Mesoporous materials with active metals

FIELD: technological processes; chemistry.

SUBSTANCE: method involves reaction of raw material containing organic component with a catalyst composition. Processing method is selected out of alkylation, acylation, hydrotreatment, demetallisation, catalytic deparaffinisation, Fischer-Tropsch process and cracking. Catalyst composition includes mainly mesoporous silicon dioxide structure containing at least 97 vol.% of pores with size in the interval from ca. 15 Å to ca. 300 Å, and at least ca. 0.01 cm3/g of micropores. Mesoporous structure features at least one catalytically and/or chemically active heteroatom in amount of at least ca. 0.02 mass %, selected out of a group including Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W and their combinations. The catalyst composition radiograph has one 0.3° to ca. 3.5° peak at 2θ.

EFFECT: highly efficient method of organic compound processing in the presence of catalyst composition without zeolite.

20 cl, 31 ex, 17 tbl, 22 dwg

 

CROSS-REFERENCE TO RELATED APPLICATIONS

The present invention is a partial continuation of application U.S. serial No. 09/955227 dated November 27, 2001, incorporated here by reference, which is a partial continuation of application U.S. serial No. 09/390276 of 7 September 1999, accepted now as U.S. patent No. 6358486 B1, which is a stated priority.

Background of the invention

1. The technical field to which the invention relates.

The present invention relates to mesoporous materials, especially catalytic materials, and use of mesoporous materials for the conversion of organic compounds, especially hydrocarbons.

2. Prior art

The majority of today's technologies hydrocarbon processing based on zeolite catalysts. Zeolite catalysts are well known in the art and are well-ordered porous systems with uniform pore sizes. However, these materials tend to have either only micropores or mesopores. Micropores are defined as pores having a diameter of less than about 2 nm. The mesopores are defined as pores having a diameter in the range from about 2 nm to about 50 nm.

Because these reactions of hydrocarbons limited by mass transfer, utilizator with the ideal pore size will facilitate the transport of reactants to the active catalytic centers and the transfer of products from the catalyst.

There is still a need for improved materials with functional centres within the porous structure to processes for the catalytic conversion and/or adsorption of hydrocarbons and other organic compounds.

The INVENTION

In this application proposes a method of processing organic compounds. The method includes: (a) providing a composition that includes, essentially, the mesoporous structure of silica containing at least 97% pores with pore size in the range from about 15 Å up to about 30 Å and with the volume of micropores, at least about a 0.01 cm3/g, where the mesoporous structure of the embedded catalytically and/or chemically active heteroatoms in the amount of at least about 0.02 wt.%, selected from the group consisting of Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Pt and W, and where the said catalyst has an x-ray with one peak between 0.3° to 3.5° 2θ; and (b) interaction of organic raw materials under the reaction conditions mentioned catalyst, where the processing method selected from the group consisting of alkylation, acylation, oligomerization selective oxidation, Hydrotreating, isomerization, demetilirovania, catalytic dewaxing, hydroxylation, hydrogenation, maximiliane, dehydrogenation, cracking adsorbsia.

In one aspect, the invention relates to an improved catalytic process for demetilirovania and desulfurization of mineral oils, preferably residual fractions with undesirable high content of heavy metals and/or sulfur and/or nitrogen and/or carbon residue on Conradson (PPC). Particularly, the invention relates to a method of Hydrotreating to reduce the content of heavy metals, sulfur, nitrogen and KUO mineral oils, again preferably containing residual hydrocarbon components.

Residual fractions of mineral oil obtained by atmospheric or vacuum distillation of crude oil; they usually have a high content of metals, sulfur, nitrogen and KUO. This is because all metals and KUO, present in the original crude oil remain in the residual fraction, and a disproportionate amount of sulfur and nitrogen source of crude oil remains in this fraction. The major polluting metals are Nickel and vanadium with the audience sometimes with iron and small amounts of copper.

The content of heavy metals, sulfur, nitrogen and KUO in the residual fractions usually limits their effective use as feedstock for the subsequent catalytic processing, such as catalytic cracking and hydrocracking. Metal contamination on the put on special catalysts for these methods cause cracking and premature aging of the catalyst and/or undesirable side reactions, such as cracking to coke, petroleum gas and hydrogen. During the process the FCC (fluid catalytic cracking) of the way the majority of the sulphur hits the FCC coke-catalyst, which is burned during regeneration, leading to a significant allocation of SOx. Another significant part of the residual sulfur enters the cracking products, such as gasoline and light cycle oil (optional component for diesel fuel and fuel for home heating). Part of the nitrogen leads to the separation of NOxand part of the nitrogen basic nitrogen compounds) associated with the active centers of FCC catalyst and makes them ineffective. KUO, which is a measure of the tendency of molecules to coxworthy more than to cracking and/or distillation, is also undesirable property for downloadable flows during catalytic cracking. At high temperature, used in catalytic cracking, the molecules tend to KUO, thermally and/or catalytically destroyed to coke, light gases and hydrogen. Catalytic cracking usually turns hydrocarbons lighter than the residual fraction, which typically have a density according to API less than 20. Often the raw material for cracking is a gas installation for coking and/or crude oil, top zipper vacuum columns and so on, and this raw material has a PI-density from about 15 to about 45. As these feedstocks for cracking distillates are, they do not contain a significant share of large molecules, in which the concentrated metals. Such cracking is usually carried out in a reactor operating at a temperature of from about 425 to 800°C, a pressure of about 1 to 5 atmospheres, and a flow rate of approximately 1 to 1000 WHSV (hourly average mass flow rate).

Pollutant metals and sulphur create similar problems in hydrocracking operations that are normally carried out on raw materials, even easier than raw material for cracking. Typical conditions of the hydrocracking reactor comprise a temperature from 200 to 550°and a pressure of from 700 to 20,000 kPa.

Obviously, there is a need for an effective method of reducing the content of metals and/or sulfur and/or nitrogen and/or KUO in hydrocarbons and, particularly, in the residual oil fractions. Although the technology to achieve this in the case of distilled fractions largely developed, attempts to apply this technology to the residual fractions fail because of the very rapid deactivation of the catalyst, mainly due to contamination by metals and coke deposition.

BRIEF DESCRIPTION of DRAWINGS

Different ways of implementation are described below with reference to the drawings, in which

Figure 1 is a radiograph ("RDG") mesoporous mA is eriala of example 1;

Figure 2 is a snapshot of the transmission electron microscope ("TEM") mesoporous material of example 1;

Figure 3 is a graph showing a distribution of pore sizes of mesoporous material of example 2;

Figure 4 is a RDH mesoporous material of example 2;

Figure 5 is a RDH mesoporous materials of examples 3A, 3B and 3C;

6 is a graph showing a distribution of pore sizes of mesoporous material of example 3A;

Fig.7 is a RDH vanadium-containing mesoporous material of example 5;

Fig is a RDH titanium containing mesoporous material of example 6;

Fig.9 is a graph showing the sorption isotherms of nitrogen in the titanium-containing mesoporous material of example 6;

Figure 10 is a graph showing a distribution of pore sizes titanium-containing mesoporous material of example 6;

11 is a RDH mesoporous materials of examples 7, 8 and 9;

Fig is a RDH aluminum and vanadium-containing mesoporous material of example 10;

Fig is a graph showing a distribution of pore sizes aluminum and vanadium-containing mesoporous material of example 10;

Fig is a RDH iron metaphoricalmargarita of example 11;

Fig represents a spectrum in the UV and visible regions of iron-containing mesoporous material of example 11;

Fig is a graph showing a distribution of pore sizes of iron-containing mesoporous material of example 11;

Fig is a RDH chrome-containing mesoporous material of example 13;

Fig is a spectrum in the UV and visible regions of chromiferous mesoporous material of example 13;

Fig is a graph showing the size distribution of mesopores mesoporous material of example 13;

Fig is a RDH molybdenum-containing mesoporous material of example 15;

Fig is a spectrum in the UV and visible regions mesoporous material of example 15; and

Fig is a graph showing the size distribution of mesopores mesoporous material of example 15.

A DETAILED DESCRIPTION of the PREFERRED OPTION(S)

The catalyst according to the present invention includes a stable three-dimensional porous silicon dioxide with essentially mesoporous structure. This silicon dioxide is non-crystalline, but regular (pseudocrystalline structure. Mesoporous materials are described in U.S. patent No. 6358486 B1, which is incorporated here by reference in its entirety.

Amorf the first material based on silicon dioxide according to the present invention usually contains mesopores, and micropores. Micropores are defined as pores with a diameter of less than about 2 nm. The mesopores are defined as pores with a diameter from about 2 nm to about 50 nm. Inorganic oxide material of the present invention has a volume percent mesopores of at least about 97%, and preferably at least about 98%.

The preferred method of preparation of a porous catalyst carrier containing silicon dioxide, is described in U.S. patent No. 6358486 B1. The average size of the mesopores of the preferred catalyst, defined by N2-Parametrii, is in the range from about 2 nm to about 25 nm.

The catalyst includes, and is functionalized, or one or more heteroatoms catalytically active metals embedded in porous silica structure. Heteroatoms of catalytically active metals (i.e. silicon atoms) can be selected from groups IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIII, IVA and IIIA of the Periodic system of elements. Suitable heteroatoms metals include, for example, aluminum (Al), titanium (Ti), vanadium (V), chromium (Cr), zinc (Zn), iron (Fe), tin (Sn), molybdenum (Mo), gallium (Ga), Nickel (Ni), cobalt (Co), indium (In), zirconium (Zr), manganese (Mn), copper (Cu), magnesium (Mg), palladium (Pd), platinum (Pt) and tungsten (W). Embedded heteroatoms can be isolated and/or distributed in the form to the of esterow in a porous matrix. They can be in atomic form or molecular form (e.g., oxide). The content of heteroatoms in the catalyst is at least about 0.02 wt.%. The atomic ratio of heteroatoms to the silicon atoms in the catalyst may vary up to about 0.9, preferably from about 0.0001 to about 0.5.

