroscopy (EDX) and confirmed the presence of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 1.14.

The study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed near 530 nm, while there was wide scope absorption characteristic of NiO2over the range of wavelengths from 200 to 800 nm.

The reaction was conducted in the same manner as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein was 22.4%, and the selectivity of the formation of methyl methacrylate was 92.4 per cent.

Reference example 4

The catalyst coated with Nickel in the amount of 1.5 wt.% (NiO/γ-alumina) was obtained in the same manner as in (1) of example 1, except that no was added an aqueous solution of palladium chloride and did not carry out the reduction with hydrogen.

The reaction was conducted in the same manner as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein amounted to 3.1%, and the selectivity of the formation of methyl methacrylate was 35.2 per cent.

Comparative example 1

The catalyst coated with palladium in the amount of 0.5 wt.% (Pd/γ-alumina) was obtained in the same manner as in (1) of example 1, except that no added nitrate Nickel. In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the crystal palladium. Calculations of the average size of these crystallites in accordance with the formula sherrer gave a value of about 3 nm.

The reaction was conducted in the same manner as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein was 10.3% and the selectivity of the formation of methyl methacrylate was 52.4 percent.

Comparative example 2

The catalyst coated silver amount of 1.5 wt.% (Ag/γ-alumina) was obtained in the same manner as in (1) of example 1, except that used the aq is th silver nitrate solution instead of an aqueous solution of palladium chloride was not added nitrate Nickel. In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the crystals of silver. Calculations of the average size of these crystallites in accordance with the formula sherrer gave a value of about 5 nm. The study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to silver nanoparticles was observed near 405 nm.

The reaction was conducted in the same manner as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein was 2.1% and the selectivity of the formation of methyl methacrylate was 25.3%.

Comparative example 3

The catalyst was coated with 1.5 wt.% Nickel and 1.4 wt.% silver (NiAg/γ-alumina) was obtained in the same manner as in (1) of example 1, except that used aqueous silver nitrate solution instead of an aqueous solution of palladium chloride and changed the atmosphere of the heat treatment with air to hydrogen.

Based on the results of powder x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS), it was confirmed that the Nickel is reduced to the metallic state, and it was confirmed that the formed alloy of Nickel and silver.

The reactions is carried out in the same way, as in (2) of example 1, using this catalyst. As a result, the degree of conversion of methacrolein was 1.5% and the selectivity of the formation of methyl methacrylate (MMA) was 5.1%.

Table 1 presents the physical properties and the results of the reaction for catalysts used to produce complex ether carboxylic acids of examples 1-3, reference example 4 and comparative examples 1-3.

Table 1
No.Applied composite nanoparticlesThe amount deposited Ni and X (wt.%)The atomic ratio of Ni/(Ni + X) (mol.%)The results of the reaction
NiXThe degree of conversion (%)The selectivity of the formation of MMA (%)
Example 1NiOPd/Al2O31,50,50,8418,274,5
Example 2NiOAg/Al2O3 1,61,30,696,255,1
Example 3NiOAu/Al2O31,40,40,9222,492,4
Reference example 4NiO/Al2O31,50-3,135,2
Comparative example 1Pd/Al2O300,5-10,352,4
Comparative example 2Ag/Al2O301,5-2,1to 25.3
Comparative example 3NiAg/Al2O31,51,4-1,5 5,1

Example 4

The magnesium compound was applied to a commercially available silica (CARiACT Q-15, Fuji Silysia Chemical, Ltd.) impregnation in a hot water bath using an aqueous solution containing magnesium acetate. Then, the resulting impregnated product was dried for 12 hours at 120°C, and then annealed in air for 6 hours at 600°C. In the received media based on a system of silicon oxide-magnesium oxide (SiO2-MgO), which contained 5 wt.% magnesium oxide per Mg.

Then 100 ml of an aqueous solution containing a specified amount of an aqueous solution of Nickel nitrate and an aqueous solution soloconsolidation acid, was heated at 80°C. 30 g of the carrier on the basis of the silicon oxide-magnesium oxide, obtained above, was added to this solution, after which withstood the mixture under stirring for one hour, precipitating thereby, the components of Nickel and gold on the media. Then this mixture was given quietly to settle and removing the supernatant, and then washed with distilled water until until Cl ions was no longer detected. After that, the mixture was filtered, dried for 16 hours at 105°C and annealed for 3 hours in air at 500°C, obtaining a catalyst coated with 1.0 wt.% Nickel and 0.8 wt.% gold (NiOAu/SiO2-MgO). The atomic ratio of Ni/(Ni + Au) obtained in katal is the jam was 0.81.

In accordance with the results of powder x-ray diffraction (XRD) of the catalyst described above was observed broad diffraction peak characteristic of gold, and the calculations of the average crystallite size based on the distribution of the line width of the diffraction peak from the plane of the Au (111) gave a value of 3 nm. On the other hand, since there were no diffraction pattern caused by Nickel, it was assumed that Nickel is present in the amorphous phase. Regarding the chemical state of Nickel was confirmed by the valence equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS).

The microstructure of the above catalyst was observed using a transmission electron microscope (TEM/STEM). As shown in figure 1, spherical particles with a particle diameter of 2 to 3 nm is uniformly deposited on the surface of the media. Srednesemennyh the particle diameter of the nanoparticles was 3.0 nm (number of nanoparticles used for calculation: 100). The nanoparticles was observed with further increase of the images (figure 2), to obtain data on the structure of the lattice. In accordance with the results of the analysis with the Fourier transform plane of the lattice, corresponding to the lattice period for Au (200) (d = 2,039 Å), intersect at an angle of 90°, respectively, indicating that this picture is the m lattice Au (200). Thus, the nanoparticles contain crystalline gold. The structure of the lattice, corresponding to the period lattice Au (200) and Au (111)was also observed in other particles.

Further, analysis of the composition points using STEM-EDS for each of the nanoparticles showed that Nickel and gold were found in each particle. The average value of the ratio of atoms of Nickel and gold nanoparticles (nanoparticles used for calculation: 50) was 0.82. Only trace amounts of Nickel were detected at the analysis points out the nanoparticles. Moreover, the analysis of nanoplasma observed particles (figure 3) atomic ratio of Ni/Au in the center of the particle (measurement point 1) was 0.73, while its value at the edge of the particles (measuring point 2) was $ 2,95. Only trace amounts of Nickel have been identified in other parts of the particles (measuring point 3). As a result of performing such measurements 20 times the Nickel in larger quantities was discovered on the edges of all particles. The observed distribution of Nickel and gold is almost entirely consistent with the data obtained on the basis of the results of the elemental mapping EDS. In addition, in accordance with a linear composition profiles (figure 4), Nickel was allocated in such a way that its distribution profile was surrounded by the profile of the distribution of gold in all directions, scanning (1, 2). In affect, the, since Nickel is distributed over gold, and Nickel is determined in large quantities along the edges of the particles, the nanoparticles contained in the above catalyst, are considered as having a form in which the surface of gold nanoparticles coated with Nickel.

Figure 5 shows the absorption spectra of the catalyst particles NiOAu/SiO2MgO is obtained with the use of spectroscopy in the UV and visible part of the spectrum (UV-Vis). Sample Au/SiO2MgO has the gold nanoparticles deposited on the same carrier (catalyst obtained in comparative example 4 described later), and absorption of surface plasmons due to gold nanoparticles, is shown near 530 nm. Sample NiO/SiO2-MgO catalyst obtained in reference example 5, described later) and the sample NiO2/SiO2-MgO (synthesized by oxidative treatment of the sample obtained in reference example 5, using hypochlorous acid) are fine particles of NiO and NiO2printed on the same media, and a wide area of the absorption over the wavelength interval from 200 to 800 nm, observed for NiO2/SiO2MgO was not observed for NiO/SiO2-MgO. This result means that a wide area of the absorption over the wavelength interval from 200 to 800 nm is evident in the case of this highly oxidised Nickel oxide (NiO2). In ioproject this, the absorption of surface plasmons of gold near 530 nm is not seen in the case NiOAu/SiO2-MgO, and a wide area of the absorption characteristic of NiO2observed over the range of wavelengths from 200 to 800 nm.

On the basis of these results suggest that the catalysts NiOAu/SiO2-MgO have a form in which the gold atoms are not present on their surface, and, most likely, the surface of gold nanoparticles covered with this highly oxidised Nickel oxide.

0.3 g of the catalyst obtained above, 1.0 g of methacrolein and 10 ml of methanol were loaded into the reaction vessel in the form of a high pressure autoclave (total volume: 120 ml)made of SUS316 and equipped with a magnetic stirrer, and the autoclave was closed and the atmosphere inside the system was replaced with nitrogen gas, the gas mixture-based nitrogen containing 7 vol.% oxygen was injected into the headspace site, and the pressure inside the system was increased to 5.0 MPa.

Then the reaction vessel was placed in an oil bath and the reaction was conducted for 2 hours at the reaction temperature of 60°C and under stirring. After cooling down the residual pressure and opening the autoclave, after which the catalyst was filtered and the filtrate analyzed by gas chromatography.

As a result, the degree of conversion of methacrolein was $ 61.3% and selectivity clicks the education of methyl methacrylate was 95.7 per cent.

Reference example 5

The catalyst coated with Nickel in the amount of 1.0 wt.% (Ni/SiO2-MgO) was obtained in the same manner as in example 4, except that he had not added an aqueous solution soloconsolidation acid.

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein was 3.2% and the selectivity of the formation of methyl methacrylate was 30.1 per cent.

Comparative example 4

The catalyst coated with gold in an amount of 0.9 wt.% (Au/SiO2-MgO) was obtained in the same manner as in example 4, except that no added nitrate Nickel. The average crystallite size calculated according to the powder x-ray diffraction (XRD)was 3 nm.

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein accounted for 9.7% and the selectivity of the formation of methyl methacrylate was 75,0%.

Comparative example 5

The catalyst coated with 1.0 wt.% Nickel and 0.8 wt.% gold (NiAu/SiO2-MgO) was obtained in the same manner as in example 4, except that changed the atmosphere of the heat treatment with air to hydrogen. In accordance with the results of x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) for this is utilizator Nickel was restored to its metallic state and was confirmed that is formed of an alloy of Nickel and gold.

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein amounted to 11.3% and the selectivity of the formation of methyl methacrylate was 62.4 per cent.

Comparative example 6

The catalyst coated with 1.1 wt.% iron and 0.9 wt.% gold (Fe2O3Au/SiO2-MgO) was obtained in the same manner as in example 4 except for the use of nitrate of iron instead of Nickel nitrate. The atomic ratio Fe/(Fe + Au) in the obtained catalyst was 0.81.

In accordance with the results of spectrometry in the UV and visible region (UV-Vis) for this catalyst was observed absorption of surface plasmons due to gold nanoparticles (about 530 nm).

