A method of producing a catalyst containing gold and titanium

 

(57) Abstract:

A method of producing a catalyst comprising gold on a titanium containing catalyst. The method involves the impregnation of the support with a solution of gold compounds, a solution of a reducing agent and, optionally, the promoting metal and reducing agent and/or a carrier containing titanium and, optionally, includes heating the impregnated carrier. The catalyst can be used to hydrocyclone olefins, such as propylene, oxygen in the presence of hydrogen in oxides of olefins, such as propylene oxide. The technical result - the use of simple methods of impregnation and ensuring better regulation of the amount of gold deposited on the carrier. 3 C. and 16 h.p. f-crystals, 1 table.

This invention relates to a process for the preparation of oxidation catalyst containing gold and titanium.

Catalysts containing gold and titanium, can be used to hydrocyclone of olefins to olefin oxides. For example, it is known oxidation of propylene with oxygen in the presence of hydrogen and of a catalyst containing gold and titanium, to obtain propylene oxide. Propylene oxide is a commercially important source material CLASS="ptx2">

The catalyst used in the above method hydrocyclone more specifically includes gold on titanium containing media. The carrier may be selected, for example, titanosilicates, titanium dioxide, titanium dispersed on silica, and some metal titanates. The catalyst may optionally, but not necessarily to contain the promoting metal, such as alkali, alkaline earth, or lanthanide rare earth metal, with the aim of increasing the catalytic efficiency. Representing the specified method and catalyst composition prior art publications include patent PCT WO 98/00413, WO 98/00414 and WO 98/00415.

A known method of producing catalyst hydrocyclone comprising a platinum group metal on titanosilicate carrier by impregnation. The way this type of patent publication WO 96/02323, describes the impregnation of a solution of the metal salt of the platinum group titanosilicates media and then restore the impregnated carrier hydrogen to control the state of power relations platinum group metal. Hydrogen reduction may require high temperatures, which is undesirable because of the recovery nevoso, including ultramercial gold particles deposited on the titanium dioxide obtained by the method of coating deposition. This method includes obtaining an aqueous solution of a soluble gold salts, regulation of pH between 7 and 11 and then adding titanium dioxide to the solution. The resulting composite calicivirus to get ultramatic gold particles deposited on the titanium dioxide as a carrier.

An alternative but similar method, examples of which are given in U.S. patent 4839327 and EP-A1-0709360 includes the coprecipitation method. Here, an aqueous solution of gold compounds with pH between 7 and 11 is added dropwise to an aqueous solution of a soluble titanium salt, adjusted to the same pH range, to form a joint sediment. Joint sediment calicivirus to produce metallic gold, deposited on the oxide of the metal.

In another method of deposition deposition, examples of which are given in U.S. patent 4937219 receive a catalyst comprising ultramercial gold particles immobilized on a mixed oxide of alkaline earth metal and titanium. Receiving involves the dissolution or suspension of the compound of the alkali metal-titanium, such as titallium agent, in order to make ultramercial gold particles deposited on the alkali earth metal titanate. Indicates that the regenerating agent is formalin, hydrazine or citrate salt. A variant of this method is disclosed in U.S. patent 5051394, where the pH of an aqueous solution containing a compound of gold and a water-soluble salt of titanium, regulate alkaline compound for product education co-deposition, to which is added carboxylic acid or its salt. The thus treated product co-deposition heat with the formation of a catalyst comprising metallic gold is deposited on the titanium oxide.

All of the above methods of deposition deposition and codeposition have many drawbacks. In particular, the methods of the prior art require accurate control of the conditions of deposition over a long period of time. In addition, when using a reducing agent, and particles of gold can be recovered in the solution to adhesion to the carrier, which leads to inefficient use of gold. Because there is little control over the exact amount of gold, which is deposited on the carrier, additional efforts are required for the methods of the prior art temperature-sensitive. They also require the use of large quantities of solvents and pH regulation. Finally, the methods of the prior art can lead to insufficient adhesion of the gold particles to the media.

From the point of view of the above, it would be desirable to find a simple, effective and reproducible method of obtaining the active oxidation catalyst comprising gold, pending on such media. It would be desirable if the method was deprived of the disadvantages of the methods of deposition deposition and sausagey. It would be more desirable if the method was adapted for practical forms of catalyst such as granulated and extruded titanium containing media. It would be even more desirable if the method did not require the stage of extraction of gold. This method could reduce the effort of obtaining a catalyst and its cost and, equally important, to keep the gold.

This invention is a method of obtaining a catalyst composition comprising gold on a titanium containing media. The method involves the impregnation of the catalyst carrier connection gold and regenerating agent under conditions sufficient to obtain kataliticheskom according to this invention includes titanium, the source of titanium should be present in the process of preparation of the catalyst. This requirement is fulfilled when the media and/or reducing agent containing titanium. In line with this, the words “of such media, which are used to describe the catalyst, widely include ways in which the media initially containing titanium as titanium dioxide, titanosilicate or metal titanate; or, alternatively, titanium derived from a reducing agent, was dispersed on the carrier, which originally did not contain titanium, such as titanium dispersed on silica; or, alternatively, titanium derived from a reducing agent, was dispersed on the carrier that originally contained titanium, such as titanium, dispersed on titanium dioxide.

The present invention provides a simple, efficient and reproducible method of obtaining a oxidation catalyst comprising gold, pending on such media. The advantage of this method of the invention is the use of simple methods of impregnation, and not as complex and time-consuming methods of deposition deposition and codeposition disclosed in known levels of the ar technique is what it allows you to use smaller amounts of solvent and does not require regulation of pH. Another advantage is that the method of this invention provides better regulation around the amount of gold deposited on the carrier. Since the method of the present invention effectively uses the gold, there is no need to remove unused gold, as required in the methods of the prior art. As a further advantage, the method of the invention can be used to obtain a practically usable form of the catalyst, namely catalysts obtained granulated and extruded by the media. Finally, in the method of this invention, the recovery simply perform the impregnation of the carrier regenerating agent in contrast to the method of recovering hydrogen prior art. All these advantages provide a method of producing a catalyst which is effective for the price and is more suitable for commercial purposes.

In another aspect, the invention is a catalytic composition comprising gold on a titanium containing media. The catalyst was prepared in the above manner, including the th agent and/or carrier includes titanium, moreover, the impregnation is conducted under conditions sufficient to obtain a catalytic composition. The catalyst optionally may be heated prior to use.

As noted here previously, the catalyst comprising gold on a titanium containing media, finds use for hydrocyclone of olefins to olefin oxides. The term “hydrocyclone” means that the oxidation of olefins carried out with oxygen in the presence of hydrogen with the formation of olefin oxide. Water is formed as a by-product of this process, but water can also be formed by direct combustion of hydrogen. When the gold-titanium catalyst receive the preferred methods of the invention, the catalyst forms a smaller amount of water in the process hydrocyclone compared with the catalysts of similar composition produced by the methods of the prior art, which is also an advantage. Illustration of the above method of oxidation is hydrocyclone propylene to propylene oxide using a catalyst comprising gold on a titanium containing media. When the catalyst was prepared by the method according to this invention, an advantage of the catalyst is the formation of oxide prop is of interest.

