The method of pre-sulfatirovnie catalyst for conversion of hydrocarbons, pre-sulfated catalyst and method for conversion of hydrocarbons
(57) Abstract:The invention describes a process (method) pre-sulphurization of porous catalyst particles capable of solifidian containing at least one metal or metal oxide, which includes, (a) impregnation of the catalyst inorganic polysulfide solution and at least one water-soluble oxygendemanding hydrocarbon to obtain a catalyst containing sulfur, in which at least part of the sulphide or sulphur introduced into the pores of the catalyst; (b) heating serosoderjaschei catalyst in the presence of an oxidizing environment; pre-sulfated catalysts and their use in processes for the conversion of hydrocarbons. The technical result is an increase in the activity of the catalyst. 3 C. and 10 C.p. f-crystals, 1 table. This invention relates to a method (process) of the provisional sulfonation or prior sulfatirovnie catalysts for conversion of hydrocarbons to pre-sulfonated catalysts and their use in processes for the conversion of hydrocarbons.It is well known that often you want to apply a stage of "pre-sulfatirovnie" or "predvaritelnaya hydrocarbons, or before their initial use, that is, before using a fresh catalyst, either before their reuse after regeneration. Usually the catalysts for conversion of hydrocarbons: such as catalysts hydrobromide, hydrocracking catalysts and catalysts for processing of associated gas, is subjected to such "pre-sulfatirovnie".The catalyst hydrobromide can be defined as any catalyst composition, which can be used to catalyze the hydrogenation of hydrocarbons, and particularly to hydrogensulfate special ingredients raw materials: such as sulfur-, nitrogen - and metal-containing organic compounds and unsaturated compounds. The hydrocracking catalyst may be defined as any catalyst composition, which can be used for cracking (splitting) of large and complex molecules derived from oil, in order to achieve the molecules of smaller size with a concomitant joining of hydrogen to molecules. The catalyst for the processing of associated gas can be defined as any catalyst composition, which can be used to catalyze the conversion of s hydrogen sulfide, which can be easily extracted and converted into elemental sulfur. The recovered catalyst can be defined as any catalyst composition, which contains the metal in a reduced state such as, for example, catalytic hydrogenation of olefins. These metals usually recover a reducing agent such as, for example, hydrogen or formic acid. The metals in the recovered catalyst can be fully restored or partially restored.Catalytic compositions (compositions) for hydrogenation catalysts are well known and some are commercially available. Usually the active phase of the catalyst based on at least one metal of group VIII, VI, IV, IIB or IB of the Periodic table of elements. Typically, the hydrogenation catalysts contain at least one element selected from Pt, Pd, Ru, Ir, Rh, Os, Fe, Co, Ni, Cu, Mo, W, Ti, Hg, Ag, or Au, is usually located on the media: such as aluminum, silicon, silicon-aluminum and carbon.Catalytic composition for hydrobromide and/or hydrocracking or for processing of associated gas are well known and some are commercially available. Catalysts based on oxides of metals, caused usually aluminum, silicon and silicon-aluminum media, including zeolites. Also, other catalysts on the basis of the elements transition metals can be used for this purpose. In General, the catalysts containing at least one element selected from V, Cr, Mn, Re, CO, Ni, cu, Zn, Mo, W, Rh, Ru, Os, Ir, Pd, Pt, Ag, Au, Cd, Sn, Sb, Bi and Te, are disclosed as suitable for these purposes.For maximum effectiveness, these catalysts based on metal oxides transform, at least partially in the sulphides of the metals. Catalysts based on metal oxides can be sulfatirovanne in the reactor by contact at elevated temperatures with hydrogen sulfide or sulfur-containing oil or raw material (in-situ).However, for the user it is advantageous to have catalysts based on metal oxides with sulfur in elemental form or in the form serosoderjaschei organic compounds included in them. These pre-sulfated catalysts can be loaded into the reactor and brought to reaction conditions in the presence of hydrogen, prompting sulfur or structurae compound to react with hydrogen and oxides of the metals, thereby turning them into sulfides without neobhodimuu benefit (the benefit of) the operator and allow you to avoid many dangers: such as Flammability and toxicity, facing the operator when using hydrogen sulfide, liquid sulfides, organic polysulfides and/or mercaptans to sulfatirovnie catalyst.There are several ways of pre-sulphurization of the catalyst