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein was 10.4% and the selectivity of the formation of methyl methacrylate was 55.2 per cent.

Comparative example 7

The catalyst coated with 1.2 wt.% cobalt and 0.8 wt.% gold (Co3O4Au/SiO2-MgO) was obtained in the same manner as in example 4 except for the use of nitrate of cobalt instead of Nickel nitrate. The atomic ratio of Co/(Co + Au) in the obtained catalyst was 0,83.

In accordance with resultsetmetadata in the UV and visible region (UV-Vis) for this catalyst was observed absorption of surface plasmons, due to the gold nanoparticles (about 530 nm).

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein was 2.6% and the selectivity of the formation of methyl methacrylate was 45.8 per cent.

Comparative example 8

The catalyst coated with 1.0 wt.% copper and 0.8 wt.% gold (CuOAu/SiO2-MgO) was obtained in the same manner as in example 4 except for the use of nitrate of copper instead of Nickel nitrate. The atomic ratio Cu/(Cu + Au) in the obtained catalyst was 0,79.

In accordance with the results of spectrometry in the UV and visible region (UV-Vis) for this catalyst was observed absorption of surface plasmons due to gold nanoparticles (about 530 nm).

The reaction was conducted in the same manner as in example 4, using this catalyst. As a result, the degree of conversion of methacrolein was 9.2% and the selectivity of the formation of methyl methacrylate was 58.1%.

Table 2 lists the physical properties and the results of the reaction for catalysts used to produce complex ether carboxylic acid of example 4 reference example 5 and comparative examples 4-8.

Table 2
No.Applied composite nanoparticlesThe amount deposited Ni and Au (wt.%)The atomic ratio of Ni/(Ni + Au) (mol. %)The results of the reaction
NiAuThe degree of conversion (%)The selectivity of the formation of MMA (%)
Example 4NiOAu/SiO2-MgO1,00,80,8161,395,7
Reference example 5NiO/SiO2-MgO1,001,003,230,1
Comparative example 4Au/SiO2-MgO00,9-the 9.775,0
Comparative example 5NiAu/SiO2-MgO1,00,8 0,8111,362,4
Comparative example 6Fe2O3Au/SiO2-MgO1,11)0,90,814)10,455,2
Comparative example 7Co3O4Au/SiO2-MgO1,22)0,80,835)2,645,8
Comparative example 8CuOAu/SiO2-MgO1,03)0,80,796)9,2to 58.1
1)the applied amount of Fe2)the applied amount of Co3)the applied amount of Cu,
4)the atomic ratio Fe/(Fe + Au),5)the atomic ratio of Co/(Co + Au),6)the atomic ratio Cu/(Cu + Au)

Examples 5-10, reference example 6, comparative example 9

2 kg Zola silica (Snowtex N-30 manufactured by Nissan Chemical Industries, Ltd. (the content of SiO2: 30 wt.%)) add the Yali to 128 g Zola titanium dioxide (STS-018 production Ishihara Techno Co., Ltd. (the content of TiO2: 30 wt.%)) and mixed, and then kept in suspension for 24 hours at 15°C and dried by a spray device to spray drying with an installed outlet gas temperature of 130°C, obtaining a solid material.

Then received media based on a system of silicon oxide-titanium dioxide by calcination for 2 hours in air at 300°C and then for 3 hours at 600°C. the Ratio of the silicon oxide/titanium dioxide calculated on the oxide was 93.6/6,0. Specific surface area with her determination by adsorption of nitrogen was 236 m2/g and the pore volume was 0.26 ml/g Average particle diameter of the carrier was 60 μm in accordance with the results obtained by particle size analyzer by laser diffraction radiation. In addition, the form of the medium was determined as close to spherical on the basis of visual studies using scanning electron microscope (SEM).

Then 30 g of the carrier on the basis of the silicon oxide-titanium dioxide, obtained as described above was added to a glass container containing 100 ml of distilled water, then stirring at 90°C, was added dropwise in the specified quantities of an aqueous solution of Nickel nitrate and an aqueous solution soloconsolidation acid, brought the pH of the aqueous solution to 7 by the addition of 0.5 N. vodno the solution of sodium hydroxide and continued the stirring for 1 hour. After this aqueous solution was given quietly to settle and removing the supernatant, then washed the precipitate with distilled water up until Cl ions was no longer found, were dried for 16 hours at 105°C and annealed for 3 hours at 400°C in air, obtaining a catalyst in which the atomic ratio of Ni/(Ni + Au) was changed in the range from 0 to 1.0 (despite the fact that the total amount of Nickel and gold remained constant), and then reaction was performed in the same manner as in example 4. Table 3 presents the physical properties of the obtained catalysts, along with the activity of formation of methyl methacrylate (MMA) per unit molar amount of Nickel and gold (mol MMA/h/mol Ni+Au).

Table 3
No.Applied composite nanoparticlesThe amount deposited Ni and Au (wt.%)The atomic ratio of Ni/(Ni + Au) (mol. %)The activity of formation of MMA (mol MMA/h/mol Ni+Au)
NiAu
Example 5NiOAu/SiO2-TiO21,2 0,40,9125,2
Example 6NiOAu/SiO2-TiO21,10,70,8341,3
Example 7NiOAu/SiO2-TiO20,91,30,7063,5
Example 8NiOAu/SiO2-TiO20,81,70,6152,1
Example 9NiOAu/SiO2-TiO20,72,10,5343,7
Example 10NiOAu/SiO2-TiO20,33,50,2214,0
Reference example 6NiO/SiO2-TiO21,301,00Comparative example 9Au/SiO2-TiO204,308,3

Example 11

The reaction of formation of methyl acrylate was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in example 4 (NiOAu/SiO2-MgO), and participation in the reaction of acrolein instead of methacrolein.

As a result, the degree of conversion of acrolein was 71,3% and the selectivity of the formation of methyl acrylate was 96.8 per cent.

Example 12

Reaction formation acrylate was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in example 4 (NiOAu/SiO2-MgO), participation in the reaction of acrolein instead of methacrolein and participation in the reaction of ethanol instead of methanol.

As a result, the degree of conversion of acrolein was 81.5% and the selectivity of the formation of ethyl acrylate was 96.2%.

Example 13

Reaction formation ethylbenzoic was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in example 4 (NiOAu/SiO2 -MgO), participation in the reaction of benzaldehyde instead of methacrolein and participation in the reaction of ethanol instead of methanol.

As a result, the degree of conversion of benzaldehyde was 88,2% and the selectivity of the formation of ethylbenzoic was 98.2%.

Example 14

The reaction of formation of methyl methacrylate was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in example 4 (NiOAu/SiO2-MgO), and participation in the reaction metallolomnogo alcohol instead of methacrolein.

As a result, the degree of conversion metallolomnogo alcohol was 59.2% and the selectivity of the formation of methyl acrylate was 94,1%.

Example 15

The reaction of formation of ethyl acetate was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in example 4 (NiOAu/SiO2-MgO), participation in the reaction of ethanol instead of methacrolein and methanol and the reaction at a temperature of 80°C.

As a result, the degree of conversion of ethanol was 30.4% and the selectivity of the formation of ethyl acetate was $ 91.2%.

Example 16

The reaction of formation of methylglucose was performed using the same methodology and the same reaction conditions as in example 4 except for using the catalyst obtained in p is the emer 4 (NiOAu/SiO 2-MgO), and participation in the reaction of ethylene glycol instead of methacrolein.

As a result, the degree of conversion of ethylene glycol was $ 42.4% and the selectivity of the formation of methylglucose was 90.5 per cent.

Example 17

(1)Preparation of media

An aqueous solution in which 4,16 kg nonahydrate of aluminium nitrate and 540 g of 60%nitric acid was dissolved in 5.0 l of pure water was gradually filed under stirring 20,0 kg of a solution or Sol of silica with colloidal particles with a diameter from 10 to 20 nm, supported at 15°C (Snowtex N-30 manufactured by Nissan Chemical Industries, Ltd. (the content of SiO2: 30 wt%)), receiving a mixed suspension or Sol of silicon oxide and aluminum nitrate. Thereafter, the mixed slurry was subjected to aging by maintaining at 50°C for 24 hours. After cooling to room temperature, the mixed slurry was dried by a spray device to spray drying with an installed outlet gas temperature of 130°C, obtaining a solid material.

Then the obtained solid material was placed a layer thickness of about 1 cm in stainless steel container with an open top, after which it was heated in an electric furnace from room temperature to 300°C for 2 hours and then kept at this temperature for 3 hours. After additional heating to 600°C for 2 hours with the consequences of the current maintaining at this temperature for 3 hours solid material is gradually cooled, receiving a media system based on silica-alumina. The amount of aluminum in the resulting medium was 10 mol.% in the calculation of the total molar amount of silicon and aluminum. Specific surface area, determined by adsorption of nitrogen, was 145 m2/g, pore volume amounted to 0.27 ml/g, and average pore diameter was 8 nm. The average particle diameter of the carrier, in accordance with the measurement results of the particle size analyzer by laser diffraction radiation was 62 μm. In addition, it was found that the form of the medium is close to spherical, on the basis of visual studies with a scanning electron microscope (SEM).

(2)Obtaining catalyst

1.0 l of a solution containing 22,30 g of uranyl nitrate Nickel and 20 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/l, was heated to 80°C. 300 g of the carrier system based on silica-alumina, obtained above, was placed in this aqueous solution, after which brought the pH of the aqueous solution to 7 by the addition of 0.5 N. aqueous sodium hydroxide solution, while maintaining at 80°C with stirring and continued stirring for 1 hour, precipitating components of Nickel and gold on the media.

Then, after keeping calm, removing the supernatant and washed the precipitate several times distillirovanna the th water the liquid was filtered. After drying of the filtrate for 16 hours at 105°C the product was annealed for 5 hours at 450°C in air, receiving the catalyst coated 1,43 wt.% Nickel and 1.45 wt.% gold (NiOAu/SiO2-Al2O3). The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,768, and the atomic ratio of Ni/Al was 0,144. Specific surface area, as determined by adsorption of nitrogen, was 150 m2/g, pore volume was estimated at 0.28 ml/g, and average pore diameter was 8 nm. The average diameter of the catalyst particles, in accordance with the measurement results of the particle size analyzer by laser diffraction radiation was 61 μm. In addition, it was found that the shape of the catalyst is close to spherical, on the basis of visual studies with a scanning electron microscope (SEM).

Based on the results of powder x-ray diffraction (XRD) the XRD pattern corresponding to the Nickel was not observed, and it was confirmed that the Nickel is present in an amorphous state. On the other hand, although he could not be defined as a distinct peak, was attended by a broad peak corresponding to the gold crystals. Although the magnitude of this peak was close to the detection limit of the powder x-ray diffraction (2 nm), the calculations of the average crystallite size using the formula W is RERA gave a value of about 3 nm.