The invention described herein relates to a method for producing a catalyst composition comprising gold on a titanium containing media. The method involves the impregnation of the catalyst carrier connection gold and regenerating agent under conditions sufficient to obtain a catalytic composition. Since titanium is an essential element described here, the catalytic composition, the source of titanium is required in the process of preparation of the catalyst. In accordance with this, the media can provide titanium in the form of media, including titanium dioxide. Alternatively, the reducing agent can provide titanium, as illustrated regenerating agent, technologicheski connection, such as titanocene, or coordination compound, such as titaniumalloy. In the alternative case, as the carrier, and reducing agent can provide a source of titanium. In an alternative embodiment, after the stage of impregnation of the catalyst warm up before using.

In the preferred embodiment of the present invention the method comprises the impregnation of the catalyst carrier connection gold and regenerating agent which does not contain titanium, media, coticosteroids media. After impregnation stage, the catalyst can optionally be warmed before use.

In another preferred embodiment of the present invention the method comprises the impregnation of the catalyst carrier connection gold and titanium containing regenerating agent which does not contain titanium, under conditions sufficient to obtain a catalyst composition comprising gold on a titanium containing media. Such reducing agent is preferably selected from technologicheskij compounds and coordination compounds of titanium. Similarly, the catalyst can optionally be heated after the impregnation stage and prior to use.

In the third preferred embodiment of the present invention, the catalyst further includes at least one promoting metal. As a promoter you can use any metal or metal ion, which improves the performance of the catalyst in the oxidation method. The promoting metals are described more specifically below. Upon receipt of the catalyst containing the promoting metal, the carrier is impregnated with a compound of gold, at least one compound promoting metal and regenerating agent services agent or catalyst carrier, or both contain titanium. The catalyst can optionally be warmed up after treatment and before use.

In another preferred embodiment, after stage(s) impregnation and before the optional stage of the heating medium is washed. If the washing removes the desired ions promoting metal, then in another preferred embodiment of the invention, the carrier can be treated with a solution of ions of the promoting metal stage after washing and before optional stage heating to replenish the supply of ions promoting metal to the media.

As indicated here above, the catalyst obtained by the method according to this invention, includes gold and titanium containing media. The catalyst can, optionally, include at least one promoting metal, which is preferably selected from metals of group 1, group 2, silver, lanthanide rare earth metals and actinide metals of the Periodic table and mixtures thereof. Gold can exist in the degree or degrees of oxidation, comprising from about +3 to 0, as determined by photoelectron spectroscopy. It is considered that the reducing agent to be placed from about +3 to oxidation, less than approximately +3. Gold can exist in the form of ions or charged clusters, and/or discrete particles of gold, and/or mixed particles of gold-the promoting metal and/or gold atoms or clusters of atoms dispersed throughout the carrier surface. Gold particles can be visible or may not be visible in the analysis of transmission electron microscopy, high-resolution (HR-TEM) and/or Mie-scattering. The average size of gold particles is preferably less than 500 , more preferably less than 200, and very preferably less than 100 . Titanium is typically present in a positive oxidation state, as determined by photoelectron and x-ray absorption spectroscopy.

Download gold of such media can be any load, provided that the catalyst is active in the here described method hydrocyclone, where the olefins are oxidized by oxygen in the presence of hydrogen in the oxide olefin. Download gold is generally greater than about 0.001 weight percent (10 parts per million) calculated on the total weight of gold and the media. Download gold, preferably, higher than 0.005, and more preferably, higher than 0.010 massowah is. the downloading of gold, preferably less than 10.0, more preferably less than 5,0 mass percent.

The impregnation techniques known in this field, such as, for example, the techniques described Charles N. Satterfield in Heterogeneous Catalysis in Practice, McGraw-Hill Book Company, New York, 1980, pp. 82-84. In this procedure, the carrier is wetted with a solution containing interest soluble compound or a water soluble compound of interest ion. In this case, use a solution containing the compound of gold, and a solution containing a reducing agent. Impregnation can be performed to the point of initial wetting, or to the point of a smaller wetting, or more to the point of excess wetting solution, as it is desirable. Impregnation is preferably carried out to the point of initial wetting or point less wetting. The temperature of deposition typically is from about ambient temperature (21C), up to about 100C, preferably from about S to about 50C. The deposition is usually carried out at ambient pressure. The media can be processed by multiple impregnations. More specific details of the impregnation method described below.

In this way izopet the solution for impregnation. You can use water and nonaqueous solvents. Non-limiting examples of soluble gold compounds include hartlot acid, chloraurate sodium, chloraurate potassium gold cyanide, mixed cyanide of potassium and gold, trichlorohydrin diethylaminoethoxy acid, acetate, gold, alkyltrimethylenedi, preferably chloride, and aurate alkaline minerals, including Aurat lithium Aurat sodium, Aurat potassium, Aurat rubidium and Aurat cesium. The connection of gold is preferably chlorproma acid or its salt is an alkali metal. Alkyltrimethylenedi, preferably chloride, suitable for use with non-aqueous solvents. In a typical case, the both molarity soluble gold compounds in the solution for impregnation is from about 0.001 M to the saturation point of soluble gold compounds, preferably from 0.005 M to 1.0 M

Any reducing agent which can be dissolved to form solution a long impregnation, can appropriately be used in the method of the present invention.

Reducing agent can be classified into two categories: those that do not contain titanium, and those that contain titanium. In the first category typical and restoring the surrounding agents include, not limited to, carboxylic acids and their salts, alcohols and their alkoxide salt, sugar, alkanolamines and alkylamines followed. Specific types of illustrating, but not limiting these groups include acetic acid, lactic acid, citric acid, maleic acid, cinnamic acid and acetates, lactates, citrates, maleate and cinnamate alkali and alkaline earth metals, and also alkali metal gluconate, glucose, methanol, ethanol, propanol, ethanolamine, and Isopropylamine. Reducing agent is preferably selected from C6-20-sugars, WITH2-20-carboxylic acids, C1-15-aliphatic alcohols, C1-15-alkylamines followed, salts of alkaline and alkaline earth metals of the above sugars, carboxylic acids and alcohols and mixtures of any of the above compounds. The most preferred reducing agent is selected from methanol, ethanol, ISO-propanol, ethanolamine, acetic acid, lactic acid, citric acid, maleic acid, cinnamic acid, sodium acetate, sodium lactate, sodium citrate, maleate sodium, cinnamate sodium and mixtures thereof. In a typical case, the both molarity organic reducing agent in the solution for impregnation is from about 0.001 M to the saturation point in the eh of the solution for impregnation can also act as a reducing agent, as may be the case with alcohols such as methanol and ethanol.