based on metal oxides. The catalysts of hydrobromide previously had sulfurously by introducing serosoderjaschei compounds in porous catalyst before hydrobromide hydrocarbons. For example, U.S. patent 4,530,917 discloses a method of pre-sulphurization of the catalyst hydrobromide organic polysulfides. U.S. patent 4,177,136 discloses a method of pre-sulphurization of the catalyst by treating the catalyst elemental sulfur. Then use the hydrogen as a reducing agent for the conversion of elemental sulfur to hydrogen sulfide without selection. U.S. patent 4,089,930 reveals pre-treatment of the catalyst elemental sulfur in the presence of hydrogen. U.S. patent 4,943,547 discloses a method of pre-sulphurization of the catalyst hydrobromide by sublimirovanny elemental sulfur inside the pores of the catalyst, then heating the mixture of sulfur and catalyst to pace the data of the PCT Application WO 93/02793 discloses a method of pre-sulphurization of the catalyst, where elemental sulfur embedded in a porous catalyst, and simultaneously or sequentially processing the catalyst liquid olefinic hydrocarbon.However, these separately (ex-situ) pre-sulfated catalysts must be subjected to a single stage activated prior to contact with the hydrocarbon feedstock in a reactor for processing hydrocarbons.Thus, the purpose of the present invention is to produce activated, pre-sulfonated or pre sulpicianus catalyst, either fresh or regenerated, which is stable in air and which does not require a separate activation treatment prior to contact with the hydrocarbon feedstock in the reactor.Therefore, according to the present invention, is provided a process (method) pre-sulphurization of porous catalyst particles capable of sulfonation, containing at least one metal or metal oxide, which includes:
(a) impregnation (impregnation) of the catalyst inorganic polysulfide solution and at least one water-soluble oxygendemanding hydrocarbon to obtain serosoderjaschei catalyst, in which Creator in the presence of a non-oxidizing atmosphere (environment).The present invention also provides a pre-sulfated catalyst obtained by the method in accordance with the invention.Used in this description, the term "inorganic polysulfide" refers to polysulfide ions having the General formula S(x)2-where x is an integer greater than 2, that is, x is an integer having a value of at least 3, preferably from 3 to 9, and more preferably from 3 to 5, and the terminology "non-organic" in this context probably refers to the nature of polysulfide half than to the counterion, which can be organic. Used herein, the term "inorganic polysulfide solution" refers to a solution containing inorganic polysulfides. Used in this description, the terms "metal(s), oxide(s) of metals and sulfide(s) of metal-containing catalysts include catalyst precursors, which are then used as the actual (real) catalysts. In addition, the term "metal(s)" includes the metal(s) in a partially oxidized form. The term "oxide(s) of metals" includes the oxide(s) of metals in partially restored form. The term "sulfide(s) of metals"federovna metals. The above terms include partially other components such as carbides, borides, nitrides, oxychloride, alkoxides and the alcoholate.In one aspect of the present invention, metal - or metal oxide-containing catalyst capable of pre-solifidian, impregnated with an inorganic polysulfide solution containing at least one water-soluble oxygenated hydrocarbon, in order to pre-proliferate catalysts based on metals or metal oxides capable of sulfonation at a temperature and for a time effective to implement sulfide or sulfur inside the pores of the catalyst. After impregnation the catalyst is heated in a non-oxidizing conditions for a time sufficient to consolidate the embedded sulfide or sulfur in the catalyst. I believe that the introduction of water-soluble oxygendemanding hydrocarbon in the inorganic polysulfide solution gives pre solifidianism the catalyst in air stability.The catalysts referred to here as "catalyst(s) based on metal oxides capable of sulfonation can be precursors of catalysts that IP is their methods of this invention can be applied to the regenerated catalysts, which may have the sulfides of the metals is not completely converted into the oxides, the term "catalyst(s) based on metal oxides capable of sulfonation" also refers to these catalysts, in which part of their metals is solifidianism condition.In a preferred implementation, before the impregnation of inorganic polysulfide solution containing a water-soluble oxygenated hydrocarbon, the particles or pellets of the catalyst based on a metal or metal oxide hydratious to equilibrium with the air in order to reduce the initial heat.In the implementation (method) of the