Regarding the chemical state of Ni was confirmed by the valence equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS). Moreover, the chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,458, and the chemical shift (ΔE) was 0,331. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Visual examination of the enlarged images of the nanoparticles showed that the nanoparticles had the structure of the lattice, corresponding to the period lattice Au (111). Analysis of the composition in precisely the Ah by STEM-EDS for each nanoparticles confirmed the Nickel and gold contained in each particle. The average value of the ratio of atoms of Nickel and gold composite nanoparticles (nanoparticles used for calculation: 50) was made 0.83. Moreover, the analysis of nanoplasma observed particles of Nickel was distributed over gold in all the particles, and Nickel in larger quantities was discovered on the edges of all particles.

Further, in the study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed near 530 nm, while there was wide scope absorption characteristic of NiO2over the range of wavelengths from 200 to 800 nm.

Based on these results, it was established that the nanoparticles contained in the catalyst in accordance with this embodiment, take the form, in which the surface of gold nanoparticles coated with Nickel, and have a surface electronic state different from the state for the gold nanoparticles containing a single metal component.

(3)Synthesis of ester carboxylic acid

200 g of the catalyst (NiOAu/SiO2-Al2O3), obtained above, was loaded into the reaction vessel with stirring, made the military stainless steel with liquid-phase site 1.2 liters and equipped with a cage catalyst. The oxidation reaction of the formation of ester of carboxylic acid is then carried out using an aldehyde and alcohol, or one or more types of alcohols, stirring the contents of the reaction vessel at a rate of end plate 4 m/C. a Solution of 36.7 wt.% methacrolein in methanol is continuously fed into the reaction vessel at a flow rate of 0.6 l/h, along with a continuous flow of a solution of 1-4 wt.% NaOH in methanol at a flow rate of 0.06 l/h, breathed air so that the reaction temperature was 80°C and oxygen concentration at the outlet when the pressure of the reaction of 0.5 MPa was equal to 4.0 vol.% (which is equivalent to the partial oxygen pressure of 0.02 MPa), and the concentration of NaOH is supplied to the reaction tank was regulated so that the pH value of the reaction system was 7. The reaction product was continuously removed from the outlet of the reaction tank overflow, and reactivity was investigated by analysing by gas chromatography.

After 200 hours after the start of the reaction, the conversion rate of methacrolein was 61.5%, the selectivity of the formation of methyl methacrylate was a 94.6%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 7,60 mol/h/kg of catalyst. Acciona capacity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein of 61.7%, the selectivity of the formation of methyl methacrylate in 94.7% and the activity of formation of methyl methacrylate 7,628 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases, thus confirming that suppressed peeling and leaching of Ni and Au, which are active components of the catalyst, as well as the leaching of Si, which is a component of the carrier. When the catalyst was recovered after reaction for 500 hours and explored the scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, the pore volume of the catalyst, as determined by adsorption of nitrogen was estimated at 0.28 ml/g, and average pore diameter was 8 nm.

Next, a visual examination of the catalyst after the reaction using a transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,0 nm). Analysis of the composition points using STEM-EDS for each of the nanoparticles was confirmed that the Nickel and gold is uderjalis in each nanoparticle. The average value of the ratio of atoms of Nickel and gold composite nanoparticles (nanoparticles used for calculation: 50) was 0.85. In addition, when analyzing nanoplasma observed particles of Nickel was distributed over gold in all the particles, and Nickel in larger quantities was discovered on the edges of all particles. In addition, in the study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed near 530 nm.

Based on these results, it was confirmed that the physical properties of the catalyst and the structure of the nanoparticles in this variant implementation did not change after the reaction compared to the initial state.

Example 18

The media system based on silica-alumina having a specific surface area of 110 m2/g, was obtained in accordance with the same method as in (1) of example 17, except that the aluminum nitrate was added so that the amount of aluminum was 15 mol.% in the calculation of the total molar amount of silicon and aluminum, and has established a firing temperature of 700°C.

Then got the catalyst in the same manner as in (2) of example 17 except for the use the of the above media and the use of 4.46 g of uranyl nitrate Nickel.

The amount deposited Nickel and gold in the obtained catalyst was 0.25 wt.% and 1.43 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,370, and the atomic ratio of Ni/Al was 0,017.

In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average size of the crystallite calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,452, and the chemical shift (ΔE) was 0,341. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual studies is the W form the active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX) and confirmed the presence of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 0.81.

In addition, in the study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction within 200 hours accounted for 58.4%, the selectivity of the formation of methyl methacrylate stood at 94.7%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 7,220 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 58,6%, the selectivity of the formation of methyl methacrylate was 94.9% and the activity of the OBR is tion of methyl methacrylate 7,260 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and explored the scanning electron microscope (SEM), it was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.4 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 19

300 g of commercially available silica (CARiACT Q-10, Fuji Silysia Chemical, Ltd.) added to a glass container containing 500 ml of distilled water, and then was gradually added to a solution of silica gel to 98.5 g of nonahydrate of aluminium nitrate as a source of aluminum, dissolved in a solution of silica gel and evaporated by drying on a hot water bath.

The obtained solid material was placed a layer thickness of about 1 cm in stainless steel container with an open top, after which it was heated in an electric is Oh furnace from room temperature to 300°C for 2 hours and then kept at this temperature for 3 hours. After additional heating to 600°C for 2 hours, followed by keeping at this temperature for 3 hours solid material is gradually cooled, receiving a media system based on silica-alumina. The amount of aluminum in the resulting carrier was 5 mol.% in the calculation of the total molar amount of silicon and aluminum. Specific surface area, as determined by adsorption of nitrogen, was 183 m2/year

Then got the catalyst in the same manner as in (2) of example 17, except for using the above media and the use of uranyl nitrate Nickel in the amount of 66,89,

The amount deposited Nickel and gold in the obtained catalyst was 4.50 wt.% and 1.44 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,913, and the atomic ratio of Ni/Al was 0,914.

Based on the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average size of the crystallite calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent what icely, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,403, and the chemical shift (ΔE) was 0,336. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 2,9 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the presence of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 0.85.

In addition, according to a study of the changes in the electronic excited state of this catalysis is a torus with spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 57.6%, selectivity of the formation of methyl methacrylate was 93.6%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 7,038 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 57.1%, and the selectivity of the formation of methyl methacrylate 93,8% and the activity of formation of methyl methacrylate 6,992 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), it was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter whom ozanich nanoparticles, as determined using transmission electron microscope (TEM), was 3.1 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 20

Commercially available compound silicon oxide-aluminum oxide (N631HN production of Nikki Chemical Co., Ltd., the amount of alumina based on the total molar amount of silicon and aluminum: 30 mol.%)) put a layer thickness of about 1 cm in stainless steel container with an open top, after which it was heated in an electric furnace from room temperature to 300°C for 2 hours and then kept at this temperature for 3 hours. After additional heating to 800°C for 2 hours, followed by keeping at this temperature for 3 hours solid material is gradually cooled, receiving the target substance. Specific surface area, as determined by adsorption of nitrogen, was $ 348 m2/year

Then got the catalyst in the same manner as in (2) of example 17, except for using the above media. The amount deposited Nickel and gold in the resulting catalyst comprised of 1.40 wt.% and of 1.42 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,768, and the atomic ratio of Ni/Al was 0,046.

On the results there of powder x-ray diffraction (XRD) was attended by a broad peak, suitable crystals of gold. The average size of the crystallite calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,492, and the chemical shift (ΔE) was 0,329. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,0 nm). Elemental analysis (20 points) was performed for each enabledevice nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and it was confirmed the presence of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 0,80.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17 except for the use of this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 60,4%, the selectivity of the formation of methyl methacrylate was 94.3%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 7,436 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 61,0%, the selectivity of the formation of methyl methacrylate was 94.2% and the activity of formation of methyl methacrylate 7,501 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and Kon is entrace Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 21

An aqueous solution in which 4.86 kg of nonahydrate of aluminium nitrate and 1.53 kg of rubidium nitrate was dissolved in 5.0 l of pure water was gradually filed under stirring 20,0 kg of a solution or Sol of silica with colloidal particles with a diameter from 10 to 20 nm, supported at 15°C (TX11561 production Nalco Co., Ltd. (the content of SiO2: 30 wt%)), obtaining a mixed suspension or Sol of silicon oxide, aluminum nitrate and rubidium nitrate. Then the mixed suspension was subjected to aging by keeping at room temperature for 24 hours. Then, the mixed slurry was dried by a spray device to spray drying with an installed outlet gas temperature of 130°C, obtaining a solid material. The obtained solid material was placed a layer thickness of about 1 cm in the containers is R stainless steel open top, then was heated in an electric furnace from room temperature to 400°C for 2 hours and then kept at this temperature for 3 hours. After additional heating to 580°C for 2 hours, followed by keeping at this temperature for 3 hours solid material is gradually cooled, receiving a media system based on a silicon oxide-aluminum oxide-rubidium. The amount of aluminum was 11.5 mol.% in the calculation of the total molar amount of silicon and aluminum, and the atomic ratio of (alkali metal + 1/2 × alkaline earth metal + 1/3 × rare earth metal)/Al was $ 0,80. Specific surface area, as determined by adsorption of nitrogen, was 127 m2/the Average particle diameter of the carrier, according to the measurement results of the particle size analyzer by laser diffraction radiation was 64 μm. In addition, it was found that the form of the medium is close to spherical, on the basis of visual studies with a scanning electron microscope (SEM).

Next, 1.0 l of a solution containing 14.9 g of uranyl nitrate Nickel and 13 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/l, was heated to 90°C. 300 g of the carrier on the basis of the silicon oxide-aluminum oxide-RB, obtained above, was placed in this aqueous solution and then kept the ri 90°C and under stirring, stirring was continued for 1 hour, precipitating components of Nickel and gold on the media.

Then, after keeping calm, removing the supernatant and washed the precipitate several times with distilled water, the liquid was filtered. After drying of the filtrate for 16 hours at 105°C the product was annealed for 3 hours at 500°C in air, receiving the catalyst coated to 0.97 wt.% Nickel and 0.95 wt.% gold (NiOAu/SiO2-Al2O3-Rb2O). The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,774, and the atomic ratio of Ni/Al was 0.11, while the atomic ratio of Ni/Rb was 0,137. According to the results of powder x-ray diffraction (XRD) the XRD pattern corresponding to the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. Attended peak, while broad, as described above, corresponding to the gold crystals, and the average crystallite size was 3.0 nm.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα-SP is ktrah. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,432, and the chemical shift (ΔE) was 0,345. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 2,8 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and it was confirmed that the Nickel and gold contained in all the particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 1.02.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except e is th catalyst and the use amount of the catalyst 240, As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 55.3%, the selectivity of the formation of methyl methacrylate was 95,1%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 5,721 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 54,9%, the selectivity of the formation of methyl methacrylate to 95.3% and the activity of formation of methyl methacrylate 5,692 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to p is ronically state.