The composition according to the present invention has a characteristic x-ray ("RDG"), which is present at least one peak 2θ 0.3° to 3.5°that corresponds to the interplanar distances from 25 Å up to 440 Å. Tests with nitrogen adsorption shows that adjustable pore size is in the range from about 15 Å (1.5 nm) to about 300 Å (30 nm)and surface area in the range from about 300 m2/g to about 1,250 m2/g, and a pore volume from about 0.3 cm3/g to about 2.5 cm3/year

The composition according to the present invention has a three-dimensional random-linked system of mesopores, which promotes mass transfer of the reactants and products, and prevents blocking of the pores.

As a rule, mesoporous material based on silicon dioxide of the present invention is prepared from a synthetic mixture containing at least one source of silica, at least one source of heteroatoms and at least one performership organic with Andrenyi agent.

In the first step of the method of preparation of the catalyst according to the invention a source of silica, a source of heteroatoms and organic standard agent(you) are combined in aqueous solution with formation of a synthetic mixture (usually gel).

At the intermediate stage of the method of the volatile components of the synthetic mixture (for example, water, alcohol) are removed by conventional means, such as drying in the presence or absence of forced air flow. Drying can be performed, for example, in the range from 40°With up to approximately 130°for up to about 72 hours, more preferably from about 60°C to about 120°C for 6 to 36 hours.

At the final stage of organic performership standard agent(you) is removed by conventional means, such as calcination or extraction. Typically, the calcination is carried out at a temperature from about 450°With up to approximately 900°in the oxygen-containing gas (e.g. air) for 2 to 20 hours, preferably from 540°With up to approximately 700°With for about 4 to 15 hours. The extraction can be performed using organic solvents at temperatures from about 30°C to about 100°depending on the used solvent. Some non-toxic or slightly toxic alcohols are preferred as solvents.

More the positive method can include aging synthetic mixture at 10° C for up to 24 hours before removing the volatile components of the synthetic mixture.

Additionally, a synthetic mixture can be heated in an autoclave at a temperature of from about 100°C to about 220°C for about 10 days, preferably at a temperature of from about 120°With up to about 200°C for up to 96 hours before removing performership agent. Stage heating in the autoclave can adjust misopristol so as to satisfy specific requirements. During the heating of inorganic particles such as silicon or aluminum, coalescent with the formation of the inorganic skeleton, while performership agent forms aggregates, giving form inorganic skeleton. The size distribution of the aggregates determines the size distribution of mesopores. However, the size of aggregates, mainly depends on the nature performership agent heating temperature and duration of heating. Therefore, when a certain performership the agent misopristol the final material can be adjusted by manipulating the temperature and time of heating.

In particular, in the first stage, the source of silicon dioxide, or a precursor of silicon oxide may be silicon compound containing some organic groups. Such compounds can be the alkoxide is mi, for example tetraethylorthosilicate ("TEOS"), or silatrane, for example triethanolamine-substituted silatranes. Alternatively, the source of silicon dioxide may be inorganic, such as anhydrous or aqueous silica gels or hydrogels of silica. The source of silicon dioxide can also be geothermal silica, but to ensure the reactivity of the preferred non-crystal source.

Organic performership standard agent preferably contains a hydroxyl (-OH) groups, which form hydrogen bonds with inorganic particles (i.e. silicon dioxide and the heteroatom). They can have atoms with electron pair, which is associated with silicon or heteroatoms. Such organic standard agents include glycols (e.g. propylene glycol, glycerin, diethylene glycol, triethylene glycol, tetraethylene glycol), alkanolamine (for example, triethanolamine ("tea"), triisopropanolamine), dibenzoate of ietilpigos, triethylenediamine, starch and sulfolan. Organic standard agent should have a boiling point above 150°C, preferably above about 180°C.

Source heteroatoms may or may not contain organic groups and is usually added in the form of a solution. For example, in the case of the aluminum source may be an alkoxide of aluminum (n is an example, isopropoxide aluminum), aluminum oxide, aluminum hydroxide, aluminum nitrate, aluminum sulfate or aluminum chloride.

Synthetic mixture may also include alkali or acid to adjust the pH of the mixture. Alkali typically include organic bases, such as the hydroxide of tetraethylammonium ("TEON") and the other of tetraalkylammonium hydroxide, urea and the like, or inorganic bases such as ammonium hydroxide, sodium hydroxide, sodium carbonate, and the like.

Solvents, reaction conditions, the order of adding and mixing the components and pH may depend on the heteroatom and must be chosen in such a way as to avoid premature separation (e.g., deposition) of the heteroatom. Premature separation can lead to failure of the introduction of heteroatoms in the structure of silicon dioxide.

The composition according to the invention can be used as a catalyst, co-catalyst (part of the catalyst), the catalyst carrier, adsorbent, and molecular sieves. Depending on the functionality implemented heteroatoms composition may be weak, medium or strong acidity, respectively, it can catalyze the cracking, isomerization, alkylation, acylation, oligomerization/polymerization, de-hydration of organic compounds and the desulfurization Composition may also have redox properties, which can catalyze the epoxidation of alkenes (e.g., cyclohexene, octene, ethylene or propylene), selective oxidation of alkanes (for example, cyclododecane, cyclohexane), alcohols and amines, hydroxylation of aromatics and maximiliana ketones. The composition can be used as co-catalysts or catalyst carriers. For example, adding a noble metal such as Pd and/or Pt, for this composition gives the functionality in hydrocracking, hydrogenation, dehydrogenation and desulphurization. This composition may also contain all types of zeolites and zeolite like structures together with all possible heteroatoms mentioned above.

A typical example of the composition of the invention, which has acidity, is a composition containing aluminum and/or gallium. Alkylation is a group of industrially important reactions are commonly used in corrosion Lewis acid, such as AlCl3and HF, and produce large amounts of waste. The composition of the present invention is environmentally friendly and can replace the conventional catalysts. It can catalyze the alkylation of alkanes or aromatics (including alkylation by Friedel-Crafts) using olefins, alkylhalogenide or alcohols as alkylating agent is C. Aromatic compounds mainly include benzene, naphthalene, phenanthrene and their derivatives, such as toluene, xylene, isopropylnaphthalene, diphenyloxide or 2,4-di-tert-butylphenol. Olefinic alkylating agents mainly include alpha-olefins, preferably the number of carbon atoms greater than two, preferably more than four. Suitable olefins include, for example, ethylene, propylene and 1-hexadecene. Alcohol alkylating agents mainly include methanol, ethanol, isopropanol, benzyl alcohol and cinnamic alcohol. The alkylation reaction can be conducted at a temperature of from about 80°With up to approximately 400°at a pressure of from 1 to 50 bar, preferably from about 90°up to about 300°and from 1 to 30 bar.

Oligomerization and polymerization of olefins can give fractions for gasoline, jet fuel, diesel fuel and lubricating base oil. The catalytic compositions according to the invention, particularly those containing heteroatoms aluminum, chromium, gallium, or iron, can be used for the oligomerization of olefins, such as alpha-olefins with the number of carbon atoms greater than three. Reaction conditions, depending on the specific raw materials and the products you want, include a temperature in the range of from about 25°up to about 300°and a pressure in the range from masterlogo pressure up to about 70 bar.

The catalytic composition of this invention can be used for the selective oxidation of organic compounds. Particularly preferred compositions containing one or more heteroatoms, selected from among transition metals, including, for example, copper, zinc, iron, titanium, chromium, vanadium, molybdenum and tin. For example, the composition containing titanium, zinc, chromium, iron and manganese, can catalyze the epoxidation of olefins, including aromatics, such as phenanthrene, anthracene and TRANS-stilbene. The oxidizing agents used in this type of reaction include organic and inorganic peroxides, oxides of nitrogen, oxygen, or any gaseous mixture containing oxygen. Composition containing copper and zinc is particularly preferred for catalysis selective oxidation of alcohols into the corresponding aldehydes. Hydroxylation of phenol and 1-naphthol can be performed using a catalytic composition comprising tin, iron, copper, cobalt and vanadium.

In prior art acylation of aromatics usually carried out using a Lewis acid such as AlCl3, FeCl3H2SO4etc. that produce large amounts of waste. On the contrary, the composition of the present invention, especially its variant implementation, which contain aluminum, iron, gallium, is NDI etc., replaces Lewis acid. Alleluya agents mainly include acylhomoserine, anhydrides of carboxylic acids. Aromatic compounds mainly include benzene, naphthalene, phenanthrene and their derivatives. The acylation can be carried out at a temperature of from about 40°up to about 300°under pressure from about 0.5 bar to about 20 bar, preferably from about 60°With up to approximately 250°and a pressure of from about 1 to 15 bar.

Being introduced as heteroatoms in mesoporous silica according to the invention, transition metals such as cobalt, Nickel, molybdenum, tungsten or combinations thereof, or noble metals such as platinum, palladium or combinations thereof, provide catalysts especially suitable for the method of Hydrotreating, such as (1) the hydrogenation of aromatics in gasoline, jet fuel, diesel fuel and lubricating oil; (2) hydrocracking of heavy fractions, such as vacuum gas oil, residual fractions, and liquids produced from coal (coal oil); (3) reduction KUO diazotoluene, desulfurization and demeterova hydrocarbons, including the aforementioned factions. Demeterova particularly suitable for the removal of iron, Nickel, vanadium and arsenic. Reaction conditions of Hydrotreating typically include a reaction temperature range is from about 60° With up to 350°and a pressure ranging from atmospheric pressure to about 300 bar.

Isomerization of hydrocarbons (e.g. n-butane, n-pentane, 1-butene and xylene) can kataliziruetsa through the use of the catalyst according to this invention. The preferred catalyst composition for the isomerization contain zirconium, tungsten, gallium, iron, titanium and aluminum as heteroatoms.