present invention, the porous particles of the catalyst are in contact and react with the inorganic polysulfide solution and at least one water-soluble oxygendemanding hydrocarbon under conditions which induce implemented sulfides or sulfur-containing compounds inside the pores of the catalyst by impregnation. Catalysts comprising inorganic polysulfides or sulfur-containing compounds will be categorized as "catalysts, including sulfur".Inorganic polysulfide solution is usually prepared by restorani is, tetraethyl ammonium, and so on). Preferred polysulfides include inorganic polysulfides of the General formula S(x)2-in which x is an integer more than 2, preferably from 3 to 9 and more preferably from 3 to 5: such as, for example, S3)2-, S(4)2-, S(5)2-, S(6)2-and mixtures thereof.Inorganic polysulfide solution - red color solution, in which the dark coloring brings a long chain of polysulfide, and a lighter coloration gives the solution of the shorter chain polysulfide. Inorganic polysulfide solution, thus prepared, are used for impregnation (impregnation) of the catalyst particles using the method of "filling volume of pores or through emerging wettability: such that the pores of the catalyst filled without exceeding the amount of the catalyst. The amount of sulfur used in the current process (the way), will depend on the amount of catalytic metal present in the catalyst that is required for conversion to sulfide. For example, a catalyst containing molybdenum, will require two moles of sulfur or compounds containing one atom of sulfur, for turning each melirovannyh catalysts, the existing level of sulfur can be considered as a factor when calculating the required number of sulfur.Water-soluble oxygenated hydrocarbon is preferably selected from the group consisting of sugars, glycols and mixtures thereof. Suitable glycols are, as a rule, the glycols having a molecular weight (Mnin the range from 200 to 500. Suitable sugars include monosaccharides, disaccharides and mixtures thereof. Non-limiting examples of suitable monosaccharides include glucose, fructose, mannose, xylose, arabinose, mannitol and sorbitol. Non-limiting examples of suitable disaccharides include lactose, sucrose, maltose and cellulose. In a preferred implementation, a water-soluble oxygenated hydrocarbon is a sugar selected from the group consisting of sorbitol, sucrose, mannitol, glucose and mixtures thereof.The amount of sulfur is usually present in the inorganic polysulfide solution is in the range from 5 to 50 wt.% from the total mass of the solution. Higher concentrations of sulfur can be obtained by increasing the concentration of the original solution of ammonium sulfide. Inorganic polysulfide solution is usually to have a ratio of CE the polysulfide solution is, usually such that the amount of sulfur introduced into the catalyst particles, it is usually sufficient to provide the stoichiometric conversion of metal-containing components of their oxide forms in sulphide form and typically is in the range from 2 to 12 wt.% from the total mass of sulfated catalyst.It was found that the addition of pre-sulfureuse sulfur in amount up to approximately 50 % of the stoichiometric quantity required results in a catalyst having adequate (appropriate) hydrodenitrification activity, which is an important property of the catalysts hydrobromide and catalysts for the first stage hydrocracking. Thus, the amount of pre-sulfureuse sulfur used for introduction of the catalyst will usually be in the range from 0.2 to 1.5 times the stoichiometric amount, and preferably from 0.4 to 1.2 times the stoichiometric amount.For catalysts hydrobromide/hydrocracking and processing of associated gas containing metals of Group VI and/or group VIII used the number of pre-sulfureuse sulfur is usually WriteLine sulfureuse sulfur is from 4 to 12 wt.% from the whole mass of the loaded catalyst.Stage impregnating grey usually performed at a temperature in the range from 0 to 30oWith or higher, up to 60oC. the lower temperature limit is set by determining the freezing point of the inorganic polysulfide solution in the special conditions of impregnation, while the upper temperature limit is set primarily by determining the temperature of decomposition of the inorganic polysulfide solution of volatile compounds and elemental sulfur.After impregnation the catalyst particles of inorganic polysulfide solution and at least one water-soluble oxygendemanding hydrocarbons, the catalyst comprising sulfur, subjected to heat treatment by injecting non-oxidizing gas such as, for example, nitrogen, carbon dioxide, argon, helium and mixtures thereof, at a temperature sufficient to wytestone greater part of the residual water from pore size to retain sulfur in the