Example 22

The media system based on a silicon oxide-aluminum oxide-strontium was obtained in the same manner as in example 21, except that used 2.90 kg of strontium nitrate instead of rubidium nitrate. The amount of aluminum was 11.5 mol.% in the calculation of the total molar amount of silicon and aluminum, and the atomic ratio of (alkali metal + 1/2 × alkaline earth metal + 1/3 × rare earth metal)/Al was $ 0.53 per share. Specific surface area, as determined by adsorption of nitrogen, was 138 m2/the Average particle diameter of the carrier, in accordance with the measurement results of the particle size analyzer by laser diffraction radiation was 62 μm. In addition, it was found that the form of the medium is close to spherical, on the basis of visual studies with a scanning electron microscope (SEM).

Then got the catalyst coated 3,98 wt.% Nickel and 0.97 wt.% gold (NiOAu/SiO2-Al2O3-SrO) in the same manner as in example 21, except that used as mentioned above, the media, and the number of uranyl nitrate Nickel was 59,46,

The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,932, and the atomic ratio of Ni/Al was 0,421, while the atomic ratio of Ni/Sr was 0,398.

Based on the results of powder d is chenovsky diffraction (XRD) was attended by a broad peak, suitable crystals of gold. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,464, and the chemical shift (ΔE) was 0,339. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,0 nm). Elemental analysis (20 points) was performed for each of the nab is udasina nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 1.1.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except that used this catalyst, and the amount of catalyst was 240, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 52,5%, the selectivity of the formation of methyl methacrylate was 95,0%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 5,426 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 52,8%, the selectivity of the formation of methyl methacrylate was 94.9% and the activity of formation of methyl methacrylate 5,451 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au is left of 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 23

The media system based on a silicon oxide-aluminum oxide-magnesium-lanthanum was obtained in the same manner as in example 21, except that used nonahydrate of aluminium nitrate in the amount of 1.88 kg and added 3.5 kg of magnesium nitrate and 1.0 kg of hydrate chloride instead of lanthanum nitrate rubidium. The amount of aluminum was 4.8 mol.% in the calculation of the total molar amount of silicon and aluminum, and the atomic ratio of (alkali metal + 1/2 alkaline earth metal + 1/3 alkaline earth metal)/Al was $ 1,514. Specific surface area, as determined by adsorption of nitrogen, was 115 m2/the Average particle diameter of the carrier, in accordance with the measurement results analyzer R is smera particle diffraction of laser radiation, was 62 μm. In addition, it was found that the form of the medium is close to spherical, on the basis of visual studies using scanning electron microscope (SEM).

Then got the catalyst in the same manner as in example 21, except for using the above media and the use of uranyl nitrate Nickel in the amount of 4.46,

The applied amount of Nickel and gold in the obtained catalyst was 0.25 wt.% and of 1.02 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,451, and the atomic ratio of Ni/Al was 0,064, while the atomic ratio of Ni/(Mg + La) was 0,061.

In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical condition is Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,493, and the chemical shift (ΔE) was 0,335. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 1,09.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

Reaction etc who drove the same way as in (3) of example 17, except that the catalyst and the amount of used catalyst 240, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 53,6%, the selectivity of the formation of methyl methacrylate 95,3%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 5,557 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 53,3%, the selectivity of the formation of methyl methacrylate 95.2% and the activity of formation of methyl methacrylate 5,520 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM, was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Table 4 presents the physical properties of catalysts for production of esters of carboxylic acids of examples 17-23.

Table 4
No.CatalystThe compositions of silicon oxide and aluminum oxide (mol. %)The applied amount of Ni and Au (wt.%)The ratio of the constituent elements of the catalyst (atomic ratio)
SiAlNiAuNi/(Ni+Au)Ni/AlNi/base metal
Example 17NiOAu/SiO2-Al2O390,010,01,431,450,7680,144-
Example 18 NiOAu/SiO2-Al2O385,015,00,251,430,3700,017-
Example 19NiOAu/SiO2-Al2O395,05,04,50the 1.440,9130,914-
Example 20NiOAu/SiO2-Al2O370,030,01,401,420,7680,046-
Example 21NiOAu/SiO2-Al2O3-Rb2O88,511,50,970,950,7740,1100,137
Example 22NiOAu/SiO2-Al2O3-SrO88,5 11,53,980,970,9320,4210,398
Example 23NiOAu/SiO2-Al2O3-MgO-La2O3for 95.24,80,251,020,4510,0640,061

Example 24

Reaction formation acrylate was performed using the same methodology and the same reaction conditions as in (3) of example 17, except for using the catalyst obtained in (2) of example 17 (NiOAu/SiO2-Al2O3), participation in the reaction of acrolein instead of methacrolein and participation in the reaction of ethanol instead of methanol.

As a result, the degree of conversion of acrolein after completion of the reaction for 200 hours was 71.2 percent, the selectivity of the formation of ethyl acrylate were 96.2%, and the activity of formation of acrylate per unit mass of catalyst was 8,942 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of acrolein 71,5%, the selectivity of the formation of acrylate 96,1% and the asset is ity education acrylate 8,970 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.4 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 25

(1)Getting media

An aqueous solution in which 3,75 kg nonahydrate of aluminium nitrate, 2,56 kg of magnesium nitrate and 540 g of 60%nitric acid was dissolved in 5.0 l of pure water was gradually filed under stirring 20,0 kg of a solution or Sol of silica with colloidal particles with a diameter from 10 to 20 nm, supported at 15°C (Snowtex N-30 manufactured by Nissan Chemical Industries, Ltd. (the content of SiO2: 30 wt%)), receiving a mixed suspension or Sol of silicon oxide, aluminum nitrate and magnesium nitrate. After this mixed WM is enzio was subjected to aging by maintaining at 50°C for 24 hours. After cooling to room temperature, the mixed slurry was dried by a spray device to spray drying with an installed outlet gas temperature of 130°C, obtaining a solid material.

The obtained solid material was placed a layer thickness of about 1 cm in stainless steel container with an open top, after which it was heated in an electric furnace from room temperature to 300°C for 2 hours and then kept at this temperature for 3 hours. After additional heating to 600°C for 2 hours, followed by keeping at this temperature for 3 hours solid material is gradually cooled, receiving media. The amount of silicon, aluminum and magnesium in the resulting media was 83,3 mol.%, of 8.3 mol.% and 8.3 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium. Specific surface area, as determined by adsorption of nitrogen, was 148 m2/g, the pore volume was 0.26 ml/g, and average pore diameter was 8 nm. The average particle diameter of the carrier, in accordance with the measurement results of the particle size analyzer by laser diffraction radiation was 64 μm. In addition, it was found that the form of the medium is close to spherical, on the basis of visual studies using scanning electroneg the microscope (SEM).

(2)Obtaining catalyst

1.0 l of a solution containing 23,78 g of uranyl nitrate Nickel and 19 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/l, was heated to 90°C. 300 g of the carrier on the basis of the silicon oxide-aluminum oxide-magnesium oxide obtained above was placed in this aqueous solution and kept at 90°C and under stirring, and then stirring was continued for 1 hour, precipitating components of Nickel and gold on the media.

Then, after keeping calm, removing the supernatant and washed the precipitate several times with distilled water, the liquid was filtered. After drying of the filtrate for 16 hours at 105°C the product was annealed for 3 hours at 500°C in air, receiving the catalyst coated of 1.52 wt.% Nickel and 1,49 wt.% gold (NiOAu/SiO2-Al2O3-MgO). The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,774, the atomic ratio of Ni/Al was 0,179, and the atomic ratio of Ni/Mg was 0,179. Specific surface area, as determined by adsorption of nitrogen, was 150 m2/g, pore volume was estimated at 0.28 ml/g, and average pore diameter was 5 nm.

The average diameter of the catalyst particles in accordance with the measurement results of the particle size analyzer by laser diffraction radiation was 65 μm. It was found that the shape of the AC is of Aligator close to spherical, on the basis of visual studies with a scanning electron microscope (SEM).

According to the results of powder x-ray diffraction (XRD) the XRD pattern corresponding to the Nickel was not observed, and it was confirmed that the Nickel is present in an amorphous state. On the other hand, although he could not be defined as a distinct peak, was attended by a broad peak corresponding to the gold crystals. Although the magnitude of this peak was close to the detection limit of the powder x-ray diffraction (2 nm), the calculations of the average crystallite size using the sherrer formula gave a value of about 3 nm.

Regarding the chemical state of Ni was confirmed by the valence equal to 2, based on the results of x-ray photoelectron spectroscopy (XPS). Moreover, the chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,489, and the chemical shift (ΔE) was 0,340. Full is Irina at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,0 nm). Visual examination of the enlarged images of the nanoparticles showed that the nanoparticles had the structure of the lattice, corresponding to the period lattice Au (111). Analysis of the composition in points by STEM-EDS for each nanoparticles confirmed that gold and Nickel contained in each of the nanoparticles. The average value of the ratio of atoms of Nickel and gold composite nanoparticles (nanoparticles used for calculation: 50) was 0.85. Moreover, the analysis of nanoplasma observed particles of Nickel was distributed over gold in all the particles, and Nickel in larger quantities was discovered on the edges of all particles.

Further, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed near 530 nm, while there was wide of the absorption region, characteristic of NiO2over the range of wavelengths from 200 to 800 nm.

Based on these results, it was established that the nanoparticles contained in the catalyst in accordance with this embodiment, take the form, in which the surface of gold nanoparticles coated with oxidized Nickel, and have a surface electronic state different from the state for the gold nanoparticles containing a single metal component.

(3)Synthesis of ester carboxylic acid

The reaction was conducted in the same manner as in (3) of example 17, using the catalyst obtained above (NiOAu/SiO2-Al2O3-MgO). As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 65.3%, the selectivity of the formation of methyl methacrylate was 96.1 per cent, and the activity of formation of methyl methacrylate per unit mass of catalyst was 8,192 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein of 65.1%, the selectivity of the formation of methyl methacrylate 96,0% and the activity of formation of methyl methacrylate 8,159 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start is eacli, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases, confirming thereby that was suppressed peeling and leaching of Nickel and gold, which are the active components of the catalyst, as well as the leaching of silicon oxide, which is a component of the carrier. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, the pore volume of the catalyst, as determined by adsorption of nitrogen, was of 0.27 ml/g, and average pore diameter was 5 nm. In addition, visual examination of the catalyst after the reaction using a transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Analysis of the composition in points by STEM-EDS for each of the nanoparticles was confirmed that the Nickel and gold contained in each of the nanoparticles. The average value of the ratio of atoms of Nickel and gold composite nanoparticles (nanoparticles used for calculation: 50) was 0.82. Moreover, the analysis of nanoplasma observed the provided Nickel particles was distributed over gold in all particle and Nickel in larger quantities was discovered on the edges of all particles. In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed near 530 nm.