The dehydrogenation of saturated hydrocarbons to unsaturated hydrocarbons can kataliziruetsa with the use of a composition containing mainly vanadium, iron, gallium, cobalt and chromium. Saturated hydrocarbon can be, for example, propane, isobutane and benzene. Hourly space velocity of gas (COG) is typically in the range from 100 to 2000 h-1preferably from 500 to 1000 h-1. Working pressure is typically in the range from about 7 kPa to about 600 kPa, preferably from about 7 kPa to about 400 kPa. The reaction temperature is usually from about 350°C to about 650°C, preferably from about 450°With up to approximately 600°C.

The cracking of hydrocarbons may preferably be carried out using the invented catalytic compositions containing Nickel, tungsten, molybdenum, aluminum and/or gallium. In addition, the catalytic composition according to this the invention can be used alone or together with zeolites. The hydrocarbon may be raw material for cracking with a fluidized bed of catalyst, hydrocracking, etc. This catalytic composition may also catalyze the cracking of polymer waste to return useful fractions of desired chemicals.

The composition may be used as catalyst for the method of Fischer-Tropsch. This method includes the interaction of the source stream containing hydrogen and carbon monoxide with a catalyst in the reaction zone that supports accelerating the conversion conditions effective to obtain the exit stream containing hydrocarbons. Hourly volumetric feed rate (COSP) gas flow may be in the range of from about 100 volumes per hour per volume of catalyst (h-1) to about 10000 h-1preferably from about 300 h-1to about 2000 h-1. The reaction temperature is usually from about 160°up to about 300°C, preferably from about 190°C to about 260°C. the Reaction pressure is usually from about 5 bar to about 60 bar, preferably from 8 bar to about 30 bar.

The composition may be used for efficient and selective adsorption of certain compounds. Thanks to its adjustable pores and the functionalized pore walls composition allows different link is to penetrate into the pores and interact with heteroatomic functional groups on or in the wall. For example, embedded heteroatoms may be high, but unsaturated coordination number, which allow the heteroatoms to form coordination with oxygen, nitrogen and sulfur compounds, thus effectively removing these compounds from streams. The interaction can also be acid-base. For example, the composition containing aluminum may be removed from the flow of toxic compounds such as cyanuric acid and p-chlorophenol. Essentially, the composition can be used as adsorbents and molecular sieves.

In the description of the present invention presents a new type of mesoporous or meso-microporous silicate containing heteroatoms, with randomly-connected three-dimensional pore structure with controlled pore size. It offers a new efficient method for the synthesis of mesoporous silicate without the inclusion of any surfactants. And it provides a way of applying this composition in catalysis and separation.

Various features of the invention are illustrated by the examples below. X-ray diffraction (RDH) powders obtained materials were recorded using CuKαradiation diffractometer Philips PW 1840 with graphite monochromator. The samples were scanned in the range of 2θ ot,5 to 40° with a step of 0.02°. Transmission electron microscopy (TEM) was performed using an electron microscope Philips CM30T with LaB6 filament as the electron source, working at 300 kV. Adsorption isotherms of nitrogen were measured on a Quantachrome Autosorb-6B at 77 K. Misoprostol was calculated using the method of Barrett, Joyner and Halenda (BHJ). All parts of the compositions are by weight unless otherwise stated.

EXAMPLE 1

This example shows how to introduce aluminum into the silicon dioxide without heating in an autoclave before roasting.

First, 1 part isopropoxide aluminum (Al(ISO-OS3H6)3) was added 26 parts of an aqueous solution of hydroxide of tetraethylammonium (TEON, 35%) under stirring. After dilution was added into the above solution under stirring 38 parts of triethanolamine (tea) together with 8 parts of water. Then, with vigorous stirring, was added 26 parts of tetraethylorthosilicate (TEOS). Received a clear solution. Stirring was continued for 1 hour and then the synthetic mixture was left at room temperature overnight and dried at 98°C in air for 24 hours. At the end of the synthetic mixture was progulivali at 570°C for 10 hours in air with a heating rate of 1°C/min

Figure 1 shows its RDH-intensive reflection at about 1.1° 2θcharacteristic of mesoporous mA is Arial. Moreover, the absence of resolved peaks from aluminum oxide means that the phase volume of the aluminum oxide is not formed. Figure 2 represents a snapshot transmission electron microscopy (TEM), showing accident-related mesoporous structure. Elemental analysis showed the ratio of Si/Al about 24.8, which is consistent with the ratio in the original synthetic mixture equal to 25. Adsorption of nitrogen gives the surface area of 983 m2/g, a total pore volume of 1.27 cm3/g and a narrow distribution of mesopores with center at 4.2 nm, shown in figure 3.

EXAMPLE 2

This example demonstrates the introduction of heteroatoms by heating in an autoclave before annealing. 3.3 parts of isopropoxide aluminum was added to the flask with 42 parts of TEOS and was stirred for one hour. A mixture of 7.6 parts of tea and 25.8 parts of water was added to a mixture of TEOS and Al(ISO-OC3H6)3under stirring. After 2-hour stirring 21 part TEON was added dropwise to the above mixture, and formed a thick gel. The gel was dried in an oven at 98°C for 22 hours and then kept in an autoclave at 190°C for 16 hours. At the end of the gel was progulivali at 600°C for 10 hours in air.

Figure 4 shows its RDH-intensive reflection at a small angle in 2θcharacteristic of mesoporous material. Element and the Alize showed a ratio Si/Al of about 24,5, that is consistent with the ratio in the original synthetic mixture equal to 25. Adsorption of nitrogen gives the surface area of 799 m2/g, a total pore volume of 1.24 cm3/g and a narrow distribution of mesopores with center at 4.5 nm.

EXAMPLE 3A

The example demonstrates the introduction of aluminium and its stability in the composition. 3 parts of isopropoxide aluminum was added to the flask with 38,8 parts of TEOS and was stirred for 1.5 hours. A mixture of 23 parts of tea and 21 parts of water was added to the above mixture under stirring. After a 2 hour mixing 23 part TEON was added dropwise to the above mixture, and after 0.5 hour stirring it turned into a clear solution. The solution was dried in a drying Cabinet at 100°C for 4 days and then kept in an autoclave at 190°C for 7.5 days. In the end it was progulivali at 600°C for 10 hours in air at a heating rate of 1°C/min

Elemental analysis showed the ratio of Si/Al equal to 99.2. Figure 5 shows its RDH intensive peak. Adsorption of nitrogen shows a narrow distribution of mesopores with center at 17 nm, as shown in Fig.6, which shows a surface area of approximately 385 m2/g and the pore volume was approximately 1.32 cm3/year

EXAMPLE 3B

The material obtained in example 3A, boiled in water for 17 hours, but his RDH, depicted in figure 5, still displays the intense peak, a similar peak in the source material. This means that the composition has a high hydrothermal stability compared to other mesoporous materials.

EXAMPLE 3C

The material obtained in example 3A, was progulivali at 900°s on the air, but his RDH (figure 5) still shows a strong peak, demonstrating that the mesoporous structure is preserved. This result means that the composition has a high thermal stability up to 900°C.

EXAMPLE 4

This is an example of the use of inorganic sources of heteroatoms to the introduction of aluminum into silicon dioxide. 7.2 parts of nonahydrate of aluminium nitrate was dissolved in 20 parts of water. Then added 61.4 parts of TEOS and was stirred for 0.5 hour. Another mixture of 56.3 parts of tetraethyleneglycol and 24 parts of water was added to the above mixture under stirring. After 1 hour stirring was added 49 parts of an aqueous solution of hydroxide of tetraethylammonium (TEON, 35% wt.), and after 0.5 hour of stirring the final mixture turned into a thick gel. The gel was dried in a drying Cabinet at 100°during the night and then kept in an autoclave at 180°C for 3 hours. In the end it was progulivali at 600°C for 10 hours in air at a heating rate of 1°C/min

Elemental analysis showed the ratio of Si/Al equal to 15.3. His RDH who had a strong peak around 1 degree 2θ . Adsorption of nitrogen showed a narrow distribution of mesopores with center at 4.5 nm, the specific surface area of about 786 m2/g and the total volume of pores is about 1,02 cm3/year

EXAMPLE 5

The example illustrates the introduction of vanadium in silicon dioxide. 1 part acetylacetonate, vanadium (IV) was added to the flask with 41 part TEOS and was stirred for 2 hours. A mixture of 30 parts of tea and 25 parts of water was added to the above mixture under stirring. After 2-hour stirring 20 parts TEON was added dropwise to the above mixture, and after 0.5 hour stirring it turned into a solid gel. The gel was kept at room temperature for 24 hours and dried in a drying Cabinet at 100°during the night, and then progulivali at 700°C for 10 hours in air, and in the end he turned into an orange powder.

Elemental analysis showed the ratio of Si/V, is equal 50,5. Fig.7 shows his RDH with an intense peak for mesostructure and without any peaks from the phase of vanadium oxide. Adsorption of nitrogen showed a narrow distribution of mesopores with the center of 4.1 nm, specific surface area of about 835 m2/g and a pore volume of about of 0.91 cm3/year

EXAMPLE 6

This example demonstrates the introduction of titanium. 1 part of butoxide titanium (IV) was added to the flask with 31 part TEOS and was stirred for 2 hours. A mixture of 22.5 cha the TEI of tea and 17 parts of water was added to the above mixture under stirring. After 1 hour stirring 18.5 parts TEON was added dropwise to the above mixture, and after 0.5 hour stirring it turned into a thick gel. The gel was kept at room temperature for 22 hours and was dried in an oven at 98°during the night, and then progulivali at 700°C for 10 hours in air, and in the end she turned into a white powder.