Download organic reducing agent to the medium may vary within a wide range, so that the catalyst was active in the way hydrocyclone described here. Usually the molar ratio of the organic reducing agent for gold is greater than 0.5:1, preferably greater than 1:1. In some embodiments of the invention the molar ratio of the organic reducing agent for gold may be less than 100:1 and preferably less than 20:1. In other embodiments of the invention, for example, when the reducing agent also acts as solvent for impregnation, the molar ratio of the organic reducing agent for gold may be greater than 10000:1 and may even reach infinity, especially when the gold concentration is low.

In the second category reducing agent itself contains titanium, more specifically, in the form of technologicheskogo connection or coordination compounds of titanium. The term “technologicheskoe connection” is defined as a compound containing the titanium-carbon bond or a titanium-carbon bond. Titanium-upperdog-link find for example, in cyclopentadienylmagnesium connections and aristotelic compounds, such as titanocene. The term “coordination compound titanium” is defined as a compound containing an atom or ion titanium associated with organic molecule either neutral or anionic valence, such as alkylamine, alkoxylate or carboxylate. In a typical case, neutral or ionic organic donor molecule contains a pair of electrons. In the method according to this invention can use any technologicheskoe connection or coordination compound of titanium, while the organic component compounds can be oxidized. Non-limiting examples of such reducing agents include titanium alkoxides, suchas isopropoxide titanium, propoxy titanium, atoxic titanium, piperonyl of glycolate, titanium and titanium; titanium carboxylates, such as titanium oxalate, titanium lactate, titanium citrate and titaniumalloy; and dicyclopentadienyltitanium, such as dicyclopentadienyltitanium and other organotitanate. Technologicheskoe compound is preferably selected from compounds of cyclopentadienide and compounds of alkylsilane. Coordinate by both molarity of such a reducing agent in the solution for impregnation is from about 0.001 M to the saturation point technologicheskogo connection preferably from 0.005 M to 1.0 M

The download of such reducing compounds on the carrier can be varied within wide limits, while the resulting catalyst is active in the way hydrocyclone described here. In General, titanium containing reducing agent to be loaded on the carrier until the desired loading of titanium. Download titanium is usually higher than 0.02 mass%, preferably higher than 0.1 mass% and more preferably higher than 0.5 mass% based on the mass of the carrier. Download titanium is usually less than 20 mass% and preferably less than 10 weight percent based on the weight of the carrier.

Suitable solvents to obtain solutions for impregnation include inorganic and organic solvents and their mixtures, in which the connection to be dissolved, soluble, and stable. Typically, the solvent should be easily evaporate, because subsequently the solvent for impregnation removed from the media. Non-limiting examples of suitable solvents include water, aliphatic alcohols and polyols, aliphatic and aromatic hydrocarbons, ketones, esters, ethers, and mixtures thereof. In the elegance for organic reducing agent. However, if the water interacts with technologicheski connection or coordination compound of titanium, this compound is preferably dissolved in directionspanel organic solvent. As indicated here above, solvents such as alcohols, can also act as a reducing agent.

If the reducing agent does not contain titanium, is then required of such media. Such a medium may take many forms, including forms, described below.

A. Titanium dioxide

Amorphous and crystalline titanium dioxide can be suitably used as such media. The crystalline phase include anatase, rutile and brookite, included in this category phase are composites comprising titanium dioxide deposited on a metal oxide, such as silicon dioxide and aluminum oxide.

b. The metal titanates

As the catalyst carrier can be applied also suitable stoichiometric and non-stoichiometric compounds, including metal titanates. The metal titanates can be crystalline or amorphous. The titanates metals are preferably selected from ti is s 2 and the lanthanide and actinide metals. The titanate promoting metal is preferably selected from magnesium titanate, calcium titanate, barium titanate, strontium titanate, sodium titanate, potassium titanate and titanate erbium, lutetium, thorium, and uranium.

C. Titanosilicates

Crystalline and amorphous titanosilicates, preferably porous titanosilicates also suitably used as a carrier. Titanosilicates have a frame structure formed of SiO+4where a portion of the silicon atoms are replaced by titanium. Inside the frame structure of porous titanosilicates there is a regular or irregular system of pores and/or channels. May be empty cavity, called “cells”. Pores can be isolated or interconnected, and they can be one-, two - or three-dimensional. The pores are preferably of the micropores or mesopores, or in a number of their combinations. Used herein, the term " micropore has a pore diameter (or critical dimension, as in the case of recirculating perpendicular cross-section) of about 4 to about 20 , while the mesopores have a pore size or the critical size of more than 20 to when the of its pore volume and more preferably 80 percent or more of the total volume of pores. The remainder of the pore volume will be macropores, which have a pore diameter of more than 200 . Macropores include empty space between the particles or crystallites.

The pore size (or critical dimension), the distribution of pore size and surface area of porous titanosilicate can be obtained from measurements of adsorption isotherms and pore size. In a typical case, the measurements are carried out on titanosilicate in powdered form, using as adsorbate nitrogen at 77 K or argon at 88 K and using any suitable adsorption analyzer, such as a tool Micromeritics ASAP 2000. The volume of micropores is obtained from the amount of adsorption of pores having a diameter in the range from 4 to 20 . Similarly, the volume of mesopores is obtained from the amount of adsorption of pores having a diameter in the range of over 20 to about 200 . On the basis of the shape of the adsorption isotherms is possible to make a quantitative identification of the type of porosity, for example, microporous or macroporous type. In addition, increased porosity can be correlated with increased surface area. The pore size (or critical dimension) can be calculated from these data using the equations described by Charles N. Sa is inosilicate can be identified by means of x-ray diffraction (XRD), any comparison of x-ray XRD interest material with previously published standard or analysis x-ray single crystal XRD to determine the frame structure and, if present in the pores of the pore geometry and pore size.

Non-limiting examples of porous titanosilicates, which are suitably used in the method of the present invention include porous amorphous titanosilicates; porous layered titanosilicates; crystalline microporous titanosilicates, such as silicalite-1 titanium (TS-1), silicatic-2 titanium (TS-2), titanosilicate beta (Ti-beta), titanosilicate ZSM-12 (Ti-ZSM-12) and titanosilicate ZSM-48 (Ti-ZSM-48); and mesoporous titanosilicates, such as Ti-MCM-41.

The porous structure of TS-1 includes two interconnected, generally cylindrical, 10-ring pores with a diameter of approximately 5 . 10-Ring pore formed of only ten tetrahedra (SiO4-4and TiO4-4). Silicatic titanium and its characteristic x-ray XRD have been described in U.S. patent 4410501. TS-1 can be obtained commercially, but it can also be synthesized by methods described in U.S. patent 4410501. Other methods of obtaining were described in the following he in Zeolites, 1993, 13, pp. 454-461; by A. Tuel and Y. Ben Taarit in Zeolites, 1994, 14, pp. 272-281; and by A. Tuel. and Y. Ben Taarit in Microporous Materials, 1993, 1, pp. 179-189.