Based on these results, it was confirmed that the physical properties of the catalyst and the structure of the nanoparticles in this variant implementation did not change after the reaction compared to the initial state.

Example 26

A carrier having a specific surface area of 155 m2/g was obtained in the same manner as in (1) of example 25, except that the added aluminum nitrate and magnesium nitrate to solo of silicon oxide so that the number of aluminum and magnesium contained in the media, 13.6 mol.% and 4.3 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium, and have established a firing temperature of 700°C.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media and the use of uranyl nitrate Nickel in the amount of 3,72,

The applied amount of Nickel and gold in the resulting catalyst comprised of 0.20 wt.% 1.48 wt.%, respectively. Also what about the, the atomic ratio of Ni/(Ni + Au) was 0,312, and the atomic ratio of Ni/Al was of 0.014, while the atomic ratio of Ni/Mg was 0,046. According to the results of powder x-ray diffraction (XRD) the XRD pattern corresponding to the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. Attended peak, while broad, as described above, corresponding to the gold crystals, and the average crystallite size was in accordance with the calculations of 3.0 nm.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,480, and the chemical shift (ΔE) was 0,334. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,3 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX) and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 0,79.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction within 200 hours amounted to 64.4%, the selectivity of the formation of methyl methacrylate was 95,8%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 8,054 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 64,6%, the selectivity of the formation of methyl methacrylate 95.7% and the efficiency of formation of methyl methacrylate 8,071 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.4 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 27

A carrier having a specific surface area of 138 m2/g was obtained in the same manner as in (1) of example 25, except that the added aluminum nitrate and magnesium nitrate to solo of silicon oxide so that the number of aluminum and magnesium contained in the medium was 22.3 mol.% and 5.6 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium, and have established a firing temperature of 800°C.

Then got the catalyst in the same manner as in (2) of example 25, excluded the eating of the use of the above media and the use of uranyl nitrate Nickel in the amount of 77,29,

The applied amount of Nickel and gold in the obtained catalyst was 5.0 wt.% and for 1.49 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,918, and the atomic ratio of Ni/Al was 0,217, while the atomic ratio of Ni/Mg was 0,858.

According to the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was about to 3.0 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,479, and the chemical shift (ΔE) was 0,327. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: about 3.1 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 0,93.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 64.1%, and the selectivity of the formation of methyl methacrylate stood at 95.6%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 8.0 mol/h/kg of catalyst. Reactivity after 500 hours was estimated is on how not changed significantly and provides a degree of conversion of methacrolein 63,9%, the selectivity of the formation of methyl methacrylate 95.7% the activity of formation of methyl methacrylate 7,983 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 28

A carrier having a specific surface area of 123 m2/g was obtained in the same manner as in (1) of example 25, except that the added aluminum nitrate and magnesium nitrate to solo of silicon oxide so that the number of aluminum and magnesium contained in the media, 36.6 mol.% 17.2 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium, which have established a firing temperature of 800°C.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media, the use of uranyl nitrate Nickel in the amount of 16,35 g and using 13 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/L.

The applied amount of Nickel and gold in the obtained catalyst was 1.0 wt.% and 0.90 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,789, and the atomic ratio of Ni/Al was 0.025, while the atomic ratio of Ni/Mg was 0,053.

Based on the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at Polo the ine-height (FWHM) Ni Kα spectrum of the catalyst, as obtained from the measured spectrum was 3,487, and the chemical shift (ΔE) was 0,344. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 2,8 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average) amounted to 1.03.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except that the catalyst and the use amount of the catalyst 240, re is the query result of the conversion degree methacrolein after completion of the reaction for 200 hours was 63.4 per cent, the selectivity of the formation of methyl methacrylate 95,3%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 6,573 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 63,6%, the selectivity of the formation of methyl methacrylate 95,4% and the activity of formation of methyl methacrylate 6,601 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.0 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 29

Sulfuric acid was added to 10 kg of a solution of silicate intothree the No. 3 (SiO 2from 28 to 30 wt.%, Na2O: 9 to 10 wt.%), to bring the pH to 9, and then added Al2(SO4)3to bring the pH to 2. In addition, then add the sodium aluminate to bring the pH to 5-5 .5, and then partially dehydrational getting hydrogel containing about 10 wt.% silicon oxide-aluminum oxide. After spray drying using the device for spray drying at 130°C, the hydrogel was washed as long as the content of Na2O not amounted to 0.02 wt.% and the content of SO4not amounted to 0.5 wt.% or less. Then it was mixed with 300 g of MgO in the form of suspension was subjected to heat treatment for 3 hours at 80°C, filtered and washed, and then dried for 6 hours at 110°C, was heated for 3 hours to 700°C, kept at this temperature for 3 hours and then gradually cooled. The resulting carrier contained 79,1 mol.%, 14,7 mol.% and 6.3 mol.% silicon, aluminum and magnesium, respectively, based on the total molar amount of silicon, aluminum and magnesium. Specific surface area, as determined by adsorption of nitrogen, was 223 m2/the Average particle diameter of the carrier was 60 μm, in accordance with the results obtained by particle size analyzer by laser diffraction radiation. On the basis of visual studies using scanning electron microscopy is a (SEM) was found, what form of media was almost spherical.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media, the use of uranyl nitrate Nickel in the amount of 47,56 g and using 13 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/L.

The applied amount of Nickel and gold in the obtained catalyst amounted to 3.02 wt.% and 0.95 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,914, and the atomic ratio of Ni/Al was 0,202, while the atomic ratio of Ni/Mg was 0,471.

In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin

divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection is, on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,490, and the chemical shift (ΔE) was 0,336. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 2,9 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX) and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 1,12.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, the and with the exception of the use of this catalyst and the use amount of the catalyst 240, As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 66,2%, the selectivity of the formation of methyl methacrylate was 95,8%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 6,899 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 66,1%, the selectivity of the formation of methyl methacrylate 95.9% and the activity of formation of methyl methacrylate 6,896 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.0 nm, showing, thus, the practical absence of any change after the reaction compared to the PE the initial state.

Example 30

A carrier having a specific surface area of 167 m2/g was obtained in the same manner as in (1) of example 25, except that the added nitrate aluminum and magnesium hydroxide to solo of silicon oxide so that the number of aluminum and magnesium contained in the medium was increased by 10.2 mol.% and 7.2 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium, and have established a firing temperature of 600°C.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media, the use of uranyl nitrate Nickel in the amount of 112,97 g and use 38 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/L.

The applied amount of Nickel and gold in the obtained catalyst was 7,50 wt.% and 3,10 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0.89, and the atomic ratio of Ni/Al was 0,724, while the atomic ratio of Ni/Mg was 1.0.

In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 5 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus, Tarida, that Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,487, and the chemical shift (ΔE) was of 0.333. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 4 to 5 nm (srednesemennyh particle diameter: 4,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (cf is dnaa value) amounted to 0.71.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except that the catalyst and the use amount of the catalyst 100, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 63,4%, the selectivity of the formation of methyl methacrylate was accounted for 95.2%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 15,759 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein to 63.2%, the selectivity of the formation of methyl methacrylate was 94.9% and the activity of formation of methyl methacrylate 15,66 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 hours/million or less in both cases, and the concentration of Si was 1 hour/million or less in both cases. When the catalyst was removed after completion of the reaction is over 500 hours and examined using a scanning electron microscope (SEM), it was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 4.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 31

A carrier having a specific surface 134 m2/g was obtained in the same manner as in (1) of example 25, except that the added nitrate aluminum and magnesium hydroxide to solo of silicon oxide so that the number of aluminum and magnesium contained in the media, was 15.1 mol.% and 37.5 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium, and have established a firing temperature of 600°C.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media, the use of uranyl nitrate Nickel in the amount 46,0 g and use 38 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/L.

The applied amount of Nickel and gold in the obtained catalyst was 3.0 wt.% and 2.99 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,771, and the atomic ratio of Ni/Al sostav the lo 0,174, while the atomic ratio of Ni/Mg was 0,07.

In accordance with the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 5 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,478, and the chemical shift (ΔE) was 0,334. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles the maximum distribution of particle diameter of from 4 to 6 nm (srednesemennyh particle diameter: 5,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 0,65.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except that the catalyst and the use amount of the catalyst 100, the degree of conversion of methacrolein after completion of the reaction for 200 hours was $ 61.3%, the selectivity of the formation of methyl methacrylate was 95.4 percent, and the activity of formation of methyl methacrylate per unit mass of catalyst was 15,269 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 61,2%, the selectivity of the formation of methyl methacrylate is 95.6% and the activity of formation of methyl methacrylate 15,276 mol/h/kg of catalyst.

To the ome, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 5.1 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 32

A carrier having a specific surface area of 144 m2/g was obtained in the same manner as in (1) of example 25, except that the added aluminum nitrate and magnesium nitrate to solo of silicon oxide so that the number of aluminum and magnesium contained in the media, was 5.6 mol.% and 4.4 mol.%, accordingly, based on the total molar amount of silicon, aluminum and magnesium.

Then got the catalyst in the same manner as in (2) of example 25, except for using the above media used what I uranyl nitrate Nickel in the amount 5,94 g and 12 ml of an aqueous solution soloconsolidation acid concentration of 1.3 mol/L.

The applied amount of Nickel and gold in the obtained catalyst was to 0.30 wt.% and 0.90 wt.%, respectively. In addition, the atomic ratio of Ni/(Ni + Au) was 0,528, and the atomic ratio of Ni/Al was 0,053, while the atomic ratio of Ni/Mg was 0.069.

According to the results of powder x-ray diffraction (XRD) was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. On the other hand, the diffraction pattern caused by the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,411, and the chemical shift (ΔE) was 0,331. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 2,8 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average) amounted to 1.15.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis), absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, except that the catalyst and the use amount of the catalyst 240, the degree of conversion of methacrolein after completion of the reaction within 200 hours amounted to 62.1%, the selectivity of the formation of methyl methacrylate was accounted for 95.2%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 6,432 mol/who/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of methacrolein 62,3%, the selectivity of the formation of methyl methacrylate 95,1% and the activity of formation of methyl methacrylate 6,445 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.0 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Table 5 presents the physical properties of catalysts for production of esters of carboxylic acids of examples 25-32.