Elemental analysis showed the ratio of Si/Ti equal 49,6. Fig shows his RDH with an intense peak for mesostructure and no resolved peaks from titanium oxide. Adsorption isotherms of nitrogen shown in Fig.9, which shows the distribution of mesopores with the center of 4.7 nm, shown in figure 10, the specific surface area of about 917 m2/g and the total pore volume of about 0,84 cm3/year

EXAMPLES 7-9

In these examples demonstrates the implementation of three different heteroatoms. 42 parts of tetraethylorthosilicate (TEOS) was mixed with 30 parts of triethanolamine (tea) for 1 hour, obtaining a mixture of I. a Mixture II was prepared by dissolving sources of heteroatoms in 22 parts of water. 1 part of gallium nitrate, 0,54 parts of zinc chloride and 0.9 parts of chloride of tin used in examples 7, 8 and 9, respectively. Mixture II was added dropwise to the mixture I with stirring. Thereafter, a combination of mixtures I and II was stirred for 0.5 hour while stirring on to ply was added 24.5 parts hydroxide of tetraethylammonium. After stirring for 2 hours each of the three mixtures became a transparent solution, and in the end was added 0.5 g of ammonium hydroxide (27 to 30 wt.%). After stirring for a further 2 hours the mixture is statically maintained throughout the night. The mixture was dried at 98°within 24 hours, and each turned into a dried gel. Dried gels were kept in an autoclave at 180°C for 2.5 hours and at the end was progulivali at 600°C in air for 10 hours.

11 shows RDH gallium-, zinc - and tin-containing silicate obtained in examples 7, 8 and 9, respectively. Table 1 represents misoprostol and chemical composition of the three materials.

Table 1
Misoprostol gallium-, zinc - and tin-containing silicates in examples 7, 8 and 9, respectively
ExampleHeteroatom MThe content of M

(wt.%)
Dp*< / br>
(nm)
SBET*< / br>
(m2/g)
vtotal*< / br>
(cm3/g)
7Ga1,348300,71
8Zn1,956900,69
9Sn3,34,57800,67
Dpmean diameter of pores, SBETmean specific surface area, vtotalmeans the total pore volume

EXAMPLE 10

This example illustrates the simultaneous introduction of two types of heteroatoms in silicon dioxide. First of 2.7 parts of isopropoxide aluminum was mixed with 0,86 parts acetylacetonate, vanadium (IV) and 34 parts of tetraethylorthosilicate (TEOS) to obtain the first mixture. The second mixture contained 34 of the tea and 21 of the water. Then the second mixture was added dropwise to the first mixture under stirring. After stirring for 1.5 hours was added dropwise 16.8 parts of hydroxide of tetraethylammonium under stirring. Synthetic mixture turned into a thick gel. This gel statically kept over night at room temperature, dried at 100°C for 42 hours and then was heated in an autoclave at 180°C for 3 days. In the end it was progulivali at 650°C in air for 10 hours.

Fig shows RDH aluminum and vanadium-containing silicate. Adsorption of nitrogen showed that the composition has a narrow pore distribution of about 11 nm (shown in Fig), a surface area of about 433 m2/g and the total pore volume of about 1.25 cm3/, e is emanny analysis showed that Si/Al=13.5 and Si/V=49,1.

EXAMPLE 11

This example shows getting a Fe-containing mesoporous silicate. One part of nitrate of iron (III) was dissolved in 5 parts of deionized water and then added to a 27.4 parts of tetraethylorthosilicate (TEOS), and was stirred for 1 hour. Another solution consisting of 19.8 parts of triethanolamine (tea) and 30.4 parts of deionized water was introduced dropwise into the first mixture. After 1 hour stirring to this mixture was added dropwise 16.2 parts of hydroxide of tetraethylammonium (TEON). Finite homogeneous pale yellow solution was kept at room temperature for 24 hours, dried at 100°within 24 hours and in the end was progulivali at 650°C for 10 hours, obtaining a pale yellow powder.

Fig shows RDH with one intense peak at a small angle from about 0.5 to 2.2°indicating mesostructure characteristics. Elemental analysis showed the atomic ratio Si/Fe 48,8. Spectroscopy in the UV-visible region (Fig) showed a peak of about 220 nm, characteristic of chetyrehhodovogo iron, as well as a shoulder in the range from 250 to 350 nm, typical for octahedral coordination of iron in the matrix of silicon dioxide. Measurement of the adsorption of N2given the surface area by BET of about 630 m2/g, average diameter of mesopores about 4.8 nm (cf Fig) and in total the initial pore volume of about 1,24 cm 3/year

EXAMPLE 12

The methods of preparation of Fe-containing silicate is similar to the method in example 11; however, used only 0,52 parts of iron nitrate (III). After annealing the elemental analysis showed that the powder has an atomic ratio Si/Fe 98,6. Adsorption of nitrogen showed a specific surface area of 580 m2/g, an average pore diameter of 5,96 nm and pore volume 1,82 cm3/year

EXAMPLE 13

This example shows getting a Cr-containing silicate. 1,2 part of nonahydrate of chromium nitrate was dissolved in 5 parts of deionized water and then added to 26,3 parts of tetraethylorthosilicate (TEOS) and was stirred for 1 hour. Another solution consisting of 19 parts of triethanolamine (tea) and 22.2 parts of deionized water was dropwise introduced into the above solution. After stirring for another 1 hour to the mixture was added dropwise to 26.2 parts of hydroxide of tetraethylammonium. Finite homogeneous pale green solution was kept at room temperature for 24 hours, dried at 100°within 24 hours and in the end was progulivali at 650°C for 10 hours, receiving a yellow-orange powder that contains chrome.

Fig shows RDH with one intense peak at a small angle from about 0.5 to 2.2°indicating mesostructure characteristics. Spectroscopy in the UV-visible region (Fig) showed two is izlechimym peak around 220 and 390 nm, typical four-coordinated chromium, as well as the shoulder about 480 nm, typical for octahedral coordination polychromatic (-Cr-O-Cr-)nin the matrix of silicon dioxide. Measurement of the adsorption of N2given the surface area by BET of about 565 m2/g, average diameter of mesopores 1,96 nm (cf Fig) and the total pore volume of about 1,54 cm3/year

EXAMPLE 14

Method for producing Cr-mesoporous silicate is similar to the method in example 13; however, used 1,31 part of chromium nitrate. After annealing the elemental analysis showed that the powder has an atomic ratio Si/Cr 40,3. Adsorption of nitrogen showed a specific surface area of 572 m2/g, a pore diameter of 2.35 nm and pore volume of 1.7 cm3/year

EXAMPLE 15

This example illustrates a composition containing Mo. 1.6 parts of the tetrahydrate of heptamolybdate ammonium [(NH4)6Mo7O24·4H2O] was dissolved in 5 parts of deionized water and then added to 27,1 part of tetraethylorthosilicate (TEOS), and was stirred for 1 hour. In the above-mentioned solution was added dropwise to another solution consisting of 19.6 parts of triethanolamine (tea) and 30.4 parts of deionized water. After another stirring for 1 hour 16,1 part of the hydroxide of tetraethylammonium (TEON) was added dropwise to this mixture. Finite homogeneous pale yellow is actor kept at room temperature for 24 hours, dried at 100°within 24 hours and in the end was progulivali at 650°C for 10 hours, obtaining a white powder.

Fig shows RDH with one intense peak at a small angle from about 0.5 to 2.2°indicating mesostructure characteristics. Spectroscopy in the UV-visible region (Fig) shows a peak around 220 nm, characteristic of chetyrehhodovogo molybdenum in the matrix of silicon dioxide. Measurement of the adsorption of N2given the surface area by BET of about 500 m2/g, average diameter of mesopores about 8,91 nm (cf Fig) and the total pore volume of about 1.31 cm3/year

EXAMPLE 16

Method for producing Mo-mesoporous silicate is similar to the method in example 15; however, used 3,9 part of the tetrahydrate of heptamolybdate ammonium [(NH4)6Mo7O24·4H2O]. After annealing the elemental analysis showed that the powder has an atomic ratio Si/Mo 39,8. Adsorption of nitrogen showed a specific surface area of 565 m2/g, an average pore diameter of 3,93 nm and pore volume of 0.98 cm3/year

EXAMPLE 17

Demonstrates the simultaneous introduction of both Ni and Mo in the mesoporous material. First, 7.7 parts of uranyl nitrate Nickel (II) and 32 parts of tetrahydrate of heptamolybdate ammonium was dissolved in 54 parts of water with stirring. Then added to the above solution under intensive is remesiana 67 parts of tetraethylorthosilicate (TEOS). After stirring for 1.5 hours was added dropwise with stirring, 40 parts of a hydroxide of tetraethylammonium (TEON). Synthetic mixture turned into a thick gel. This gel is still kept at room temperature overnight, dried at 100°C for 24 hours and then was heated in an autoclave at 180°C for 3 hours. At the end of the synthetic mixture was progulivali at 600°C in air for 10 hours.

RDH end of the powder shows an intense peak around 1.1° 2θindicating the characteristics of the mesoporous material. Adsorption of nitrogen shows that the material has a narrow pore distribution of about 2.3 nm, a surface area of approximately 633 m2/g and a total pore volume of about 0,86 cm3/, Elemental analysis shows that the resulting powder contains of 6.1 wt.% Ni and 10.5% Mo.

EXAMPLE 18

This example illustrates the simultaneous introduction of both Ni and W in the mesoporous material. First, 5.8 parts of uranyl nitrate Ni (II) and 35 parts of hydrate metavolume ammonium was dissolved under stirring 42.3 parts of water. Then, the resulting solution was added 50.5 parts of tetraethylorthosilicate (TEOS) with vigorous stirring. After stirring for 1.5 hours was added dropwise a hydroxide of tetraethylammonium under stirring. Synthetic mixture turned the ü in a dense gel. The gel was kept still at room temperature overnight, dried at 100°C for 24 hours and then kept in an autoclave at 180°C for 3 hours. Finally it was progulivali in air at 600°C for 10 hours.

RDH end of the powder shows an intense peak of about 1.0° 2θindicating the characteristics of the mesoporous material. Adsorption of nitrogen shows that the material has a narrow pore distribution of about 2.4 nm, a surface area of about 649 m2/g and the total pore volume of about 0,81 cm3/, Elemental analysis shows that the resulting powder contains about 6.4 wt.% Ni and 12.0% W.