catalyst. Heat treatment of the catalyst, including sulfur, preferably performed using a method of changing the temperature at which the catalysts, including sulfur, is first heated to a temperature in the range from 50 to 150oWith, preferably up to 120ooWith and preferably from 230 to 350oWith, to consolidate put sulfur in the catalyst. After this heat treatment, the catalyst is cooled to room (ambient) temperature. The resulting catalysts are stable when working with them on the air.Pre-sulfonated or pre sulpicianus the catalyst of the current invention can then load, for example, in the reactor for hydrobromide and/or hydrocracking or in the reactor processing of associated gas, the reactor is heated up to the job (for example, hydrobromide and/or hydrocracking or processing of associated gas) conditions, and then immediately the catalyst is brought into contact with the hydrocarbon feedstock, without the need for activation of the catalyst with hydrogen prior to contact of the catalyst with a hydrocarbon feedstock. Not wishing to be bound by any particular theory, I believe that a long period of activation with hydrogen, typically required for catalysts separately (ex-situ) pre solifidian, no need for catalysts, pre-solifidian in accordance with the present invention, because in this way the majority of the sulphur has already reacted with metallizator to such an extent, she does not come out from the pores of the catalyst to turn into sulfide.The method of the present invention also is applicable to the sulfonation of spent catalysts, which were hydroxy-regenerated. After the usual process hydroxy-regeneration, hydroxy-regenerated catalyst may be pre-prosulfuron as "fresh" catalyst by the method described above.This method is particularly suitable for application to catalysts hydrobromide and/or hydrocracking or catalysts for the processing of associated gas. These catalysts typically include metals Group VI and/or group VIII deposited on a porous media such as aluminum, silicon, silicon-aluminum and zeolites. These materials are well defined in this area of research and may be obtained using the techniques described in this respect, as, for example, in U.S. patent 4,530,911 and U.S. patent 4,520,128. Preferred catalysate of hydrobromide and/or hydrocracking or processing of associated gas will contain a metal of Group VI selected from molybdenum, tungsten and mixtures thereof, and the metal of group VIII selected from Nickel, cobalt and mixtures thereof, deposited on alumina. Multidisciplinary ("Mnogosetochnykh reaction conditions, are catalysts based on Nickel-molybdenum and cobalt-molybdenum supported on alumina. Sometimes add phosphorus as activator. A versatile catalyst for the processing of associated gas, which shows good activity at different reaction conditions, is a catalyst based on cobalt-molybdenum supported on alumina.The way the individual (ex-situ) pre-sulfonation of this invention allows for quicker time to run the reactors hydrobromide, hydrocracking and/or processing of associated gas by providing in the reactor immediate contact with the hydrocarbon feedstock and by eliminating time-consuming stage of activation by hydrogen, which is necessary for catalysts, pre-sulfonated traditional individual (ex-situ) method.Thus, the present invention also provides a method for conversion of hydrocarbons (i.e., the method of converting hydrocarbons, which comprises contacting the feedstock with hydrogen at elevated temperature in the presence of pre-sulfonated catalyst in accordance with the invention.Conditions hydrobromide include a temperature from 400 to 2500 psig (from 2.76 to 17,23 MPa). The partial pressure of hydrogen will typically be in the range of from 200 to 2,200 psig (1,38 up 15,17 MPa). The feed rate of hydrogen will generally be in the range of from 200 to 10,000 standard cubic feet per barrel (SCF/BBL") (47467,1 to 2373356 l/m3). The feed rate will usually have the volumetric rate of fluid per hour ("LHSV") in the range from 0.1 to 15.The hydrocracking conditions include a temperature in the range from 200 to 500oC and pressures above 40 bar (of 4.05 MPa). The total pressure will usually be in the range from 400 to 3000 psig (from 2.76 to 20,68 MPa). The partial pressure of hydrogen will typically be in the range of from 300 to 2600 psig (from 2.07 to 17,93 MPa). The feed rate of hydrogen will generally be in the range from 1000 to 10,000 standard cubic feet per barrel (SCF/BBL") (237335,6 to 2373356 l/m3). The feed rate will usually have the volumetric rate of fluid per hour ("LHSV") in the range from 0.1 to 15. The reactors of the first stage hydrocracking, which carry the main hydrobromide raw materials that can operate at higher temperatures than