Table 5
No.CatalystThe elemental composition of the medium (mol.%)The applied amount of Ni and Au (wt.%)The ratio of the constituent elements of the catalyst (atomic ratio)
SiAlMgNiAuNi/(Ni+Au)Ni/AlNi/Mg
Example 25NiOAu/SiO2-Al2O3-MgO83,38,38,31,521,490,7740,1790,179
Example 26NiOAu/SiO2-Al2O3-MgO82,013,64,30,201,480,3120,0140,046
Example 27NiOAu/SiO2-Al2 O3-MgO72,022,35,65,001,490,9180,2170,858
Example 28NiOAu/SiO2-Al2O3-MgO46,236,617,21,000,900,7890,0250,053
Example 29NiOAu/SiO2-Al2O3-MgO79,114,76,33,020,950,9140,2020,471
Example 30NiOAu/SiO2-Al2O3-MgO82,610,27,27,503,100,8900,7241,030
Example 31 NiOAu/SiO2-Al2O3-MgO47,415,137,53,002,990,7710,1740,070
Example 32NiOAu/SiO2-Al2O3-MgO90,05,64,40,300,900,5280,0530,069

Example 33

Reaction formation acrylate were performed using the same methodology and the same reaction conditions as in (3) of example 17, except for using the catalyst obtained in example 25 (NiOAu/SiO2-Al2O3-MgO), participation in the reaction of acrolein instead of methacrolein and participation in the reaction of ethanol instead of methanol.

As a result, the degree of conversion of acrolein after completion of the reaction for 200 hours was 75,4%, the selectivity of the formation of acrylate accounted for 97.3%, and the activity of formation of acrylate per unit mass of catalyst was 9,577 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed is I significantly and provides a degree of conversion of acrolein to 75.2%, the selectivity of the formation of acrylate 97.4% and the activity of formation of acrylate 9,562 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.1 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 34

The reaction of formation of methylglucose were performed using the same methodology and the same reaction conditions as in (3) of example 17, except for using the catalyst obtained in example 25 (NiOAu/SiO2-Al2O3-MgO), and participation in the reaction of ethylene glycol instead of methacrolein.

As a result, the degree of conversion of ethylene glycol after completion of the reaction within 200 casasantangelo 52,4%, the selectivity of the formation of methylglucose amounted to 92.4%, and the activity of formation of methylglucose per unit mass of catalyst was 6,321 mol/h/kg of catalyst. Reactivity after 500 hours was assessed as not changed significantly and provides a degree of conversion of ethylene glycol 52,6%, the selectivity of the formation of methylglucose 92.3% and the activity of formation of methylglucose 6,33 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni and Au was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 3.2 nm, showing, thus, the practical absence of any change after the reaction compared to the initial state.

Example 35

The catalyst coated to 1.45 wt.% Nickel and 1.44 wt.% gold (NiOAu/SiO /K) was obtained in the same manner as in (2) of example 17, except that used the medium in which commercially available silica (CARiACT Q-10, Fuji Silysia Chemical, Ltd.) was impregnated with 4 wt.% potassium, and were fired at 600°C. the Atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,772. Based on the results of studies by powder x-ray diffraction (XRD) of this catalyst diffraction pattern corresponding to the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. On the other hand, was attended by a broad peak corresponding to the gold crystals, and the average crystallite size calculated using the sherrer formula, was approximately 3 nm.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and Ni Kα spectrum closely matches the spectrum of Nickel oxide, which is the only connection. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 0,325, and the chemical shift (ΔE) was 0,331. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

in Addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was $ 0,86.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 45.2 percent, the selectivity of the formation of methyl methacrylate comprised of 92.5%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 5,458 mol/h/kg of catalyst. Reactivity after 500 hours was evaluated as have the impact in the reduction reaction activity and selectivity, that led to a degree of conversion of methacrolein 40,4%, the selectivity of formation of methyl methacrylate with 91.4% and activity education of methyl methacrylate 4,821 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni was 5 hours/million and 3 hours per million, the concentration of Au was 1 hour/million and 0.6 hours/million, and the concentration of Si was 10 hours/million and 7 hours/million, showing, thus, peeling and leaching of Ni, Au and Si. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), it was observed the formation of cracks and spalling in the part of the catalyst.

In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 4.6 nm, showing thereby that the sintering of the composite nanoparticles.

Example 36

The catalyst coated 1,49 wt.% Nickel and is 1.51 wt.% gold (NiOAu/γAl2O3) was obtained in the same manner as in (2) of example 17, except for using a commercially available γ-alumina (Neobead, Mizusawa Industrial Chemicals, Ltd.). The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,768. Based on the results of studies IU the Odom powder x-ray diffraction (XRD) diffraction pattern of the catalyst, the corresponding Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. On the other hand, was attended by a broad peak corresponding to the gold crystals, and the average crystallite size calculated using the sherrer formula, was approximately 3 nm.

The chemical state of Nickel corresponds to the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and was identified as the chemical state different from the chemical state of Nickel oxide, which is the only connection on the basis of differences in Ni Kα spectra. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum, $ 3,350, and the chemical shift (ΔE) was 0,334. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: about 3.1 nm). Elemental analysis (20 points) was performed for kardasis observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX) and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 0.89.

In addition, the study of changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) absorption peaks of surface plasmons due to gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 47.2%, selectivity of the formation of methyl methacrylate was 92,8%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 5,718 mol/h/kg of catalyst. Reactivity after 500 hours was evaluated as showing the reduction reaction activity and selectivity, which led to a degree of conversion of methacrolein 41,4%, the selectivity of formation of methyl methacrylate of 91.5% and activity education of methyl methacrylate 4,945 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Al in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni was 3 hours/million and 2 hours per million, the concentration of Au was 0.9 hours/million and 0.7 h/mn, and Al concentration was 10 hours/million and 8 h/m is h, demonstrating, peeling and leaching of Ni, Au and Al. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), it was observed the formation of cracks and spalling in the part of the catalyst. In addition, srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM), was 4.2 nm, showing thereby that the sintering of the composite nanoparticles.

Example 37

The catalyst coated 1.50 wt.% Nickel and of 1.52 wt.% gold (NiOAu/SiO2-TiO2) was obtained in the same manner as in (2) of example 17, except that the media used the composition of the silicon oxide-titanium dioxide, used as a carrier in example 5. The atomic ratio of Ni/(Ni + Au) in the obtained catalyst was 0,768. Based on the results of studies by powder x-ray diffraction (XRD) of this catalyst diffraction pattern corresponding to the Nickel was not observed, thus confirming that the Nickel is present in an amorphous state. On the other hand, was attended by a broad peak corresponding to the gold crystals, and the average crystallite size calculated using the sherrer formula, was approximately 3 nm.

The chemical state of Nickel is correspond the high-spin divalent Nickel, as it is suggested on the basis of the results of rentgenolyuminestsentnye high resolution (HRXRF), and Ni Kα spectrum closely matches the spectrum of Nickel oxide, which is the only connection. The full width at half maximum (FWHM) of Ni Kα spectrum of the catalyst as obtained from the measured spectrum was 3,252, and the chemical shift (ΔE) was 0,330. The full width at half maximum (FWHM) of Ni Kα spectrum of Nickel oxide, measured as the standard substances were 3,249, and the chemical shift (ΔE) was 0,344.

In addition, visual examination of the forms of active catalyst components using transmission electron microscope (TEM/STEM) confirmed that the media were deposited nanoparticles with a maximum distribution of particle diameter of from 2 to 3 nm (srednesemennyh particle diameter: 3,2 nm). Elemental analysis (20 points) was performed for each of the observed nanoparticles using auxiliary energy dispersive x-ray detector (EDX), and was confirmed by the content of Nickel and gold in all particles. The atomic ratio of Nickel to gold in these composite particles (average value) was 0.81.

In addition, according to a study of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) peaks absorbed in the I surface plasmons, due to the gold nanoparticles was not observed (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 55.3%, the selectivity of the formation of methyl methacrylate was 92,8%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 6,699 mol/h/kg of catalyst. Reactivity after 500 hours was evaluated as showing the reduction reaction activity and selectivity, which led to a degree of conversion of methacrolein 48,8%, the selectivity of formation of methyl methacrylate of 92.1% and activity education of methyl methacrylate 5,867 mol/h/kg of catalyst.

In addition, when the concentration of ions Ni, Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the concentration of Ni was 8.0 hours/million and 3.0 hours per million, the concentration of Au was 1.3 hours/million and 0.9 h/mn, and Si concentration was 8.0 hours/million and 6.0 hours/million, showing, thus, peeling and leaching of Ni, Au and Si. When the catalyst was recovered after reaction for 500 hours and explored the scanning electron microscope (SEM), it was observed the formation of cracks and spalling in the part of the catalyst. In addition, the pore volume of the catalyst, the AK is determined by adsorption of nitrogen, was and 0.46 ml/g, and average pore diameter was 15 nm. Srednesemennyh the particle diameter of the composite nanoparticles, as determined using transmission electron microscope (TEM)was 4.4 nm, showing thus that the pore diameter of the catalyst is increased and the sintering of the composite nanoparticles.

Comparative example 10

The catalyst coated with gold in a number of 1.48 wt.% (Au/SiO2-Al2O3) was obtained in the same manner as in (2) of example 17, except that the media used the media system based on silica-alumina, obtained in (1) of example 17, and was not added to the uranyl nitrate Nickel. According to the results of powder x-ray diffraction (XRD) for this catalyst was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. When the shape of the gold particles was observed using a transmission electron microscope (TEM), it was confirmed that the carrier caused the gold particles having srednesemennyh the particle diameter of 3.5 nm. In addition, the specific surface area of the catalyst was 148 m2/g, pore volume of the catalyst, as determined by adsorption of nitrogen amounted to 0.29 ml/g, and average pore diameter was 8 nm. In addition, the research is of the changes in the electronic excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) was observed peak absorption of surface plasmons, due to the gold nanoparticles (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction for 200 hours was 25.3%, the selectivity of the formation of methyl methacrylate was 80.5%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 2,659 mol/h/kg of catalyst. Reactivity after 500 hours was evaluated as showing the reduction reaction activity and selectivity, which led to a degree of conversion of methacrolein of 17.8%, the selectivity of formation of methyl methacrylate 78.3% of the activities of the education of methyl methacrylate 1,819 mol/h/kg of catalyst.

In addition, when the concentration of ions Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the Au concentration was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, the pore volume of the catalyst, as determined by adsorption of nitrogen, was 0.41 m is/g, and the average diameter of pores was 13 nm. Srednesemennyh the particle diameter gold nanoparticles, as determined using transmission electron microscope (TEM)was 5.3 nm, showing thereby that the diameter of pores of the catalyst is increased and the sintering of gold nanoparticles.