EXAMPLE 19

It was demonstrated obtaining palladium catalysts. 65 parts of the material of example 1 was mixed with 35 parts of aluminum oxide and to this mixture was added water, so that the catalyst can be ekstradiroval. The catalyst was progulivali when 480°in a stream of nitrogen 5.about./min for 6 hours followed by the replacement of current nitrogen in the air about 5./about./min Annealing was finished with rise of temperature up to 540°and maintaining at this temperature for 12 hours. Palladium was introduced by impregnation with an aqueous solution tetraminoes salt of palladium, Pd(NH3)4Cl2. The extrudate was dried at 120°during the night and was progulivali at 300°in air is 3 hours. The final catalyst had 0,81 wt.% palladium surface area of 630 m2/g, a particle density of 0.83 g/ml and a pore volume of 1.21 cm3/year

EXAMPLE 20

The alkylation of naphthalene 1-hexadecanol conducted in the flask with a mechanical stirrer. Used catalysts of examples 1, 2 and 3A. 1 part of catalyst were loaded into a flask and heated up to 200°C in vacuum for 2 hours. Then the catalyst was cooled to 90-100°C in an atmosphere of nitrogen and a mixture of 6.5 parts by weight. naphthalene and 26 parts of 1-hexadecene, was introduced into the flask under stirring. The temperature was raised up to 200-205°and kept constant. The reaction mixture was analyzed by gas chromatography using column WAX 52 CB. The results of the reaction with different catalysts are summarized in table 2.

Table 2
The alkylation of naphthalene 1-hexadecanol over various catalysts
The catalyst CompositionReaction time (hour)The conversion of naphthalene (%)Selectivity* (%)
Example 1 Si/Al=24,84to 25.357,6
Example 2 Si/Al=24,54,527,356,7
Example 3 Si/Al=99,2 41965,3
*Selectivity towards monoalkylamines the naphthalene

EXAMPLE 21

The alkylation according to the Friedel-Crafts benzene to chlorobenzene was performed in a flask with a magnetic stirrer. Used catalysts of examples 7, 9, 11 and 12. 1 part of catalyst were loaded into a flask and heated to 180°C in vacuum for 4 hours. Then the catalyst was cooled to 80°C in nitrogen atmosphere and the flask was introduced a mixture of 102 parts of benzene and 8.2 parts of benzylchloride. The temperature was kept constant, equal to 60°s or 80°C. the Reaction mixture was analyzed by gas chromatography using column WAX 52 ST. The results of the reaction with different catalysts are summarized in table 3.

60
Table 3
The alkylation of benzene to produce difenilmetana over various catalysts
CatalystTrackReaction time (min)Temperature (°C)Conversion (%)Selectivity (%)
Example 12Si/Fe=98,62406086100
Example 11Si/Fe=50,16051100
Example 11Si/Fe=50,115060100100
Example 11Si/Fe=50,1606097100
Example 7Si/Ga=712406064,9100
Example 9Si/Sn=462406015,8100

EXAMPLE 22

Selective oxidation of ethylbenzene to acetophenone was carried out in a flask in nitrogen atmosphere with stirring. Used catalysts of examples 13, 14 and 16. One part of the catalyst was activated at 180°C for 4 hours in vacuum and then cooled to 80°C. Then a mixture consisting of 100 parts of acetone, 82 parts of ethylbenzene and 9.5 parts of tert-butylhydroperoxide (TBHP), was introduced into the flask under stirring. The reaction mixture was analyzed by gas chromatography using column WAX 52 CB. The results of the reaction with different catalysts are summarized in table 4.

Table 4
The conversion of ethylbenzene to acetophenone over various catalysts
Catalysis is tor TrackTime (min)The gas flowTemperature (°)Conversion (%)Selectivity (%)
Example 13Si/Cr=130480Dry N28068,594,5
Example 13Si/Cr=130480The air8073,6for 95.3
Example 13Si/Cr=130480The air6054,799,3
Example 14Si/Cr=40,3480The air8067,399,2
Example 16Si/Mo=39,8360The air8024,2of 58.9

EXAMPLE 23

Oligomerization of 1-mission carried out in a batch reactor, the with stirring. 1 part of catalyst was activated in a reactor by heating in a nitrogen atmosphere at 200°C for 2 hours. 25 parts of 1-mission) was added by syringe in a stream of nitrogen. The reaction was conducted at 150°C for 24 hours. After cooling the reactor product was analyzed using gas chromatography (GC) using columns WAX 52 CB. For each test mol%. converse is the mission and selectivity of dimer are presented in table 5.

Table 5
Oligomerization of 1-mission over various catalysts
CatalystTrackTime (hour)Temperature (°)Conversion (%)
Example 2Si/Al=24,5415012,6
Example 2Si/Al=24,52415025,8

EXAMPLE 24

Acylation of 2-methoxynaphthalene to 2-acetyl-6-methoxynaphthalene conducted in a batch reactor, the with stirring. The reactor with 16 parts of the catalyst obtained in example 2 was kept at 240°C for 2 hours in vacuum and then filled with dry nitrogen. After cooling the reactor to 120°in a reactor were introduced 250 parts of decalin (as a solvent), 31 part 2-methoxynaphthalene, 42 parts of acetic anhydride and 10 parts of n-tetradecane (internal standard). After reaction for 6 hours, the reaction mixture was analyzed using (GC) using columns WAX 52 CB, and it was found that the conversion of 2-methoxynaphthalene reaches of 36.5% with 100% selectivity for 2-acetyl-6-methoxynaphthalene.

EXAMPLE 25

The oxidation of cyclohexanol to cyclohexanone was carried out in reacto the e periodic action with stirring. The reactor with 1 part of the catalyst was kept at 180°C in vacuum for 4 hours and then filled with dry nitrogen. After cooling to 55°in a reactor were introduced 100 parts of acetone, 10 parts of tert-butylhydroperoxide (TBHP) and 7.5 parts of cyclohexanol; the temperature of the reaction was maintained equal to 55°C. After 5 hours reaction, the reaction mixture was analyzed using (GC) using columns WAX 52 CB, performance of different catalysts are summarized in table 6.

Table 6
The oxidation of cyclohexanol to cyclohexanone over various catalysts
CatalystTrackTemperature (°C)Time (hour)Conversion (%)Selectivity (%)
Example 15Si/Mo=97,955579,495
Example 16Si/Mo=39,855584,693

EXAMPLE 26

The material of example 17 was evaluated in relation to the modernization of the Paraho oil shale at 68 bar H2and CHOP equal to 2. The reaction temperature was varied from 260 to 400°C. Properties of oil shale are presented in the table . Properties of the product after the upgrade are presented in table 8.

Table 7
Sample properties Paraho oil shale
Density, °API21,7
Hydrogen, wt.%11,49
Nitrogen, wt.%2,2
Sulfur, wt.%0,69
Arsenic, h/mn wt.37
Iron, am/mn wt.27
Nickel, H./mn wt.2,4
Bromine number45
Environments. molecular weight307
C=C bond in the molecule0,85

Simulated distillationD2887 (°)
5%239
30%373
50%432
70%491
95%--

Table 8
Processing of oil shale in a protective camera - product properties
Temperature (°)Bromine NoIron (hours/million the speakers.) Nickel (h/mn wt.)Arsenic (wt.%)Sulfur (h/mn wt.)Nitrogen (h/mn wt.)
2600,73,51,955,30,631,98
290<0,12,61,854,20,571,89
315<0,12,01,613,10,481,78
370<0,10,21,3<0,10,251,40
400<0,1<0,10,1<0,1<0,11,18

The evaluation showed that the catalytic material of example 17 is very active to saturate olefins, removal of iron and Nickel, diazotoluene and desulfuromonas. The material is also very active for the removal of arsenic.

EXAMPLE 27

Selective hydrocracking of the lubricant was performed on Ni - and W-containing mesoporous material of example 18. The feedstock consisted of a heavy neutral distillate with the properties shown below in table 9 together with the properties of the oil after dewaxing solvent to the freezing temperature of -18#x000B0; C (ASTM D-97 or equivalent, such as Autopour). After dewaxing solvent content of nitrogen was 1500 ppm and a viscosity index of distillate ("IV") was 53. The purpose of the hydrocracking of a lubricant is to increase the level IVE not converted material to values in the range from 95 to 100 at maximizing the output of a lubricant.

Table 9
Properties of heavy neutral distillate
Hydrogen, wt.%12,83
Nitrogen, am/million1500
The main nitrogen cmln466
Sulfur, wt.%0,72
API density22,0
KV at 100°C, CSTholds 18.52
Composition, wt.%
Waxes18,3
Naphthenes32,2
Aromatics49,5
Artificial distillation, wt.%°
1BP405
5%452
10%471
95%586
Properties of the oil after dewaxing solvent
KV at 100°C, CST20,1
The viscosity index (VI)53
The point of solidification, °C0
The output of the lubricant, % wt.87

The distillate was treated at temperatures of from 385 to 401°C, hydrogen pressure 138 bar, the circulation of hydrogen 7500 SCF/B feed and from 0.55 to 0.61 of COSP. The data from these experiments are summarized in table 10 below:

Table 10
Temp., °125739754
Pressure, bar138138138
CHOP0,610,540,55
343°, conversion, wt.%22,937,647,3
Properties of a lubricant
KV at 100°C, CST11,057,89the 5.45
SUS at 100°F695398 201
YVES86,2110,2126,3
The point of solidification, °132829
The output of the lubricant, % wt.71,560,651,3
KV is the kinematic viscosity
SUS viscosity at universal seconds Sabata

The catalytic material is selective for the modernization of the heavy neutral distillate from crude distillate with YVES from 53 to product with YVES equal to 105, with the release of a lubricant (not deparaffinizing), equal to 65% wt.

EXAMPLE 28

This example shows getting a FCC catalyst using the compositions of this invention and the comparison of the results of its cracking with the results obtained when using the catalyst MCM-41. Obtaining catalyst was as follows.