The pore structure TS-2 includes one three-dimensional 10-ring of microporous system. TS-2 can be synthesized by methods described in the following references: J. Sudhakar Reddy and R. Kumar, Zeolites, 1992, 12, PP. 95-100; by J. Sudhakar Reddy and R. Kumar, Journal of Catalysis, 1991, 130, pp. 440-446; and by A. Tuel and Y. Ben Taaritf Applied Catal. A. General, 1993, 102, pp. 69-77

The porous structure of Ti-beta includes two interconnected 12-ring, in the main cylindrical pores with a diameter of approximately 7 . Structure and receiving titanosilicate beta were described in the following references: publication of patent WO 94/02245 (1994); M. A. mblor, A. Corma, and J. H. Perez-Pariente, Zeolites, 1993, 13, pp. 82-87; and M. S. Rigutto, R.de Ruiter, J. P. M. Niederer, and H. van Bekkum, Stud. Surf. Sci. Cat., 1994, 84, pp. 2245-2251.

The porous structure of Ti-ZSM-12 includes one one-dimensional 12-ring channel system size 5,67,7 , as indicated S. Gontier and A. Tuel, ibid.

The porous structure of Ti-ZSM-48 includes a one-dimensional 10-ring channel system size is 5.3 5.6 , as indicated by R. Szostak, Handbook of Molekular Sieves, Chapman and Hall, New York, 1992, pp. 551-553. Other links on the preparation and properties of Ti-ZSM-48 include C. B. Dartt, C. B. Khouw, H. X. Li, and M. E. Davis, Micgcoporous Materials, 1994, 2, pp. 425-437; and A. Tuel and Y. Ben Taarit, Zeolites, 1996, 15, pp. 164-170.

Ti-MCM-41 is galewski from about 28 to 100 . Ti-MCM-41 can be obtained, as described in the following references: S. Gontier and A. Tuel, Zeolites, 1996, 15, pp. 601-610; and M. D. Alba, Z. Luan, and J. Klinowski, J. Phys. Chem., 1996, 100, pp. 2178-2182.

The atomic ratio of silicon to titanium (Si:Ti) titanosilicate can be any ratio that provides an active and selective catalyst for the epoxidation in the here described method hydrocyclone. Usually best atomic ratio of Si:Ti is equal to or more than approximately 5:1, preferably equal to or more than approximately 10:1. Usually best atomic ratio of Si:Ti equal to or less than about 200:1, preferably equal to or less than approximately 100:1. It is noted that the atomic ratio of Si:Ti, as defined here, refers to volume ratio.

d. Titanium dispersed on silica

Other suitable carrier for catalyst according to this invention includes titanium dispersed on silica, a number of such carriers can be obtained commercially. In the alternative case, this kind of media can be obtained by the method described in patent publication PCT WO 98/00415. In the last link titanium ions is dispersed over the entire surface of silicon dioxide, essentially in the disorganized phase. The term “pafase. Preferably more than 85%, even more preferably more than 90, and very preferably more than 95 weight percent titanium exists in the disordered phase. This result implies that in a typical case, less than 20, preferably less than 15, even more preferably less than 10, and very preferably less than 5 weight percent titanium in the media exists in an organized crystalline form, especially in the form of crystalline titanium dioxide. Thus, in its typical form the media mainly contains no crystalline titanium dioxide in its most preferred form essentially contains no crystalline titanium dioxide. Transmission electron microscopy and high resolution dispersive x-ray analysis (EDX) can be used to obtain an image of gold and titanium in the catalyst.

Disordered phase titanium can be distinguished from the mainly crystalline titanium dioxide microscopy HR-TEM and/or spectroscopy of Raman scattering of light. In addition, the disordered phase has a specific x-ray diffraction (XRD). However, the XRD analysis is less sensitive at detecting crystallizes the main phases of titanium dioxide, is no convincing evidence that these phases are not present in the media. The diffusion reflective spectroscopy in the UV-visible region (UV-VIS DRS) gives the third analytical method that can distinguish between the disordered phase titanium and crystalline titanium dioxide. In the typical case any of the HR-TEM, Raman spectroscopy or UV-VIS DRS can be used to identify disordered phase. In addition, x-ray absorption spectroscopy at the edge of the K-absorption bands of titanium (XANES) can be used as a Supplement to the HR-TEM, Raman spectroscopy and/or UV-VIS DRS to identify disordered phase. These methods are described in W0 98/0000415.

Download titanium on the silicon dioxide may be any loading, which allows to obtain an active catalyst in the method according to this invention. In a typical case, download titanium more than 0.02 mass%, preferably more than 0.1 weight percent based on the weight of silicon dioxide. In a typical case, the loading of titanium is less than 20 mass percent, preferably less than 10 weight percent based on the weight of silicon dioxide.

f. Mix media

In the catalyst of this invention can use any combination or mixture of the carriers a to e described here above.

When the reducing agent provides a source of titanium, then the method of the present invention can use any heterogeneous media catalisano well known to the person skilled in the art. Suitable non-limiting examples include silicon dioxide, aluminum oxide, metroselect, such as silicates, magnesium oxide, carbon, zirconium dioxide, titanium dioxide and mixtures thereof. When the reducing agent provides a source of titanium, then preferably the catalyst carrier is silicon dioxide.

The catalyst of this invention can, optionally, include at least one promoting metal. Any metal or metal ion, which increases the efficiency of the catalyst in the oxidation method of the present invention, can be used as the promoting metal. Factors contributing to the increased efficiency include, for example, increased transformation of the connection that you want to oxidize, increased selectivity of the desired oxidation product, the reduced formation of by-product such as water, and increased service life of the catalyst. Non-limiting examples of suitable promoting metals include the metals of groups 1 to 12 of the Periodic table of elements, and rare earth lanthanides and actinides, as stated in the CRC Handbook of Chemistry and Physics, 75thed., CRC Press, 1994. The promoting metal is preferably chosen srappy 2, includes beryllium, magnesium, calcium, strontium and barium; lanthanide rare earth metals including cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and actinide metals, especially thorium and uranium. More preferably, the promoting metal is silver, magnesium, calcium, barium, erbium, lutetium, sodium, lithium, potassium, rubidium, cesium or combinations thereof. In a typical case, the degree of oxidation promoting metal is from +1 to +7, but may be metal species. The silver may be present as an ion with a +1, as elemental metal or as an alloy with gold.