the reactors for hydrobromide, and at a lower temperature than the reactor of the second stage hydrocracking.Hydrocarbons, the cat is Ah a wide range boiling point. They include lighter fractions such as kerosene fraction and the heavier fractions such as mineral oil, coking mineral oils, vacuum mineral oil, dubitatione (neasfaltirovanyj) oil, long and short residues, catalytically split circular oil, thermally or catalytically cleaved mineral oils and oils crude oil may Utumno-sand origin, shale oils, residues processing of biomass. Can also be applied to combinations of various hydrocarbon oils.Reactors for processing associated gas typically operate at temperatures in the range from 200 to 400oC and at atmospheric pressure (101.3 kPa). About 0.5-5% vol. associated gas fed to the reactor will contain hydrogen. Standard volumetric throughput rate of associated gas per hour through the reactor are in the range of from 500 to 10,000 h-1. There are several ways in which the catalysts that are the subject of the present invention can be introduced into the reactor processing of associated gas. Klaus-section of the supply of raw materials or associated gas can be used for the introduction of catalysts, OSU gas nozzle (burner), in effect when substochiometric (below stoichiometric) ratio in order to produce hydrogen.The invention will be described using the following examples, which are provided with illustrative purpose.Preparation of inorganic polysulfide solution.Inorganic polysulfide solution for use in the following examples was prepared by adding 20,64 g of elemental sulfur to carefully (vigorously) mixed solution of ammonium sulfide (100 ml, 22 wt.%). Elemental sulfur immediately began to dissolve and the resulting solution was red-orange color. The mixture was stirred until then, until it all dissolved sulfur. The actual sulfur content in solution was to 25.7 wt.%, and the ratio of sulfur to sulfide in the solution was 2.0.Example 1
The hydrocracking catalyst based on the Z-763 Ni-W, printed on an ultra-stable Y zeolite and is available in Zeolyst International Inc., previously prosulfuron in accordance with the methodology set forth below.50 g sample of the above catalyst were gidratirovana to equilibrium with air. 7.5 g of sucrose were added to the above-mentioned inorganic polysulfide solution. Then to the volume of pores 30 ml. This solution was added dropwise to the mixed layer of the balls of the catalyst, which is contained in a nitrogen purged (0.5 l/min) trehsotmillionnogo three-neck round-bottom flask, using the device type syringe pump. Holder, to which was attached a round-bottom flask was subjected to vibration, using FMC vibrating table, with an amplitude of vibration that is installed to create peremeshivayte layer of the catalyst beads. The resulting black beads were then heated from room temperature to 205oC for 1 h and Then the temperature of the catalyst is brought to the end of the maintained temperature of 260oC and maintained for 1 h Final sulfur level was 5 wt.% of the total amount of catalyst. The sulfur content in the catalyst was analyzed using SC-432 analyzer for carbon and sulfur LECO Corporation.Example 2
The hydrocracking catalyst based on the Z-763 Ni-W, printed on an ultra-stable Y zeolite and is available in Zeolyst International Inc., previously prosulfuron in accordance with the methodology set forth below.50 g sample of the above catalyst were gidratirovana to balance in the air. 7.5 g of sorbitol were added to the above aqueous solution, diluted to obtain a water pore volume of 30 ml. of This solution was added dropwise to the mixed layer of the balls of the catalyst, which is contained in a nitrogen purged (0.5 l/min) trehsotmillionnogo three-neck round-bottom flask, using the device type syringe pump. Holder, to which was attached a round-bottom flask was subjected to vibration, using F vibration table, vibration amplitude, set to create peremeshivayte layer of the catalyst beads. The resulting black beads were then heated from room temperature to 205oC for 1 h and Then the temperature of the catalyst is brought to the end of the maintained temperature 357oC and maintained for 1 h Final sulfur level was 3,91% by weight of the total catalyst. The sulfur content in the catalyst was analyzed using SC-432 analyzer for carbon and sulfur LECO Corporation.Comparative example AND
Commercial hydrocracking catalyst described in example 1 above was subjected to preliminary sulfonation essentially the same methodology described above in example 1, except that inorganic polysulfide solution is not dobaseaction, and the catalyst is sensitive to air, re hydrational using a stream of nitrogen saturated with water after the heating stage so that the catalyst could be safely manipulated on the air during loading of the reactor.Comparative example