Got about 35% wt. the composition of example 4 in the matrix of silica - alumina - clay. 130 Parts of the composition of example 4 was treated in a ball mill for 14 hours in 230 ml of H2O. the Product was washed from the mill to 52.5 ml of H2O. Received a suspension containing 827 g H2O, 33.5 parts of kaolin clay (Georgia Kaolin Kaopaque) and 175,4 parts of aqueous silicon dioxide (Philadelphia Quartz N-brand). The suspension is eremetical with the addition of 16.4 parts of H 2SO4within 30 minutes. Was added dropwise 22.9 parts of Al2(SO4)3·16H2O, dissolved in 92,2 parts of water. 396 parts of the suspension MCM-41, crushed in a ball mill (11,36% solids)was added to a suspension of silica - alumina - clay and the mixture is vigorously stirred at 800 rpm for 30 minutes and then was filtered.

The solid is again translated in suspension in H2O and spray dried. The dried aerosol product is translated into a slurry with water and dust part, floating above the suspension was discarded. The remaining solid was exchanged with 1N NH4NO3(5 cm3NH4NO3/g solids). The solid was washed with H2O, was filtered and was dried in a drying Cabinet at 120°C.

The sample weight 50 g of this material was progulivali at 540°C for one hour in N2and for 6 hours in air. The remainder of the solids after drying in a drying Cabinet handled the ferry in 45% H2O at 650°C for 4 hours. To the inlet of steam into the reactor, the sample was heated to 650°With N2. The air was gradually increased over a period of 1/2 hour, while the flow rate of nitrogen was increased. After 1/2-hour period was filled with couples on a 4-hour period.

For comparison, the FCC catalyst containing 35 mA is.% MCM-41, received as described above. The original MCM-41 had a surface area of 980 m2/g, size distribution of pores with a maximum of about 2.5 nm and pore volume to 0.72 cm3/, It contained 5.4 wt.%. Al2O3,similarly, the material of example 4 from 5.3 wt.%. Properties steamed catalysts are presented in table 11.

Table 11
Comparison of FCC catalyst containing composition according to the invention, and the catalyst containing MCM-41 after steam treatment
CatalystThe composition according to the inventionMCM-41
SiO2,wt.%72,671,8
Al2O3, wt.%13,813,7
Surface area m2/g462307
Environments. particle size, microns8692
Bulk density, g/cm30,650,43

Tests on catalytic cracking

Two catalyst shown in table 11, were evaluated for cracking Joliet Sour Heavy Gas Oil (JSHGO) in the installation with a fixed fluidized bed of fluidized catalyst at 516°and With one minute on the thread. Used JSHGO had properties that PR is dostavlennya in table 12. The ratio of the catalyst-oil was changed from 2.0 to 6.0 for the consideration of a wide range of conversions. The outputs are summarized in table 13 are based on a constant coke number (4,0 wt.%)

Table 12
Sample properties JSHGO
Density, g/cm30,8918
Aniline point, °80,8
Hydrogen, wt.%12,13
Sulfur, wt.%2,4
Nitrogen, wt.%0,41
The main nitrogen cmln382
The carbon Conradson0,54
KV 100°C, CST8,50
KV 40°C, CSTNot defined
Bromine number8,7
The refractive index, 21°C1,496
The point of solidification, °C90
Ni, h/million0,34
V, h/million0,39
Na, h/million1,3
Fe h/million0,3

Profile distillation
vol.% distillate
5314
10346
20381
30407
40428
50448
60468
70489
80514
90547
100601
% unreturned0

Table 13
Comparison of catalytic cracking over a catalyst containing composition according to the invention, over a catalyst containing MCM-41
CatalystAccording to the inventionMSM-41Delta
Coke, wt.%4,04,0
Conversion, wt.%59,956,83,1
With5+ gasoline, wt.%39,737,22,5
RON93921
LFO, wt.%31,532,2a-0.7
HFO, wt.%10,211,0-0,8
4,vol.%14,713,31,4
Light gas, wt.%6,97,3-0,4
H2,wt.%0,030,04-0,01
With5,% vol.5,5the 4.70,8
RON - road octane number
LFO - light motor oil
HFO - heavy motor oil

EXAMPLE 29

Cubic fraction obtained by hydrocracking at an average pressure, subjected to dewaxing and hydrobromide. The feedstock was processed using the cascade reactor with fixed bed. Eighty grams of HZSM-5 dewaxing catalyst was loaded in the first reactor and 240 g of the catalyst according to the invention described in example 19, was loaded into the second reactor. The feedstock is passed over both catalysts at 175 bar, 1.0 COP over the dewaxing catalyst, 0.33 CHOP over the catalyst hydrobromide. The temperature in the first reactor maintained 307-321°C, to obtain the target point pour point equal to -6,6°C. the properties of the bottom fraction is described below in table 14.

Table 14
Properties most severe 10% VAT residue conversion 45 wt.% at 377°C
Nitrogen, am/million9
Mol. weight558
The point of solidification, °C>120
KV at 100°C, CST11,3
Composition, wt.%
Waxes42,1
Mononaftisto 19.9
Polyaffineof 21.2
Aromatics16,8
Simulated distillation°F
IBP/5209/854
10/50902/982

For determination of aromatics in the base component of the lubricant used UV-absorption of the product. The absorption at 226 nm is a measure of the total aromatics, while the absorption at 400 nm (×103) is a measure of polynuclear aromatics. For comparative purposes were testing over the catalysts Pd/MCM-41 obtained by the method described in example 19. The results of the experiments are summarized in table 15.

Table 15
Lubricant after hydrobromide at 274°C
Experience12
MetalPdPd
MediaMCM-41Example 1
Total aromatics, 226 nm0,2100,120
Polynuclear aromatics, 400 nm (×103)1,300,78

Comparing the characteristics of Pd/MCM-41 catalyst with a catalyst containing Pd in the composition of the present invention, it is seen that the composition according to the present invention is much more effective for its rich flavour.

EXAMPLE 30

This example demonstrates the use of the composition according to the invention as a catalyst for hydrotreatment of coal liquids. Although specific, obtained from coal liquid, taken here as an example, is a liquid product fraction obtained by the method of production of synthetic liquid fuels based on the hydrogenation of coal (using Illinois No 6 coal as source material), other coal liquid (for example, extracts of coal-tar, solvent after cleaning, coal etc) can be handled similarly. A sample of the catalyst was obtained as described in example 3A. However, the method included a hydrothermal treatment in an autoclave p and 109° With over a relatively short period of time, equal to 4 days. Adsorption of nitrogen showed mesopores with a size of about 11 nm with a surface area of about 630 m2/, Elemental analysis showed the atomic ratio Si/Al of approximately 99,6.

The material is further impregnated with a solution of heptamolybdate ammonium. In particular, 45,12 parts of an aqueous solution containing 6.38 parts of heptamolybdate ammonium was added to 40 parts of the above material. The obtained wet material was dried at 120°and progulivali in air at 538°under conditions sufficient to destroy heptamolybdate ammonium education MoO3getting so impregnated with molybdenum material.

Impregnated with molybdenum material is then impregnated with a solution of Nickel nitrate. In particular, 48,2 parts of an aqueous solution containing of 9.3 parts of Ni(NO3)2·6H2O, was added to impregnowanego molybdenum material. The obtained wet material was dried at 121°and progulivali in air at 538°to destroy the nitrate of Nickel with the formation of NiO, thus obtaining impregnated with Nickel and molybdenum material. Elemental analysis showed that the final material contains 15 wt.% MoO3and 6.4 wt.% NiO.

For comparison used material MCM-41, which had a surface area of 992 m /g, the distribution of pore size with a maximum at 3.5 nm and a pore volume equal to 0.72 cm3/, This material was impregnated as described above, and finally it contains of 15.2 wt.% MoO3and 6.75 wt. NiO.

Their activity for Hydrotreating was estimated using Illinois H-coal as a feedstock. Table 16 shows the properties of the material.

tr>
Table 16
Properties Illinois H-coal
Density, °API25,8
Aniline point, °<-1,1
Molecular weight147
Viscosity, CST at 38°1,645
CCR, wt.%0,29
Bromine number, wt.%42
Carbon, wt.%86,96
Hydrogen, wt.%is 11.39
Sulfur, wt.%0,32
Oxygen, wt.%1,80
Total nitrogen, wt.%0,46
The main nitrogen, wt.%0,30
Iron, am/million22
Chloride, h/million32
Justify to determine the true boiling points, °
St/513/81
10/30101/167
50207
70/90242/309
95/99346/407
St - standard

These two pre-catalyst was sulfurously for 1 hour at a flow rate of, containing 10% H2S in H2at 230°equal to 500 cm3/min, and the total pressure of 680 kPa. The Hydrotreating is conducted at a temperature of 350°C, pressure 6890 kPa, flow rate 500 cm3rpm, volume time velocity of the fluid, equal to 0.33. Table 17 shows a comparison of activity diazocarbonyl, reconstruction of the carbon balance Conradson (PPC) and desulfuromonas.

Table 17
Comparison of the activity of the Hydrotreating
CatalystThis inventionMCM-41 catalyst
Diazotoluene (%)7348
Recovery KUO (%)9863
Desulfuromonas (%)9558

The catalyst of this invention shows a much higher activity, which may in part be related to E. what about the unique porous structure. It has relatively large pores with a three-dimensional joints, which may be suitable for transport of large molecules such, which are present in coal liquids.

EXAMPLE 31

This example shows getting a catalyst for Fischer-Tropsch and its catalytic performance. Twenty (20) parts of the Al-containing material obtained in example 1 was dried at 200°within half an hour in a stream of nitrogen. The material is then thoroughly mixed with 2 parts of Co2(CO)8in the glove chamber. This mixture was placed in a boat to annealing in a sealed tube was removed from the glove camera. Then the mixture was stirred in a stream of helium at 100°C for 15 minutes, increase the temperature to 200°C for 10 minutes and kept at 200°in a stream of helium within half an hour. The final catalyst contained 16 wt.% With.