The total number of the promoting metal(s) deposited on the carrier in a typical case, more than 0.01, preferably greater than 0.10 and more preferably greater than about 0.15 weight percent calculated on the total weight of the catalyst. The total number of the promoting metal(s) deposited on the carrier, typically less than 20, preferably less than 15 and more preferably less than 10 mass% per the total weight of the catalyst. The person skilled in the art should understand that when using the titanate and the flesh up to 80 mass%. In the preferred embodiment, if the promoting metal is a metal of group 8, such as a platinum group metal, then the total concentration of metal(s) group 8 is less than 0.01 mass percent of the total catalyst composition.

The catalyst carrier is impregnated with the promoting metal from aqueous or organic solution containing a soluble salt of the promoting metal. You can use any salt promoting metal with adequate solubility, including, for example, nitrates, halides, carbonates, borates and carboxylates promoting metals, including, for example, acetates, oxalates, lactates, citrates, maleate and cinnamate and mixtures thereof. Water is the preferred solvent, but can also be used organic solvents, such as alcohols, esters, ketones, and aliphatic and aromatic hydrocarbons. In a typical case, the both molarity soluble salts promoting metal in the solution for impregnation is from about 0.001 M to the saturation point, preferably 0.005 to 0.5 M

Impregnation of the carrier connection gold, regenerating agent and, optionally, the promoting metal(s) can be performed in any order which gives Katalizator regenerating agent, or the order can be measured on the reverse first impregnation regenerating agent, and then bonding the gold. When the medium contains a tyrant, and the reducing agent does not contain a preferred impregnation of such carrier regenerating agent prior to impregnation compound of gold. When the media does not contain titanium and the reducing agent contains, then preferably the deposition of gold compounds is carried out before such a reducing agent. This is the last preferred embodiment allows to obtain the catalyst, which effectively uses the hydrogen in the way hydrocyclone that proved achieved low molar ratio of water to olefin oxide. Impregnation compound or compounds of the promoting metals can be performed before, after or simultaneously with the impregnation compound of gold and/or regenerating agent. In the preferred embodiment of the connection of the promoting metal is precipitated simultaneously with the connection of gold and regenerating agent. This preferred embodiment also leads to the high efficiency of hydrogen in the way hydrocyclone that proved achieved low molar ratio of water to olefin oxide. After each impregnation moistened media typically air-dried or, if necessary, in an inert at the remote ambient temperature (S) and 150C.

After the final impregnation and drying the carrier can optionally be washed. Stage washing typically involves immersing the impregnated carrier in a solvent and stirring the suspension at ambient temperature in air for 30 minutes to 10 hours. Any solvent which can dissolve the excess reducing agent and/or any undesirable ions, which is known to be present, it may be acceptable washing liquid.

Water is the preferred solvent, but can also be used organic solvents. Typically use approximately 10 ml of wash liquid up to 200 ml of wash liquid per gram saturated media. Stage leaching can be carried out once, or if desired, the washing can be repeated.

After an optional stage of washing the impregnated carrier can optionally, be treated with a solution of one or more ions of the promoting metals. This stage serves to fill the required ions promoting metals that may be lost during the previous flush. Processing simply involves immersing the impregnated carrier in a solution containing the required and the connection of the promoting metals, preferably 0.005 to 0.5 M

As a final optional stage impregnated carrier can be heated before use. Optional heating can be conducted in an atmosphere of oxygen or oxygen-containing gas, such as air, or in an atmosphere of inert gas, such as nitrogen, or in an atmosphere of a reducing gas such as hydrogen. Optional heating is typically carried out at a temperature between 100 and 800C, preferably between 120 and S. In the alternative case, the impregnated catalyst can condense in the reactor oxidation in an atmosphere comprising inert gas, such as helium and, optionally, one or more compounds selected from hydrocarbons, for example olefin, which is necessary to oxidize hydrogen and oxygen, at a temperature between ambient temperature (S) and 600C.

The above catalyst can be used in the methods of hydrocyclone, similar to the methods described in patent PCT publications WO 98/00413, WO 98/00414 and WO 98/00415. In these methods, the olefin in contact with oxygen in the presence of hydrogen, a gold-titanium catalyst and, optionally, a diluent to obtain the corresponding olefin oxide. Can ispolzovanie various organic residues. Preferred olefins include3-12-olefins. More preferred are3-8-olefins, and most preferred is propylene. In a typical case, the amount of olefin in the flow of incoming material is greater than 1, preferably greater than 10 and more preferably more than 20 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and optional diluent. In a typical case, the amount of olefin is less than 99, preferably less than 85, and more preferably less than 70 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and optional diluent. The amount of oxygen in the flow of raw material is preferably more than 0.01, more preferably more than 1 and most preferably greater than 5 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and optional diluent. The amount of oxygen preferably is less than 30, more preferably less than 25, most preferred less than 20 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and optional diluent. Suitable amounts of hydrogen in the flow of the lar percent per total number of moles of olefin, oxygen, hydrogen, and optional diluent. Suitable amounts of hydrogen in a typical case, less than 50, preferably less than 30, and more preferably less than 20 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and optional diluent.

The diluent can be any gas or liquid that does not inhibit the method of the present invention. In gas-phase method suitable gaseous diluents include, but are not limited to, helium, nitrogen, argon, methane, carbon dioxide, water vapor m mixtures thereof. In liquid-phase method, the diluent can be any stable to oxidation and thermally stable liquid. Suitable liquid diluents include chlorinated aromatic hydrocarbons, preferably chlorinated benzenes, such as chlorobenzene and dichlorobenzene; chlorinated aliphatic alcohols, preferably chlorinated C1-10-alkanols, such as chloropropanol; and liquid polyethers, polyesters, polyesters, and polyalcohol. If using gaseous diluent, the amount of diluent in the flow of raw materials typically greater than about 0, preferably greater than 0.1, and more and diluent. The amount of gaseous diluent is typically less than 90, preferably less than 80, and more preferably less than 70 molar percent based on the total number of moles of olefin, oxygen, hydrogen, and diluent. If you use liquid diluent, then the amount of diluent in the flow of raw materials in a typical case is larger than 0, preferably greater than 5 weight percent calculated on the total weight of the olefin and diluent. The amount of liquid diluent typically less than 99, preferably less than 95 mass% per the total weight of the olefin and diluent.

How hydrocyclone can be carried out in a reactor of any conventional design suitable for gas - and liquid-phase methods. The method is typically carried out at a temperature which is above ambient temperature (C) and lower than S. Since the advantage of the catalysts obtained the preferred methods of this invention is that a smaller quantity of water than similar catalysts prepared by the methods of the prior art, the method of hydrocyclone using the catalyst of this invention can be conducted at temperatures higher causesa lower than C, preferably lower than S. Operation at higher temperatures provide credit water vapor generated educated warmth. In accordance with this method hydrocyclone can be integrated into the overall scheme of the installation, where the heat received from the water vapor, is used to actuate the additional processes, such as separation of ethylene oxide from the water.