Comparative example 11

The catalyst coated with gold in a number of 1.48 wt.% (Au/SiO2-Al2O3-MgO) was obtained in the same manner as in (2) of example 25, except that the media used the media system based on a silicon oxide-aluminum oxide-magnesium oxide obtained in (1) of example 25, and was not added to the uranyl nitrate Nickel. According to the results of powder x-ray diffraction (XRD) for this catalyst was attended by a broad peak corresponding to the gold crystals. The average crystallite size calculated using the sherrer formula, was approximately 3 nm. When the shape of the gold particles was investigated using transmission electron microscope (TEM), it was confirmed that the carrier caused the gold particles with an average particle diameter of 3.4 nm. In addition, the specific surface of the catalyst was 152 m2/g, pore volume of the catalyst, as determined by adsorption of nitrogen, was 0.25 ml/g and average pore diameter was 5 nm. In addition, the study of changes jelektronnom excited state of the catalyst by the method of spectroscopy in the UV and visible part of the spectrum (UV-Vis) was observed peak absorption of surface plasmons, due to the gold nanoparticles (about 530 nm).

The reaction was conducted in the same manner as in (3) of example 17, using this catalyst. As a result, the degree of conversion of methacrolein after completion of the reaction within 200 hours accounted for 29.3%, the selectivity of the formation of methyl methacrylate was 82.3%, and the activity of formation of methyl methacrylate per unit mass of catalyst was 3,148 mol/h/kg of catalyst. Reactivity after 500 hours was evaluated as showing the reduction reaction activity and selectivity, which led to a degree of conversion of methacrolein of 23.5%, the selectivity of formation of methyl methacrylate 80.1% of the activity and the formation of methyl methacrylate 2,457 mol/h/kg of catalyst.

In addition, when the concentration of ions Au and Si in the reaction solution were analyzed using ICP-MS after 200 and 500 hours after the start of the reaction, the Au concentration was 0.1 h/m or less in both cases, and the concentration of Si was 1 h/m or less in both cases. When the catalyst was recovered after reaction for 500 hours and examined using a scanning electron microscope (SEM), was not observed any significant cracking or chipping of the catalyst particles. In addition, the pore volume of the catalyst, as determined by adsorption of nitrogen, were 0.37 m is/g, and the average diameter of pores was 10 nm. Srednesemennyh the particle diameter gold nanoparticles, as determined using transmission electron microscope (TEM), amounted to 5.4 nm, and watched the enlarged diameter of the pores of the catalyst and the sintering of gold nanoparticles.

Based on the results described above, the catalyst to obtain a complex ester of carboxylic acid in accordance with this embodiment provides an efficient way of obtaining esters of carboxylic acids with high selectivity of the aldehyde and alcohol, or one or more types of alcohols and demonstrate excellent mechanical strength and chemical resistance of the carrier without cracking or chipping of the catalyst even after undergoing a long period of time. In addition, there was practically no any sign of peeling or leaching of the Nickel component and X, which are the active components of the catalyst, increasing the diameter of the pores of the catalyst or sintering of composite nanoparticles, thus providing the ability to maintain a high level of reactivity of the catalyst even after undergoing a long period of time.

This application is based on patent application Japan, registered by the Japan patent office on August 13, 2007 (the application is and the Japan patent No. 2007-210962), the patent application Japan, registered by the Japan patent office on October 11, 2007 (application for Japan patent No. 2007-265375), the patent application Japan, registered by the Japan patent office on October 26, 2007 (application for Japan patent No. 2007-279411) and the patent application of Japan registered with the Japan patent office on April 14, 2008 (application for Japan patent No. 2008-105103), the contents of which are incorporated herein by reference.

Industrial applicability

The present invention can be used in industry as a catalyst to obtain a complex ester of carboxylic acid by reacting the aldehyde and alcohol, or one or more types of alcohols, in the presence of oxygen.

1. Catalyst to obtain a complex ester of carboxylic acid by reacting (a) aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen containing:
oxidized Nickel; and
X, where X represents at least one element selected from the group consisting of palladium, platinum, ruthenium, gold, silver and copper supported on a carrier in the range of the atomic ratio Ni/(Ni+X) from 0.20 to 0.99.

2. The catalyst according to claim 1 containing composite nanoparticles consisting of oxidized Nickel and X, where X represents at least one element, the last of the group, consisting of palladium, platinum, ruthenium, gold, silver and copper.

3. The catalyst according to claim 2, in which the composite nanoparticle is a particle having X in its core, and the surface of the core is covered with oxidized Nickel.

4. The catalyst according to claim 2 or 3, wherein in addition to the composite nanoparticles media contains independently oxidized Nickel.

5. The catalyst according to claim 1 or 2, in which the oxidized Nickel is a Nickel oxide and/or a complex oxide containing Nickel.

6. The catalyst according to claim 1 or 2, in which the carrier is aluminium-containing composition on the basis of silicon oxide that contains silicon oxide and aluminum oxide, and the amount of aluminum is in the range from 1 to 30 mol.%, in the calculation of the total molar amount of silicon and aluminum.

7. The catalyst according to claim 6, in which the medium further comprises at least one kind of the main metal component selected from the group consisting of alkali metal, alkaline earth metal and rare earth metal.

8. The catalyst according to claim 6, in which the ratio of Nickel and aluminum oxide is from 0.01 to 1.0 in the calculation of the atomic ratio of Ni/Al.

9. The catalyst according to claim 7 or 8, in which the ratio of Nickel and base metal component is from 0.01 to 1.2 per atomic ratio of Ni/(alkali metal+alkaline is Zemelny metal+rare earth metal).

10. The catalyst according to claim 1 or 2, wherein the carrier is a composition comprising silicon oxide, aluminum oxide and magnesium oxide, and contains from 42 to 90 mol.% silicon, from 5.5 to 38 mol.% aluminum and from 4 to 38 mol.% magnesium based on the total molar amount of silicon, aluminum and magnesium.

11. The catalyst according to claim 10, in which the ratio of Nickel and aluminum oxide is from 0.01 to 1.0 in the calculation of the atomic ratio of Ni/Al, and the balance Nickel and magnesium oxide is from 0.01 to 1.2 per atomic ratio of Ni/Mg.

12. The catalyst according to claim 1 or 2, in which the specific surface area is from 20 to 350 m2/g, the diameter of pores with a maximum frequency of occurrence is 3 to 50 nm, the pore volume is from 0.1 to 1.0 ml/g, and particle diameter is from 10 to 200 microns.

13. The method of producing catalyst to obtain a complex ester of carboxylic acid according to any one of claims 1 to 12, including:
the first stage of obtaining a catalyst precursor deposition of Nickel and component X, where X represents at least one element selected from the group consisting of palladium, platinum, ruthenium, gold, silver and copper on the carrier by neutralization of the acidic solution of a soluble metal salt containing Nickel and X; and the second stage oxidation of Nickel obtained by heat treatment of the catalyst precursor and the atomic ratio of Ni/(N+X) is from 0.20 to 0.99.

14. The method of obtaining complex ether carboxylic acids, including the stage of interaction of the catalyst according to claims 1-12 (a) aldehyde and alcohol, or (b) one or more types of alcohols, in the presence of oxygen.

15. The method according to 14, in which the aldehyde is a compound selected from acrolein, methacrolein and mixtures thereof.

16. The method according to 14, in which the aldehyde is a compound selected from acrolein, methacrolein and mixtures thereof, and the alcohol is methanol.

17. The method according to 14, in which one type of alcohol is ethylene glycol, and other types of alcohol is methanol.



 

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SUBSTANCE: invention relates to an improved method for continuous production of alkyl(meth)acrylates through re-esterification of methyl(meth)acrylate with alcohols having higher boiling point than methanol, and specifically to a method for continuous production of higher esters of (meth)acrylic acid of formula (C)

, where R1 denotes a hydrogen atom or methyl, and R2 denotes a straight, branched or cyclic alkyl or aryl residue with 2-12 carbon atoms, through re-esterification of methyl esters of (meth)acrylic acid of formula (A)

, where R1 is as described above, with higher alcohols of formula (B) R2OH (B), where R2 is as described above, in the presence of a catalyst or mixture of catalysts, in which a vacuum evaporator and/or film-type evaporator is used, designed for processing still residue of the distillation column in order to separate high-boiling components, in which the end product coming from a distillation column for extracting low-boiling components is purified through distillation, with separation of an ester of formula (C) from the said distillation column as an overhead product, and the stillage residue of the vacuum evaporator and/or film-type evaporator is divided into portions and a portion of the stillage residue is fed into the reactor. Owing to special processing technology, a product having quality characteristics not achievable until recently is obtained. Also, extremely high output of the product per unit volume of the reactor, as well a overall output can be provided.

EFFECT: possibility of recycling a homogeneous catalyst and low consumption of auxiliary materials.

16 cl, 5 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: described are oligo oxypropylene acrylates for the primary layer of polymer coating of optical guides based on oligo oxypropylene glycol with molecular weight over 1000 and functionality of 2-3 with fractional conversion of hydroxyl groups into acrylate groups equal to 80-90%. Also described is a method for synthesis of oligo oxypropylene acrylates, involving acrylation of hydroxyl oligomer groups with acryloyl chloride without a solvent or in a medium of a dry organic solvent in the presence of an aliphatic tertiary amine at temperature 10-30°C. The method is distinguished by that, the hydroxyl-containing oligomer used is oligo oxypropylene glycol with molecular weight over 1000 and functionality 2-3 with fractional conversion of hydroxyl groups to acrylate groups equal to 80-90%.

EFFECT: obtaining oligo oxypropyelene acrylates with low viscosity and glass transition point, suitable for making the primary layer of frost-resistant low-modulus polymer coatings of optical guides.

2 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing butylacrylate involving: reaction of acrylic acid with butanol in the presence of water and a catalyst in a reactor; where the starting material is an aqueous solution of acrylic acid which is at least one of: (1) condensed water, obtained from vapour used in a kinetic vacuum pump which transports gas after trapping fluid process medium- vapour which is blown at high speed, (2) water for hydraulic sealing in a liquid ring pump which isolates liquid-water after air is let into the housing, (3) water used for collecting acrylic acid in the device which collects acrylic acid from an acrylic acid-containing gas, and acrylic acid which is not present in the aqueous solution of acrylic acid, where the device used for collecting acrylic acid is one or more devices selected from a group comprising a packed column, a plate-type column, a spray column and a scrubber. The invention also relates to a method of producing a super-absorbing polymer based on acrylic acid, involving the following steps: polymerisation of acrylic acid, in which the aqueous phase used is an emulsified aqueous solution of an acrylic acid monomer and water, dehydration of the obtained mixture during azerotropic distillation, where the starting material is aqueous acrylic acid solution which is at least one of the following: condensed water obtained from vapour used in a kinetic vacuum pump which transports gas after trapping fluid process medium - vapour, which is blown at high speed, water for hydraulic sealing in a liquid ring pump which isolates liquid-water after air is let into the housing, water used for collecting acrylic acid in the device which collects acrylic acid from an acrylic acid-containing gas, and acrylic acid which is not present in the aqueous solution of acrylic acid, where the device used for collecting acrylic acid is one or more devices selected from a group comprising a packed column, a plate-type column, a spray column and a scrubber.