The above catalyst was treated with hydrogen before the test. The catalyst was placed in a small quartz crucible in the chamber was purged with nitrogen with a flow rate of 8.5×10-6nm3/s at room temperature for 15 minutes. The catalyst was then heated at a rate of 1°C/min to 100°in a stream of hydrogen 1,8×10-6nm3/s and kept at 100°within hours. The catalyst was then heated at a rate of 1°C/min up to 400°and in which he had laid down at 400° With over four hours in a stream of hydrogen 1,8×10-6nm3/C. the Catalyst was cooled in hydrogen and purged with nitrogen before use.

The reactor to work under pressure, containing a catalyst and n-octane was heated to 225°under pressure 69 bar in a mixture of H2:CO (2:1) and kept at this temperature and pressure for 1 hour. The reactor was cooled with ice, blew and added internal standard di-n-butyl ether. Hydrocarbons in the interval With a11-C40analyzed relative to the internal standard for GC.

Performance With11+(g11+/h/kg of catalyst), calculated on the basis of total performance11-C40-hydrocarbon per kg of catalyst per hour was $ 234. The logarithm of the mass fraction for each number of carbon atoms ln(Mn/n) plotted on the ordinate against the number of carbon atoms in (Mn/n) on the abscissa. From the slope obtained a value of alpha equal to 0.87.

Although the description above contains many details, these should not be construed as a limitation of the framework of the invention, but only as an illustration of the preferred option implementation. Specialists in this field will see a lot of other possibilities within the scope and essence of the invention as defined by the attached claims.

1. How is the processing of organic compounds, which contains:

a) providing a catalyst composition, which comprises, essentially, the mesoporous structure of silica containing at least al. % of pores having a pore size in the range of from about 15 Å up to about 300 Åand has a micropore volume of at least about 0.01 cm3/g, and where the mesoporous structure has entered into it in the amount of at least about 0.02 wt.%, at least one catalytically and/or chemically active heteroatom selected from the group consisting of Al, Ti, V, Cr, Zn, Fe, Sn, Mo, Ga, Ni, Co, In, Zr, Mn, Cu, Mg, Pd, Ru, Pt, W, and combinations thereof, and said catalyst composition has an x-ray with one peak between 0.3° up to about 3.5° 2θ;

b) interaction of raw materials containing organic compound under the reaction conditions mentioned composition of the catalyst, and the processing method selected from the group consisting of alkylation, acylation, Hydrotreating, demetilirovania, catalytic dewaxing, the Fischer-Tropsch process and cracking.

2. The method according to claim 1, wherein the processing method is an alkylation, and in which the feedstock containing organic compound contains an aromatic compound or alkane and an alkylating agent.

3. The method according to claim 2, in which the aromatic compound libranos group, consisting of benzene, naphthalene, phenanthrene, toluene, xylene, ISO-Propylenediamine, diphenyloxide and 2,4-di-tert-butylphenol.

4. The method according to claim 3, in which the alkylating agent is an olefin or alcohol.

5. The method according to claim 4, in which at least one heteroatom is an Al and/or Ga.

6. The method according to claim 5, in which the aromatic compound is a naphthalene or benzene and the olefin is a 1-hexadecene or ethylene.

7. The method according to claim 3, in which the alkylating agent is an organic halide, and in which at least one heteroatom selected from the group consisting of Sn, Ga, Fe and combinations thereof.

8. The method according to claim 7, in which the aromatic compound is a benzene and the organic halide is a chlorobenzene.

9. The method according to claim 1, wherein the processing method is the acylation, the feedstock contains at least one aromatic compound and at least one allerease agent and at least one heteroatom selected from Al, Fe, Ga, In and combinations thereof.

10. The method according to claim 9, in which the feedstock comprises 2-methoxynaphthalene and acetic anhydride.

11. The method according to claim 1, in which the processing method includes Hydrotreating and at least one heteroatom selected from the group consisting of Ni, Mo, Co, W, Pt, Pd and combinations thereof.

12. The method according to claim 11, in which the organic feedstock comprises oil shale, or coal derived liquid, or residual oil fraction Hydrotreating includes one or more processes from diazotoluene, desulfuromonas, KUO-recovery and demetilirovania.

13. The method according to item 12, in which demeterova involves removal of iron, Nickel, copper, vanadium and arsenic.

14. The method according to item 13, in which the feedstock is a petroleum residue Hydrotreating includes one or more processes from diazotoluene, desulfuromonas, demetilirovania and KUO-recovery.

15. The method according to claim 1, in which the processing method includes cracking.

16. The method according to item 15, in which the cracking is a complex and at least one heteroatom includes one or more metals selected from the group consisting of Ni, W, Mo, Co, Al and Ga.

17. The method according to item 15, in which the cracking is a catalytic cracking unit and at least one heteroatom includes A1.

18. The method according to claim 1, wherein the processing method is a catalytic dewaxing and at least one heteroatom includes at least one atom selected from the group consisting of Al, Pt and Pd.

19. The method according to claim 1, wherein the method of processing p is ecstasy a method of Fischer-Tropsch and at least one heteroatom selected from the group consisting of Fe, Co, Ni, and Ru and combinations thereof.

20. The method according to claim 1, in which the composition of the catalyst interacts with the feedstock containing hydrogen and carbon monoxide, under conditions of: a pressure of from about 5 to about 60 bar, preferably from 8 to about 30 bar, CHOP from about 100 to about 10000 h-1preferably from 300 to about 2000 h-1temperatures from about 160 to about 300°C, preferably from about 190 to about 260°C.



 

Same patents:

FIELD: organic chemistry.

SUBSTANCE: invention refers to technology and technique of gas hydrocarbons conversion to liquid hydrocarbons stable at normal conditions. The invention concerns method of gas hydrocarbons conversion to liquid hydrocarbons under electric discharges. Converted hydrocarbons are subject to partial discharges by dispersion in dielectric organic liquid in DC electric field. Process is carried out by means of gas hydrocarbons converter including coaxial internal and outer electrodes. Outer electrode comprises sequence elements every of which is dielectrically isolated sections one of which is under tension and another one is electrically neutral. Process is carried out section by section. In addition invention concerns device for gas hydrocarbons conversion to liquid hydrocarbons.

EFFECT: developed method of gas hydrocarbons conversion to liquid hydrocarbons under electric discharges.

3 cl, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing poly-alpha-olefin compound. Method involves combined oligomerization of a mixture containing about from 60 to 90 weight% of 1-dodecene and about from 10 to 40 weight% of 1-decene in the presence of BF3 as a catalyst and alcoholic promoter at temperature in the range about from 20°C to 60°C followed by distilling the mixture and hydrogenation to yield poly-alpha-olefin. Product has kinematic viscosity in the range about from 4 to 6 centistokes at 100°C, loss by Noak mass in the range about from 4% to 9%, viscosity index in the range about from 130 to 145 and fluidity loss temperature in the range about from -60°C to -50°C.

EFFECT: improved method of synthesis.

11 cl, 9 tbl, 14 ex

FIELD: petrochemical industry; methods of production of the polyolefin bases of the synthetic oils.

SUBSTANCE: the invention is pertaining to the method of production of the polyolefin bases of the synthetic oils by cationic oligomerization of the olefinic raw and may be used in petrochemical industry. The developed method contains: the stages of preparation of the olefinic raw, preparation and batching in the reactor of the solutions and suspensions of the components of the catalytic system Al(0)-HCl-(CH3)3CCl (TBX), isomerization of alpha-olefins and oligomerizations of the highest olefins and their mixtures under action of the catalytic system Al (0)-HCl-TBX, extractions of the dead catalyst, separation of the oligomerizate for fractions and hydrogenation of the extracted fractions under action of the catalytic agent Pd (0.2 mass %)/Al2O3+NaOH. The invention ensures improvement of the stages of the developed method. For prevention of the corrosion activity of the products the method additionally contains the stage of dechlorination of the present in the oligomerizate chlorine-containing oligoolefins by the metallic aluminum, triethylaluminum, the alcoholic solutions of KOH or using the thermal dehydrochlorination of the chlorine-containing polyolefins at the presence or absence of KOH. For improvement of the technical-and-economic indexes of the method at the expense of the increase of the output of the target fractions of polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C the method additionally contains the stage of the thermal depolymerization of the restrictedly consumable high-molecular polyolefins with the kinematic viscosity of 10-20 centistoke at 100°C into the target polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C.

EFFECT: the invention ensures improvement of all the stages of the developed method.

1 cl, 15 tbl

FIELD: petrochemical industry; methods of production of the polyolefin bases of the synthetic oils.

SUBSTANCE: the invention is pertaining to the method of production of the polyolefin bases of the synthetic oils by cationic oligomerization of the olefinic raw and may be used in petrochemical industry. The developed method contains: the stages of preparation of the olefinic raw, preparation and batching in the reactor of the solutions and suspensions of the components of the catalytic system Al(0)-HCl-(CH3)3CCl (TBX), isomerization of alpha-olefins and oligomerizations of the highest olefins and their mixtures under action of the catalytic system Al (0)-HCl-TBX, extractions of the dead catalyst, separation of the oligomerizate for fractions and hydrogenation of the extracted fractions under action of the catalytic agent Pd (0.2 mass %)/Al2O3+NaOH. The invention ensures improvement of the stages of the developed method. For prevention of the corrosion activity of the products the method additionally contains the stage of dechlorination of the present in the oligomerizate chlorine-containing oligoolefins by the metallic aluminum, triethylaluminum, the alcoholic solutions of KOH or using the thermal dehydrochlorination of the chlorine-containing polyolefins at the presence or absence of KOH. For improvement of the technical-and-economic indexes of the method at the expense of the increase of the output of the target fractions of polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C the method additionally contains the stage of the thermal depolymerization of the restrictedly consumable high-molecular polyolefins with the kinematic viscosity of 10-20 centistoke at 100°C into the target polyolefins with the kinematic viscosity of 2-8 centistoke at 100°C.