Pressure method hydrocyclone is preferably from atmospheric to 400 psi (2758 kPa), more preferably from 150 psi (1034 kPa) to 250 psi (1724 kPa). For gas-phase method the hourly average gas flow rate (GHSV) of the olefin may be varied within wide limits, but in the typical case it is more than 10 ml of olefin per ml catalyst per hour (h-1), preferably more than 100 h-1and more preferably more than 1000 h-1. In a typical case, the GHSV of the olefin is less than 50000 h-1preferably less than 35000 h-1and more preferably less than 20000 h-1. Hourly average gas flow rate for components of oxygen, hydrogen and diluent can be determined from the average hourly rate of gas supply of olefin, taking into account the relative tre the molar percent, preferably more than 0.3 molar percent, and more preferably more than 0.4 molar percent. The term “transformation (conversion) of the olefin” is defined as the molar percentage of the olefin in the flow of raw materials, which interacts with the formation of products. In the typical case reaches the selectivity of the conversion of the olefin oxide, which is more than 60 molar percent, preferably more than 70 molar percent, and most preferably more than 90 molar percent. The term “selectivity conversion to olefin oxide” is defined as the molar percentage of the reacted olefin which forms the product of the olefin oxide.

It is desirable to achieve good efficiency of hydrogen in the way hydrocyclone. The efficiency of hydrogen can be optimized to achieve the lowest molar ratio of water to olefin oxide as possible. In the method of the present invention the molar ratio of water to olefin oxide in the typical case of more than 2:1, but typically less than 35:1. In preferred embodiments of the present invention the molar ratio of water to propylene oxide best way is less than 10:1 and more preferably less than 5:1.

When the activity of the gold-TC. One regeneration method includes heating the deactivated catalyst at a temperature between 150 and 500 ° C in the gas for regeneration, containing any component of hydrogen, oxygen and/or water and, optionally, an inert gas, at a temperature preferably between 200 and 400C. Hydrogen, oxygen and/or water preferably ranges from 2 to 100 molar percent of the regeneration gas. Suitable inert gases are directionspanel and include, for example, nitrogen, helium and argon.

The invention will be more clear when considering the following examples, which are intended solely for exemplary use of the invention. Other embodiments of the invention will be clear to the person skilled in the art upon consideration of this specification or practice of the invention, as described here. Unless otherwise noted, all percentages are based on molar percentage.

Example 1

Chloraurate sodium [NaAuCl4H2O, 0.28 g) was dissolved in deionized water (42 ml). In a round bottom flask (100 ml) is placed spheres of silicon dioxide (2 mm diameter, 30 nm pores, 27,41 g) and heated them at 60C for 1 h in vacuum (30 mm Od) on a rotary evaporator. Silicon dioxide is impregnated with R the CA will not get dry solid material. Dry the solid material is removed from the flask and dried in air at 60C for 12 h

Titaniumtetrachloride (0.27 g) was dissolved in methanol (22.5 ml). Processed gold spheres of silicon dioxide (9.0 g) obtained here, as described above, placed in a round bottom flask (50 ml), the air from which it is pumped for 2 h on a rotary evaporator in a water bath at 80C. The solution titaniumtetrachloride added slowly to the silica in vacuum at room temperature. The flask is returned to the water bath at 80 ° C and rotate in vacuum for 3 hours Solid material removed from the flask, washed with methanol (55 ml), filtered and dried at room temperature. The sample is placed in an oven and calicivirus in air using the following scheme calcination: heat from room temperature to C for 5 h, then maintained at C for 3 h and cooled to room temperature to obtain a catalyst comprising gold on a titanium containing media. Download gold of 0.5 mass%; the loading of titanium to 0.5 mass%, the atomic ratio of Na:Au 1:1, as determined by analysis neutron activation (NAA).

The catalyst obtained here, as described above, experience in the process of hydrocyclone cut is acai flows of helium, oxygen, hydrogen and propylene. Part of the flow of raw material is 10 percent hydrogen, 10 percent oxygen and 20 percent of propylene, and the rest is helium. Propylene, oxygen and helium are used as pure streams; the hydrogen is mixed with helium with the formation of a mixture of 202/80 (vol/vol). The total bit rate is 160 cm3/min (GHSV of olefin 480 h-1).Suppression of atmospheric temperature method is 160C. The products are analyzed using a managed computer gas chromatograph (Chrompack columnTMPoraplotTMS, 25 m) with the results shown in the table.

The impregnated catalyst of example 1 provides the initial time, the conversion of propylene 0.36% and the selectivity of the formation of ethylene oxide 92%, with 160S. The molar ratio of water to propylene oxide is only 2,04:1. The performance of propylene oxide calculated at 8,3 g RO:kg cat./hours After 24 hours the conversion is a 0.27 molar percent and the molar ratio of water to propylene oxide is 4.18:1. The catalyst was recovered at 450C in a stream of oxygen (20% in helium) without loss of activity.

Example 2

The media, including the pores 110 ) was caliciviral to remove residual organic substances according to the following scheme: heat from 80 to 300C for 4 h, incubated at 300C for 2 h, then heated from 300 to 550C for 4 h, incubated at C for 2 h, then cooled to 80 ° C and store in a sealed vial at room temperature. Whether sphere (12,16 g) was placed in a round bottom flask, which is placed on a rotary evaporator and pumped her air at room temperature for 1 h

D-Gluconate sodium (Aldrich, 2,0760 g) dissolved in double deionized water (18 ml). Spheres impregnated with a solution of gluconate in vacuum with vigorous agitation on a rotary evaporator. The spheres are then dried in a vacuum on a water bath as follows: 60 min at room temperature, 30 min at 35C, 30 min at 60C, then cooled to room temperature.

Hartlot acid (HAuCl4H2O, 0,3729 g) dissolved in double deionized water (18 ml). Spheres impregnated with a solution of gold in vacuum under vigorous stirring on a rotary evaporator. The impregnated spheres are then dried using the following chart: 60 min at room temperature, 30 min at 35C, 30 min at 60C, then cooled to room temperature. During drying the recovery of gold can be observed by the color change from yellow to greenish-purple. The catalyst techenie specified period the color of the catalyst becomes completely purple.

Impregnated, dried spheres (4.72 in) immersed in deionized water (50 ml) and incubated with occasional stirring for 30 minutes the Water is decanted, add fresh water (50 ml) and the mixture stand for another 30 minutes the Water is decanted, add fresh water (50 ml) for the third time and the mixture stand for an additional 30 minutes At the last wash add an aqueous solution of sodium nitrate (0,9995 g in 50 ml water), and the mixture is left to stand for 30 minutes then the mixture is filtered and dried in a nitrogen atmosphere at 80C overnight. The material is then calicivirus in air using the following scheme to obtain the catalyst of the invention: heat from 80 to 200C for 4 hours, heated from 200 to 500 ° C for 4 h, incubated at 500C for 2 h, then cooled to 80 ° C and store in a sealed vial at room temperature. Download gold 1,32 mass percent; download titanium 1,98 weight percent; the atomic ratio of Na:Au 4,6:1, as determined by NAA.