Commercial hydrocracking catalyst described in example 1 above was subjected to the next process sulfatirovnie without selection (in-situ).A sample of catalyst was loaded into a section for testing with the set pressure sulfiding gas (5% H2S/95% H2) 350 psig (2,4 MPa) and the flow rate set to give the volumetric gas flow rate per hour (GHSV) 1500 (for example, 40 ml of catalyst, flow rate 60 l/h). Then the temperature is brought from room temperature up to 150oC for 0.5 h and then from 150 to 370oDuring the period of time of 6 hours and Then for 2 h the temperature was maintained at 370oWith and then lowered to 150oC. Since that time, the section is switched to a flow of pure hydrogen and installed the planned speed and pressure, and then introduced hydrocarbons. The final sulfur level was 5.45 wt.% from the total mass of the catalyst. The sulfur content in katalysatorer
Catalysts, sulfatirovanne in examples 1 and 2 and comparative examples a and b above were used for hydrocracking hydroblasting catalytically-split light mineral oil in the reactor jet-flow type. The catalyst samples were diluted with silicon carbide and loaded in a tubular reactor jet-flow type. In a tubular reactor created the hydrogen pressure up to 1500 psig (10,34 MPa). Then the reactor was heated to 150oWith the above catalyst missed raw material: gidroabrazivnoy catalytically-split light mineral oil, with a bulk velocity of fluid per hour (LHSV) of 6.0. The ratio of hydrogen to the raw material in a tubular reactor amounted to 6500 standard cubic feet per barrel (SCF/BBL) (1542681,4 l/m3). The temperature was increased with a speed of 22oWith a day for four days and with a speed of 6oWith a day for five days up to 260oC. Then the temperature was regulated to obtain the target conversion 12 wt.% at 190oWith the inlet (feed) raw materials. The results are presented in table 1 below.Example 3
In accordance with example 1, catalyst hydrocracking based on Z-763 Ni-W, printed on an ultra-stable Y zeolite and the same neo below.of 16.3 ml of polyethylene glycol with a molecular weight of 400 were mixed from 13.7 ml inorganic polysulfide solution and then diluting the solution was added dropwise to 50 g of pre-hydrated catalyst Z-763. The impregnated catalyst was heated to a final temperature of 260oC. the Obtained black and gray beads catalyst had stable characteristics when working with them on the air. The final sulfur level was 3,29 wt.% of the total amount of catalyst. The sulfur content in the catalyst was analyzed using SC-432 analyzer for carbon and sulfur LECO Corporation.As can be seen from table 1, the catalysts in examples 1 and 2, which were previously prosultiamine inorganic polysulfide solution containing sucrose and sorbitol, respectively, have the appropriate characteristics to retain sulfur and activity in the hydrocracking process, which improved compared with the activity of the catalyst, which was previously prosurvival inorganic polysulfide solution and in the absence of a water-soluble oxygen-containing carbon (comparative example a) and equivalent to the activity of the catalyst, which was previously prosurvival, COI is SS="ptx2">1. The method of pre-sulphurization of porous catalyst particles capable of solifidian containing at least one metal or metal oxide of group VIB and group VIII, including (a) impregnation of the catalyst inorganic polysulfide to obtain a catalyst containing sulfur, in which at least part of the sulphide or sulphur introduced into the pores of the catalyst; C) heating the sulfur-containing catalyst in the presence of non-oxidizing environment, characterized in that the impregnation of the catalyst to carry out an inorganic polysulfide solution and at least one water-soluble oxygendemanding hydrocarbon.2. The method according to p. 1, characterized in that the inorganic polysulfide solution includes polysulfide ions of the General formula S(x)2-where x is an integer having a value of at least 3.3. The method according to p. 1 or 2, characterized in that the inorganic polysulfide solution obtained by dissolving elemental sulfur in an aqueous solution of ammonium sulfide or a derivative of ammonium sulfide.4. The method according to any of paragraphs.1-3, characterized in that the inorganic polysulfide solution contains an amount of sulfur in the range 5-what about the water-soluble oxygenated hydrocarbon selected from the group consisting of sugars, glycols and mixtures thereof.6. The method according to p. 5, characterized in that the water-soluble oxygenated hydrocarbon is a sugar selected from the group consisting of monosaccharides, disaccharides and mixtures thereof.7. The method