EFFECT: the invention ensures improvement of all the stages of the developed method.

1 cl, 15 tbl

FIELD: petrochemical processes.

SUBSTANCE: products obtained via oligomerization of propylene on phosphoric acid catalyst are subjected to rectification. Oligomerizate if first fed into first column from which top product containing unreacted hydrocarbon is withdrawn and bottom product is sent into second rectification column. Top product of the second column is constituted by propylene dimer fraction and bottom product of this column is sent into third rectification column. Top product of the third column is constituted by C7-C8-olefin fraction and bottom product of this column is constituted by propylene trimer and tetramer fraction, which is separated into desired products. A part of propylene dimer fraction obtained as top product of the second fraction is passed to reflux first column and to additionally cool bottom product of the first column used as feed for the second column and/or bottom product of the second column used as feed for the third column.

EFFECT: reduced power consumption and increased separation capacity of propylene oligomer isolation column.

2 cl, 1 dwg, 3 ex

The invention relates to the technology of organic synthesis, namely, catalytic methods of processing of hydrocarbon raw materials to produce products, which can be used either directly as motor fuel or as a component of a fuel or as raw material for separation of aromatic hydrocarbons and a catalyst for the implementation of these methods

The invention relates to methods for processing of liquid products of pyrolysis (railway checkpoint) and can be used in refining and petrochemical industries

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to production of lubricating material characterised by dynamic viscosity at -35°C, lower than 5000 cpz, as a result of fulfilling the following stages: a) introduction of feedstock containing more than 50 weight % of paraffin, in presence of hydrogen in contact with catalyst containing component based on metal of group VIII applied on carrier based on refractory oxide, and b) introduction of product of stage (a) in contact with catalyst composition, which contains noble metal of group VIII, binder and crystals of zeolite belonging according to its type, to MTW, obtaining product characterised by lower flow temperature in as compared to that of stage (b) product and index of viscosity higher than 120, and c) adding to base oil obtained at stage (b) of additive for reduction of flow temperature.

EFFECT: production of lubricating material characterised by dynamic viscosity at -35°C.

21 cl, 5 dwg, 3 tbl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: middle distillates are obtained, in particular, from paraffin charge prepared by Fischer-Tropsch synthesis wherein hydrocracking/hydroisomerization catalyst is utilized including at least one hydrocracking/hydroisomerization element selected from group constituted by group VIII metals, non-zeolite silica-and-alumina-based carrier (more than 5% and less than or equal to 95% SiO2) and having: average pore size measured by mercury porometry within a range 20 to 140 Å; total pore volume measured by mercury porometry 0.1-0.6 mL/g; total pore volume measured by nitrogen porometry 0.1-0.6 mL/g; specific surface BET between 100 and 550 m2/g; pore volume for pores with diameter above 140 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 160 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 200 Å measured by mercury porometry less than 0.1 mL/g; pore volume for pores with diameter above 500 Å measured by mercury porometry less than 0.01 mL/g; x-ray diffraction pattern containing at least principal characteristic lines of at least one transition aluminum oxides (alpha, rho, chi, eta, kappa, teta, and delta). Processes of obtaining middle distillates from paraffin charge obtained ny Fischer-Tropsch synthesis (options) using above indicated procedure are also described.

EFFECT: improved catalytic characteristics in hydrocracking/hydroisomerization processes and improved quality and yield of middle distillates.

18 cl, 6 dwg, 3 tbl, 5 ex

FIELD: hydrocarbon conversion processes and catalysts.

SUBSTANCE: invention, in particular, relates to selectively upgrading paraffin feedstock via isomerization. Catalyst comprises support and sulfated oxide or hydroxide of at least one of the elements of group IVB deposited thereon; a first component selected from group consisting of consisting of lutetium, ytterbium, thulium, erbium, holmium, and combinations thereof; and a second component comprising at least one platinum-group metal component. Catalyst preparation process comprises sulfating oxide or hydroxide of at least one of the elements of group IVB to form sulfated support; depositing the first component onto prepared support; and further depositing the second component. Invention also relates to hydrocarbon conversion process in presence of above-defined catalyst.

EFFECT: improved catalyst characteristics and stability in naphta isomerization process to increase content of isoparaffins.

13 cl, 2 dwg, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to method for obtaining highly-purified hard oil paraffins by processing oil fractions in hydrogen medium at higher pressure and temperature in presence of system of alumooxide catalysts, which possess functions of changing hydrocarbon composition and purification from element-organic compounds. As oil fraction, oil-free gatch is used; as catalyst of purification from element-organic compounds, preferably is used catalyst obtained by consecutive mixing of aluminium hydroxide of pseudobemite type with inorganic acid until uniform mass with pH 4÷5 is obtained, with salts of nickel and/or cobalt and molybdenum and/or tungstem in amounts necessary for content in end-product of molybdenum and/or tungstem oxide to be 12.0-20.0% weight, nickel and/or cobalt oxide 3.0-5.0% weight, with further evaporation to loss on ignition of not more than 53-56% weight, its formation as extrudates, drying extrudates to loss on ignition of less than 30% weight and their baking to loss on ignition of less than 3% weight.

EFFECT: elaboration of efficient method of production of highly-purified hard oil paraffins.

3 cl, 6 tbl

FIELD: chemistry.

SUBSTANCE: method of simultaneous fractioning and hydroprocession of flow of wide naphtha fraction is proposed. The method includes supply of hydrocarbons flow in temperature range of naphtha boiling, which contains organic compounds of sulphur and hydrogen, into distillation column reactor. In the reactor, the following processes take place simultaneously, i.e. separation of the said naphtha into light low-boiling naphtha and heavy high-boiling naphtha; contact of the said naphtha with hydrodesulphurisation catalyst for selective interaction of organic sulfur compounds in it with the said hydrogen with formation of H2S; isolation of part of the said low-boiling naphtha, in which the aforesaid low-boiling naphtha contains recombinant mercaptans; removal of the said heavier high-boiling naphtha from the said distillation column reactor; fractioning of the said part of light low-boiling naphtha in order to remove its lighter fraction, which, in fact, does not contain mercaptans, from counter-flow reactor before contact of the said lighter fraction with hydrogen in still layer of hydrodesulphurisasion catalyst for reduction of amount of recombinant mercaptans in it.

EFFECT: elaboration of efficient method of simultaneous fractioning and hydroprocession of flow of wide naphtha fraction.

11 cl, 1 dwg

FIELD: chemistry, organic, processing of hydrocarbons.

SUBSTANCE: invention is related to an improved method for hydroprocessing of hydrocarbon raw stock containing sulphur- and/or nitrogen-bearing contaminants. The method comprises the first contact interaction of hydrocarbon raw stock with hydrogen in the presence of at least one first catalyst based on VIII group metals on an acidic carrier, the carrier being selected from the group of zeolites and zeolite-bearing carriers, and then the flow leaving the first catalyst directly contacts hydrogen in the presence of at least one second catalyst based on a VIII group metal on a less acidic solid carrier, said solid carrier being selected from the group of carriers based on silicon dioxide-aluminium oxide and other solid carriers that are not zeolites. Said combination of two catalyst layers allows processing of raw stock with a high content of contaminating impurities without high-level cracking that involves the use of highly acidic carriers.

EFFECT: processing of hydrocarbon raw stock with contaminating impurities without high-level cracking.

14 cl, 1 ex

FIELD: petroleum processing.

SUBSTANCE: process consists in interaction of feedstock with hydrogen in presence of hydrofining catalyst under suitable conditions and includes stage wherein catalyst is moistened with water added to feedstock in amounts between 0.01 and 10 vol %.

EFFECT: prolonged service time of hydrofining reactor and increased silicon capacity of hydrofining catalyst.

2 cl, 2 tbl, 2 ex

FIELD: inorganic compounds technologies.

SUBSTANCE: invention provides porous composite particles containing alumina component and residue of at least one additional crystal growth inhibitor component dispersed within alumina component, wherein indicated composite particles have (A) specific surface area at least 80 m2/g; (B) average nitrogen-filled pore diameter 60 to 1000 Å; (C) total nitrogen-filled pore volume 0.2 to2.5 cm3/g and (D) average particle size 1 to 15 μm, and where, in indicated composite particles, (i) alumina component contains at least 70 wt % of crystalline boehmite with average crystallite size 20 to 200 Å, γ-alumina obtained from indicated crystalline boehmite, or mixture thereof; (ii) residue of additional is obtained from at least one ionic compound containing ammonium, alkali metal, alkali-earth metal cation, or mixtures thereof and wherein anion is selected from group comprising hydroxyl, silicate, phosphate, sulfate, or mixtures thereof and is present in composite particles in amounts between 0.5 and 10 % of the summary weight of alumina and additional components. Invention also provides a method to obtain composite particles, agglomerated particles prepared therefrom, and a method for hydroprocessing of petroleum feed using above-mentioned agglomerates.

EFFECT: avoided unnecessary calcination before addition of metals to increase average pore size and use of organic solvents for azeotropic removal of water.

36 cl, 2 tbl, 22 ex

FIELD: petrochemical processes.

SUBSTANCE: petroleum fractions are treated at elevated hydrogen pressure and temperature in presence of catalytic systems composed catalysts endowed with functions of varying hydrocarbon composition and removing heterorganic compounds. Process is carried out on catalytic base consisting of two or more catalyst and temperature at least 300оС, pressure at least 3.0 MPa, and hydrogen-to-feed volume ratio (nm3/m3) calculated by formula: A=B+C+D, where B is hydrogen-to-feed volume ratio for hydrogenolysis of heterorganic compounds (nm3/m3); C the same for hydrogenation of unsaturated compounds; and D the same for conversion of high-boiling hydrocarbons.

EFFECT: increased yield of light fractions with improved environmental characteristics.

9 cl, 8 tbl, 18 ex

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