EFFECT: design of an efficient method of using aqueous solution of (meth)acrylic acid with low concentration, formed at the stage for producing/storing (meth)acrylic acid.

13 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of (meth)acrylate storing. More specifically, claimed invention relates to method of storing alkyl ester of acryl or methacryl acid in reservoir during circulation or mixing at temperature from 15 for 50°C, which includes feed of gas mixture, obtained by mixing of incombustible inert gas with molecular oxygen, in reservoir, where: concentration of molecular oxygen in gas mixture is from 2 to 10 vol %; reservoir is produced from carbonaceous steel and equipped with pipe for gas input and pipe for gas output; gas has concentration of water 100 volume parts per million (vol. p/mln) or less; and alkyl ester of acryl or methacryl acid has concentration of (meth)acryl acid 30 weight parts per mln (wt, p/mln) or less.

EFFECT: reservoir for storing from less expensive and very universal material without losing stored (meth)acrylate stability.

2 cl, 3 ex

FIELD: petroleum chemistry.

SUBSTANCE: invention can be implemented in rectifying and evaporating towers. Condenser 20 consists of tubular panel 33, of a dividing chamber 31, into which from above there is supplied gas containing acrylic acid, also the condenser consists of chamber 32 wherein cooling medium is supplied. Cooling pipes 34 vertically pass through chamber 32. The first pipe for supply of polymerisation inhibitor 28 enters chamber 31 outside condenser 20, while sprayer 35 is connected with the end of the first pipe for supply of polymerisation inhibitor 28. The first pipe for supply of polymerisation inhibitor 28 is supported with holder 36 outside condenser 20.

EFFECT: stable continuous processing in condenser during long period of time due to eliminating polymerisation of readily polymerised compound in condenser of simple design wherein fumes of readily polymerised compound enter.

5 cl, 2 ex, 6 dwg

FIELD: chemistry.

SUBSTANCE: invention concerns regeneration of monomer complex ethers of substituted or non-substituted acrylic acid or styrene-containing monomers, particularly device for regeneration of monomer complex ethers of substituted or non-substituted acrylic acid or styrene-containing monomers from polymer material containing respective structural units. Device includes: heated reactor for monomer-containing gas generation from polymer material, and shifting device for propulsion of relocated product, combined with reactor or being a part of reactor. To enhance output and purity of generated monomer, heat carrier comprised by multiple spherical units with diametre within 0.075 to 0.25 mm is preferred.

EFFECT: relocated material containing polymer material and heat carrier.

2 cl, 5 dwg, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns organic compound synthesis, particularly method of obtaining 4-biphenylmetacrylate of the formula . Obtained compound is applied in production of heat and weather resistant polymer materials. Claimed method involves dissolution of 4-phenylphenol in 10 wt % aqueous solution of caustic soda, further dosage of acylating agent in the form of metacrylic acid anhydride agent in reaction mix preliminarily cooled to 0-(+5°)C at such rate so as to keep the mix temperature below +10°C at molar ratio of 4-phenylphenol and metacrylic acid anhydride of 1:(1.1-1.5), reaction mix maturing at room temperature with stirring, organic layer extraction, flushing by alkali solution, and drying.

EFFECT: enhanced output of 4-biphenylmetacrylate, admixture content of non-reacted 4-phenylphenol reduced to 0,003-0,005 wt %.

3 cl, 1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to sorbents containing nanostructure elements and may be used for treatment of fluids with technogenic impurities. Sorbent comprises the following components in wt %: bentonitic clay -10-40, glauconite - 10-50, thermally expanded carbon - 10-60. Proposed method comprises mixing initial components, adding water to produce plastic mass, granulating said mass, and thermal treatment of produced granules. Note here that thermal treatment comprises drying granules by infrared radiation at 70-150°C and SHF-heating of granules placed in quartz ceramic casing to 1000°C.

EFFECT: reduced power consumption, higher performances.

8 cl, 1 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to nanofiltration of liquid organic mixes. Proposed method comprises squeezing said mixes through membrane based on poly[1-(trimethylsilyl)-1-methyl acetylene] wherein solutions of compounds with molecular weight over 300 g/mol in solvents are used while membrane is pre-modified on anode at constant current discharge and alcohols or ketones are used as solvents. Said nanofilter allows retention of larger organic molecules for poly[1-(trimethylsilyl)-1-methyl acetylene]-membrabes exceeds (98%) that for initial modified poly[1-(trimethylsilyl)-1-methyl acetylene]-based membranes (95%).

EFFECT: higher separation efficiency.

2 cl, 2 tbl, 4 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to medication in form of ointment for treatment and prevention of fungal skin diseases. Claimed medication as antifungal agents contains bifonasol in amount 0.9-1.1 wt %, 6-10 wt % of stabilised sol of silver nanoparticles and 6-10 wt % of stabilised sol of copper nanoparticles, and as base, it contains mixture of polyethylene oxides (400, 1500, 2000 and 4000) and water.

EFFECT: increase of fungicidal activity and minimisation of side effects in application of medication.

6 ex, 1 tbl

FIELD: physics.

SUBSTANCE: in the method of producing super-thin silicon films on sapphire objects having a sapphire substrate and an initial silicon layer whose thickness is considerably greater than the thickness of the obtained thin silicon films, a large part of the silicon layer undergoes amorphisation followed by solid-phase recrystallisation where the remaining part of the silicon layer not affected by amorphisation is used as the inoculating layer, where recrystallisation is carried out using an inoculating layer adjacent to the silicon-sapphire boundary surface, and thickness of this inoculating layer during amorphisation is made as minimum as possible without deterioration of the quality of the recrystallised layer.

EFFECT: low energy for implantation during amorphisation, avoiding radiation defects in the sapphire substrate and consequently avoiding autodoping of the silicon layer with aluminium atoms during recrystallisation.

FIELD: electricity.

SUBSTANCE: invention can be used for creation of fillers of composite materials, gas-distributing layers in fuel elements, components of lubricants, hydrogen storage batteries, filter materials, carbon electrodes of lithium batteries, glue composites, carriers of catalysts, adsorbents, anti-oxidants during production of cosmetics, cold emission sources of electrons, modifying agents to special-purpose concrete, as well as for coatings screening microwave and RF radiation. Method involves pyrolysis of gaseous carbon-containing compounds on surface of metallised dust catalyst in flow reactor having the possibility of gas medium mixing. Aerosil particles containing clusters of the following metals on the surface as catalyst: nickel, cobalt or iron. Catalysts are obtained prior to the beginning of pyrolysis by reactivation of catalyst sprayed in reactor in current of hydrogen-containing gas at simultaneous mixing of gaseous medium. It is expedient to mix gaseous medium in reactor in fluidised bed mode with ultrasonic material dispersion. Outer diameter of obtained nanotubes is 5 to 35 nm; inner diameter is 4 to 12 nm; packed density is 0.3-0.4 g/cm3; total content of impurities is less than 1.2-1.5%; length is 0.5 to 3 mcm.

EFFECT: invention allows synthesising thinner nanotubes with high cleanliness, which have smaller spread in values as to diameters.

2 cl, 3 ex

FIELD: metallurgy.

SUBSTANCE: here is disclosed procedure for fabrication of high strength and wear resistant electro-technical items of chromium or chromium-zinc bronze with nano and sub-micro-crystal structure. According to the procedure source work pieces of bronze are subjected to multi-cycle equi-channel angular press forming at rate 0.4 mm/sec at room temperature and at total number of cycles facilitating reduction of average dimension of bronze grains to dimension of grain dopt, value of which is preliminary determined depending on composition of bronze in accordance with expression: dopt=4bG/(π(1-v)(σ-σi(b))), where b is Burgers vector, G is modulus of alloy shear, v is Poisson ratio, σ is external applied stress, σi(b) is internal stress from non-equilibrium borders of grains; further, the work pieces are annealed in air in one or two stages at temperature 75-450°C during from 5 min to 200 hours with successive formation of electro-technical items out of them.

EFFECT: raised processability of fabrication at increased wear resistance and combination of strength and electric conductivity of work-pieces.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention may be used in lighting engineering and construction as antirust decorative filtering and radiation-redistributing coats. Proposed composition based on zirconium compound comprises 96 wt % of ethanol, zirconium oxo chloride crystalline hydrate and fluoresceine in the following ratio, i.e. zirconium oxo chloride - 1.20-1.28; fluoresceine 0.04-0.08, ethanol making the rest. Produced film-forming solution is applied onto substrate to be subjected to thermal treatment.

EFFECT: films with high refractivity, water and chemical resistance.

1 dwg, 1 tbl, 3 ex

FIELD: nanotechnologies.

SUBSTANCE: invention refers to manufacture of electrolytic silicon in the form of nanofibres or microfibres with the use of raw material - silicon dioxide. Essence of invention: method for obtaining silicon nano- or microfibres consists in the fact that SiO2 electrolysis process is performed in melt LiF (0÷3) - KCl (10÷50) - KF (5÷50) - K2SiF6(5÷45) - SiO2 (2÷5) wt % at temperature of 650-800°C and cathode current density of 0.005-1.5 A/cm2 with further silicon sediment detachment from surface of cathode-substrate and electrolyte.

EFFECT: obtaining nanofibrous or microfibrous high-quality silicon with required fibrous structure at relative simple implementation of the process.

5 cl

FIELD: process engineering.

SUBSTANCE: invention relates to producing nanocrystalline magnetic powder used to fabricate broadband radar absorbent materials. Proposed method comprises thermal pretreatment of selected initial material representing amorphous band from magnetically soft alloys based on Fe-Co-Ni-system at (0.25-0.29)-Tliquidus for 30-90 min with air cooling and pre-mincing thermally treated band to 3-5 mm fraction. Then, grinding is performed in high-speed disintegrator due to particles collision to obtain amorphous structure powder with faction size of 20-60 mcm. Final thermal treatment of obtained amorphous powder is conducted at (0.3-0.4)Tliquidus for 30-90 min with air cooling for producing nanostructure in powder volume and isolating nanocrystals in amorphous matrix.

EFFECT: production of nanocrystalline magnetic powder from high magnetic conductivity magnetically soft alloys.

1 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemical catalysts for producing carbon nanotubes via catalytic pyrolysis of hydrocarbons. Described is a metal-oxide catalyst for growing bundles of carbon nanotubes from gaseous phase, containing iron, cobalt and aluminium oxides, molybdenum oxide in atomic ratio of molybdenum to iron, cobalt and aluminium from 1:10 to 1:50, wherein the atomic ratio of iron to cobalt ranges from 3:1 to 1:3.

EFFECT: catalyst enables to obtain bundles of carbon nanotubes with high output.

3 dwg, 2 ex

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