The catalyst was tested in the process of hydrocyclone propylene to propylene oxide in the manner described in example 1, except using 3 g of the catalyst and the raw material stream includes 19.8 percent propylene, 10.1 percent oxygen and 9.8 the initial catalyst of example 2 provides the conversion of propylene 0.40 percent, the selectivity of the formation of propylene oxide 87 percent performance 5.8 g PO/kg cat./including the Deactivation of the catalyst is not observed for up to 15 hours of operation. Found at 180C conversion of propylene is 0.64 percent; selectivity of the formation of propylene oxide is 72% and the capacity is 8.0 g PO/kg cat./'clock regenerate the Catalyst at 300C in air. Also effective regeneration in hydrogen atmosphere.

Example 3

The media, including titanium dispersed on silica (spheres 2-4 mm; surface area 360 m2/g; average pore diameter of 110 ) calicivirus using the following scheme: heat from 80 to 300C for 4 h, incubated at 300C for 2 h, then heated from 300 to C for 4 h, incubated at C for 2 h, then cooled to 80 ° C and store in a sealed vial at room temperature. Whether sphere (12,12 g) placed on a rotary evaporator and pumped the air at room temperature for 1 h

Citric acid (Aidrich, 0,7181 g) and sodium chloride (Fischer, 0,1727 g) dissolved in double deionized water (18 ml). Spheres impregnated with the solution on a rotary evaporator under vacuum and ene 60 min at room temperature, 30 min at 35C, 30 min at 60C, then cooled to room temperature. Hartlot acid (HAuCl4H2O, 0,2996 g) dissolved in deionized water (18 ml). Spheres impregnated with a solution of gold on a rotary evaporator under vacuum and under vigorous stirring. The impregnated spheres are then dried, as indicated in the previous stage, after which the vacuum is removed. The dried material is then dried in a nitrogen atmosphere at 80 ° C overnight and then calicivirus no air using the following schema heating: heat from 80 to 200C for 4 hours, heated from 200 to 500C for 4 h, incubated at 500C for 2 h, then cooled to 80 ° C and store in a sealed vial at room temperature to obtain a catalyst of the invention. Download gold 1,08 mass percent; download titanium to 2.7 mass%; atomic ratio of Na:Au and 3.8:1, as determined by NAA.

The catalyst was tested in the process of hydrocyclone propylene to propylene oxide in the manner described in example 2, with the results shown in the table. When 160S conversion of propylene is 0.24 percent; selectivity of the formation of propylene oxide is 87% and the performance is 3.3 g PO/kg cat./including the Deactivation of the catalyst is not what adowanie is 68% and the performance is 5.2 g PO/kg cat./PM After regeneration of the catalyst at 300C in an atmosphere of hydrogen, the catalyst provides the transformation of 0.45 percent, a selectivity of 85 percent and performance 6.2 g PO/kg cat./h at 160S.

Example 4

The media, including titanium dispersed on silica (spheres 2-4 mm; surface area 360 m2/g; average pore diameter of 110 ) were caliciviral to remove residual organic substances according to the following scheme: heat from 80 to 300C for 4 h, incubated at 300C for 2 hours, heated from 300 to 550C for 4 hours; maintained at C for 2 h, then cooled to 80 ° C and store in a sealed vial at room temperature. Whether the media (25,23 g) was placed in a round bottom flask, which is placed on a rotary evaporator and the air is pumped at room temperature for 2 h D-Gluconate potassium (Aldrich, 99%, 4,513 g) dissolved in double deionized water (36 ml) and the resulting solution has a pH 7,94. The carrier is impregnated with a solution of gluconate in vacuum with vigorous agitation on a rotary evaporator.

The carrier is then dried on: a rotary evaporator under vacuum using a water bath as follows: 60 min at room temperature, 30 min priestarautu in double-deionized water (36 ml) to form a solution, having a pH level of 1.32. Soaked gluconate carrier is impregnated with a solution of gold in vacuum and with vigorous agitation on a rotary evaporator. The impregnated carrier is then dried using the following schema: 90 min at room temperature, 30 min at 35C, 30 min at 60C, then cooled to room temperature. During the initial drying at room temperature, the medium changes color from yellow to yellow-green. At 60C, some particles of the medium become purple. The dried material is subjected to final drying overnight in a drying Cabinet at 80 ° C in nitrogen atmosphere with getting painted in purple color of a catalyst comprising gold on the media, including titanium dispersed on silica.

The catalyst obtained as described here above (13,14 g), immersed in double-deionized water (100 ml) with formation of a mixture with a pH 4,14, which stand with occasional stirring for 70 min (pH 3,88). The water is decanted and add fresh water (100 ml) and the mixture is left to stand for 1 h (pH 4,48). Water again decanted, add fresh water (100 ml) for the third time and the mixture is left to stand for an additional 60 min (pH 5,06). After that, the mixture is filtered and the room temperature. The composition of the catalyst: AI 1,11 mass%; Ti mass of 1.80%; atomic ratio:AI 2,4:1, as determined by NAA.

The catalyst (3 g) experience in the process of hydrocyclone propylene to propylene oxide in the manner described in the above example 2. The conditions and the method shown in the table. When carrying out the method at a temperature of between 140 and 160S reach the conversion of propylene between 0.25 and 0.36 percent and the selectivity of formation of propylene oxide is greater than 80 percent. The catalyst effectively regenerate in an atmosphere of hydrogen at 300C.

Example 5

A container with a volume of 14 liters with lid rinsed for 15 minutes with dry nitrogen. In the container is transferred Tetra(ethyl)orthosilicate (11,276 g). The silicate with vigorous stirring piperonyl titanium (236,4 g). The resulting solution is heated to 91P with continuous stirring while blowing nitrogen and kept at this temperature for a total time of heating 2 hours the Solution is then cooled to 1.9 C in a water bath for 2 hours In a polypropylene container with a volume of 16 gallons placed aqueous solution of hydroxide of tetrapropylammonium (9874 g, 40 wt.%-hydrated TRAIN) having a low alkali content (less than 20 meters D. Na). To a solution of the DISTRICT is also pumped through the outer coil stainless steel size 1/4 inch (0.6 cm), immersed in a bath of dry ice-acetone (t approximately-25C) to achieve more rapid cooling and better temperature control. The solution is cooled down to-4C. The cooled solution of the alkoxide is pumped into the container volume 16 gallons at a speed of 150 ml/min. and the Temperature of the mixture increases slowly, reaching-2C after adding about half of the alkoxide solution.