according to p. 5, characterized in that the water-soluble oxygenated hydrocarbon is polyethylene glycol having a molecular weight (Mnin the range of 200 to 500.8. The method according to any of the preceding paragraphs, characterized in that prior to stage (a) a catalyst containing at least one metal or metal oxide, hydratious to balance in the air.9. The method according to any of the preceding paragraphs, characterized in that the treatment in stage (a) is carried out at a temperature in the range of 0 - 60oC.10. The method according to any of the preceding paragraphs, characterized in that the heating in stage (b) is carried out at a temperature in the range of 50 - 400oC.11. The method according to any of the preceding paragraphs, characterized in that the heating in stage (b) is carried out in the presence of non-oxidizing gas selected from the group consisting of nitrogen, carbon dioxide, argon, helium and mixtures thereof.12. Pre the metal or metal oxide of group VIB and group VIII, characterized in that it is obtained by the method according to PP. 1-11.13. The method of conversion of hydrocarbons, which consists in the introduction to the contact of the feedstock with hydrogen at elevated temperature, characterized in that use pre-sulfated catalyst under item 12.
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
SUBSTANCE: mould catalyst for hydrocracking contains at least zeolite Y and inorganic high-melting oxide with monomodal pores distribution (by mercury porosimetre) whereat at least 50% of total volume is represented with pores having diametre in the range from 4 to 50 nm and the volume at least 0.4 ml/g. The method for carrier preparation and the carrier obtained with this method are described; the said method includes moulding of the mixture containing at least zeolite Y and high-melting oxide with calcinations losses in the range (LIR) from 55 to 75%. The catalytical composition for hydrocracking includes said carrier, at least one component of hydrogenating metal selected from the metal of groups V1B and group V111 and optionally at least one promoting element selected from silicon boron in the case when carrier virtually does not contain the alumosilicate zeolite. The method for catalytical composition preparation and composition obtained with this method are described; the said method includes optional calcinations of the said carrier, precipitation of the at least one hydrogenating metal selected from described above ones in the corresponding amount; the said precipitation is carried out by impregnation with solution containing organic compound having at least two functional groups selected from carboxyl, carbonyl and hydroxyl groups. The hydrocracking method with application of the aforementioned catalytical composition is described.
EFFECT: enhancing of the catalytical composition activity, selectivity and hydrogenation ability.
18 cl, 5 tbl
SUBSTANCE: invention relates to promoter catalysts on aluminosilicate carriers with defined content of macropores and to hydrocracking/hydroconversion and hydroprocessing methods which use these catalysts. A catalyst is described, which contains at least one hydro-dehydrogenating element chosen from a group consisting of elements of groups VIB and VIII of the periodic table of elements, 0.6 to 2.5% phosphorous. The said catalyst has total volume of pores of 0.35 to 0.74 ml/g, measured using mercury porosimetry and a non-zeolite carrier based on aluminosilicate, with the following characteristics: percentage content of silicon oxide 5 to 95 wt %; content of sodium less than 0.03%; total volume of pores, measured using mercury prosimetry, ranging from 0.45 to 0.96 ml/g; porosity, for which: i) volume of mesopores with diametre ranging from 40 to 150 Å and average pore diametre from 80 to140 Å ranges from 40 to 70% of the total volume of pores, measured using mercury porosimetry; ii) volume of macropores with diametre greater than 500 Å ranges from 30 to 60% of total volume of pores, measured using mercury porosimetry; BET specific surface area ranging from 100 to 550 m2/g; diffraction pattern in X-rays, which contains at least main characteristic bands of at least one of the transition modification aluminosilicates, which is part of a group which consists of alpha, rho, xi, eta, gamma, kappa, theta aluminosilicate modifications. Also described is a method of hydrocracking/hydroconverting hydrocarbon material, using a catalyst in one of the paragraphs described above. A method is also described for hydroprocessing hydrocarbon material, using a catalyst in accordance with one of the paragraphs described above.
EFFECT: design of a hydrocracking catalyst with high catalytic activity and selectivity.
41 cl, 16 ex, 2 tbl