Finally, to the mixture was added with stirring deionized water (5432 g). The final temperature of the mixture is 8.2 C. the Mixture is stirred for 18 h at room temperature. After that, the stainless steel autoclave with stirring at 200 rpm spend hydrothermal synthesis. The autoclave is heated up to 160S and maintain this temperature for 4 days. The reactor was then cooled to room temperature and the product is pumped from the reactor. The product contains a large organic layer, which is separated from the rest of the mixture. pH of the Aqueous lactic fluid regulate approximately 8,7 nitric acid (1,5 BC) and the product produce by centrifugation at 3000 rpm Solid material was again dispersed in deionized water and centrifuged again. The resulting solid material is dried at 110C for 12 h with th is brilliant heated 5 h at S. Powder x-ray diffraction analysis shows that the material is clean titanosilicates phase structural type MFI.

Titanium containing medium (30 g) obtained above, calicivirus in air at C for 8 h and cooled to room temperature. Get the solution, including hartlot acid (0,0035 g) and sodium acetate (0.5 g) in methanol (35 g). The sample is dried in vacuum at room temperature until, until it becomes loose, then heated in a vacuum to 100C for 2 hours to obtain a catalyst of the present invention.

The catalyst (30 g) experience in the process of hydrocyclone propylene to propylene oxide in the manner described in example 1 except that the total flow rate of 15.0 l/min; pressure of 210 psi (1448 kPa) and the temperature of the casing of the reactor is 160S. In the beginning, the catalyst was heated at 140 C for 5 h in an atmosphere of helium; then within 10 minutes of entering the propylene and hydrogen, and then to add oxygen flow. After receipt of propylene oxide at a constant speed within 1 h the temperature decrease at intervals of 15 ° C operating temperature 160S. Reach 3.2 percent conversion of propylene with a selectivity of the formation of propylene oxide 5 g), obtained as in example 5, calicivirus in air up to 600C for 8 h and cooled to room temperature. Get a solution in methanol containing sodium acetate (0.20 g in 25 g of methanol and to this solution was added a second solution in methanol containing hartlot acid (0.06 g in 5 g of methanol).

The resulting solution used for impregnation of titanium silicate initial wetting. Impregnated silicate is then dried in a vacuum drying Cabinet for 30 min and then heated in an oven at 60C for 1 h to obtain a catalyst comprising gold on a titanium containing media. Some gold particles can be seen using transmission electron microscopy high resolution. Mie scattering detects weak strip of metallic gold. As determined by x-ray photoelectron spectroscopy, 60 mass% of the total content of gold is metallic gold.

The catalyst (3.0 g) experience in the process of hydrocyclone propylene to propylene oxide in a manner similar to the method of example 5. Raw stream contains propylene (35 percent), hydrogen (10 percent), oxygen (10 percent), and the rest of the number is helium. the temperature IS the conversion of propylene is 1.5% with a selectivity of formation of oxide extended 99 percent and the molar ratio of water/RO 3,2.

1. The method for the catalytic compositions for the oxidation of the olefin with oxygen in the presence of hydrogen to olefin oxide comprising gold on a titanium containing medium, characterized in that the method comprises the impregnation of the catalyst carrier with a solution of gold compounds and a solution of a reducing agent, where the reducing agent and/or catalyst carrier includes titanium, under conditions sufficient to obtain a catalytic composition.

2. The method according to p. 1, characterized in that the connection of the gold selected from Hartley acid, chloraurate sodium, chloraurate potassium, cyanide of gold, mixed potassium cyanide and gold, trichlorohydrin diethylaminoethoxy acid, acetate, gold, alkylchlorosilanes and Euratom alkali metals.

3. The method according to p. 1 or 2, characterized in that the loading of gold more than 10 parts per million by weight calculated on the total weight of gold and the media.

4. The method according to any one of paragraphs.1-3, characterized in that the regenerating agent is an organic compound which does not contain titanium and which is selected from sugars, carboxylic acids and their salts, alcohols and their alkoxide salts, alkanolamine, bonds alkylamines and mixtures thereof.

and ISO-propanol, ethanolamine, acetic acid, lactic acid, citric acid, maleic acid, cinnamic acid, sodium acetate, sodium lactate, sodium citrate, cinnamate sodium maleate, sodium and mixtures thereof.

6. The method according to any one of paragraphs.1-5, characterized in that the molar ratio of reducing agent to the gold more than 0.5:1.

7. The method according to any one of paragraphs.1-3, characterized in that the reducing agent containing titanium and selected from technologicheskij compounds and coordination compounds of titanium.

8. The method according to p. 7, characterized in that technologicheskoe compound selected from alkylsilanes compounds and cyclopentadienylmagnesium connections and coordination compound selected from titanium alkoxides of titanium and titanium carboxylates.

9. The method according to p. 8, characterized in that the coordination compound of titanium is titaniumalloy.

10. The method according to any of paragraphs.1-9, characterized in that (a) the carrier catalyst containing titanium and selected from titanium dioxide, titanosilicates, titanium dispersed on silicon dioxide, titanates promoting metals, titanium dispersed on the silicates promoting metals and their oxides of aluminum, aluminosilicates, Zirconia, magnesium oxide, carbon, titanium dioxide and mixtures thereof; or (C) as a reducing agent, and a carrier containing titanium.

11. The method according to any of paragraphs.1-10, characterized in that the loading of titanium on the carrier by more than 0.02 wt.% and less than 20 wt.% in the calculation of the mass media.

12. The method according to any of paragraphs.1-11, characterized in that the carrier is impregnated with at least one compound promoting metal, and the promoting metal selected from metals of group I, which includes lithium, sodium, potassium, rubidium and cesium; group II, including beryllium, magnesium, calcium, strontium and barium; silver, lanthanoid rare-earth metals, actinide metals of the Periodic table and mixtures thereof.

13. The method according to any of paragraphs.1-12, characterized in that the total concentration of the promoting metal(s) is from more than 0.01 to less than 20 wt.% calculated on the total weight of the catalyst.

14. The method according to any of paragraphs.1-13, characterized in that after impregnation the carrier is washed and, optionally, after washing the carrier is treated with a solution containing at least one promoting metal.

15. The method according to any of paragraphs.1-14, characterized in that the impregnation Prov the ski solvents and their mixtures, at a temperature of 21 - 100C.

16. The method according to any of paragraphs.1-15, characterized in that after impregnation and any optional stages of washing and processing the promoting metal catalyst is heated in an atmosphere of oxygen or oxygen-containing gas, or heated in an inert atmosphere or heated in a reducing atmosphere at a temperature higher than S and lower than 800C.

17. Catalytic composition for the oxidation of the olefin with oxygen in the presence of hydrogen to olefin oxide comprising gold on a titanium containing medium, where the catalyst was prepared by the method according to any of paragraphs.1-16.

18. The method of oxidation of the olefin in the olefin oxide comprising contacting the olefin with oxygen in the presence of hydrogen and a catalyst comprising gold on a titanium containing media, in terms of the way enough to get the olefin oxide, and the catalyst was prepared by the method according to any of paragraphs.1-16.

19. The method according to p. 18, characterized in that the olefin is propylene and olefin oxide is propylene oxide.

 

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