WO2023072041A1 - 加氢-酸催化双功能催化剂及其制备方法和应用 - Google Patents
加氢-酸催化双功能催化剂及其制备方法和应用 Download PDFInfo
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- WO2023072041A1 WO2023072041A1 PCT/CN2022/127278 CN2022127278W WO2023072041A1 WO 2023072041 A1 WO2023072041 A1 WO 2023072041A1 CN 2022127278 W CN2022127278 W CN 2022127278W WO 2023072041 A1 WO2023072041 A1 WO 2023072041A1
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- Prior art keywords
- catalyst
- molecular sieve
- silica
- hydrogenation
- reaction
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- 239000003054 catalyst Substances 0.000 title claims abstract description 488
- 238000007171 acid catalysis Methods 0.000 title claims abstract description 10
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 216
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 20
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
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- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
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- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/068—Noble metals
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/633—Pore volume less than 0.5 ml/g
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- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- C07C2529/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- C07C2529/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present application relates to the field of catalysts, in particular to a hydrogenation-acid catalysis dual-function catalyst and its preparation method and application.
- Cyclohexylbenzene is an important chemical product, which has important applications in the fields of liquid crystals and rechargeable batteries. Among them, cyclohexylbenzene liquid crystal has extremely high chemical stability, photochemical stability and excellent physical properties, and is one of the ideal materials for liquid crystal displays. Cyclohexylbenzene can also be used as an additive component in the electrolyte of lithium-ion batteries, which has the function of preventing overcharge and can effectively improve battery safety. In addition, the important chemical products phenol and cyclohexanone can be obtained through further peroxidation and decomposition reactions using cyclohexylbenzene as an intermediate, which can then be used in the production of phenolic resin, caprolactam and nylon.
- cyclohexylbenzene is widely used. s concern.
- the basic information of cyclohexylphenyl is as follows: colorless liquid, CAS No. 827-52-1, density 0.95g/cm 3 , boiling point 238-240°C, melting point 5°C, flash point 98°C.
- the main methods for preparing cyclohexylbenzene include: hexenylbenzene cyclization method, and benzene hydroalkylation method.
- the basic principle of benzene hydroalkylation method is: use benzene and hydrogen as raw materials to hydrogenate part of benzene at the metal active center to obtain a 6-membered cycloalkene structure (such as cyclohexene, etc.), and further combine with benzene at the acidic active center Alkylation occurs at the position to give the cyclohexylbenzene product. Therefore, a dual-functional catalyst having both a hydrogenation center and an alkylation active center can be used in the production process of cyclohexylbenzene.
- patent CN112934251A discloses a hydrogenation metal-mordenite solution for n-heptane hydroisomerization reaction, and its isoheptane selectivity is about 60%-70%.
- Earlier US5643440, US5302279, US6190532, etc. disclosed the scheme of using noble metal-low acidity molecular sieves to catalyze the isomerization of heavy oil, but the overall lack of position regulation of hydrogenation and acid catalytic center sites did not show dual active centers optimal matching effect.
- the purpose of this application is to provide a hydrogenation-acid catalysis dual-function catalyst and its preparation method and application.
- the catalyst has dual functions of hydrogenation and acid catalysis, and is suitable for benzene hydroalkylation and alkane hydroisomerization reaction.
- the catalyst when used in the production of cyclohexylbenzene by hydroalkylation of benzene, the catalyst has the characteristics of high benzene conversion rate, good product selectivity and less by-product cyclohexane.
- the application provides a hydrogenation-acid catalysis dual-function catalyst, based on the quality of the catalyst, comprising 80-99.8% of the silica-alumina molecular sieve component, 0.2-2% of the loading on the The metal component with hydrogenation activity on the molecular sieve, and 0-20% of the hydrocarbyl modification component, wherein the hydrogenation active metal is selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, the The hydrocarbon group modification component is a C 1-20 hydrocarbon group.
- it provides the application of the catalyst of the present application in hydrocarbon hydroconversion reaction, including the step of contacting hydrocarbon feedstock with the catalyst in the presence of hydrogen.
- the present application provides a method for the one-step hydrogenation of benzene to prepare cyclohexylbenzene, comprising contacting and reacting benzene with the catalyst of the present application in the presence of hydrogen to obtain cyclohexylbenzene.
- the present application provides a method for alkane hydroisomerization, comprising contacting and reacting straight-chain alkanes with the catalyst of the present application in the presence of hydrogen to obtain isomerized products, wherein the straight-chain alkanes are Straight chain alkanes above C8.
- the catalyst of this application has dual functions of hydrogenation and solid acid, and can realize the hydroalkylation reaction of benzene to generate cyclohexylbenzene under mild reaction conditions.
- the conversion rate of benzene and the selectivity of the main product cyclohexylbenzene are very high. high, and the reaction system has good stability; especially, when using the silica-alumina molecular sieve with ATS structure as the molecular sieve component, the catalyst of the present application has a special pore structure and acidic characteristics, which is useful for reducing benzene hydrogenation alkyl
- the by-products of cyclohexane and dicyclohexylbenzene in the oxidation reaction have obvious effects;
- the catalyst of the present application has a specific composition, especially its active metal components are mainly distributed in the pores of the molecular sieve, and the metal content on the outer surface is low, thereby ensuring the content of excessive hydrogenation by-products (such as cyclohexane) less; and the outer surface of the catalyst has strong hydrophobicity, so it has better affinity with non-polar substances such as various alkanes and aromatics, ensuring that the conversion rate of benzene is maintained at a high level; and
- the catalyst of the present application is used for the isomerization of straight-chain alkanes, since the metal is mainly dispersed in the pores of the molecular sieve and the space distance between the strong acid sites is small, and the amount of acid on the outer surface is relatively small, the hydrogenation isomerization of alkanes In the hydrogenation reaction, it has the advantages of high substrate conversion and good selectivity of hydroisomerization products.
- Fig. 1 is the catalyst XRD spectrogram that preparation example 1-1 prepares
- Fig. 2 is the catalyst TEM figure that preparation example 1-1 prepares
- Fig. 3 is the SEM figure of the catalyst prepared by Preparation Example 1-1;
- Fig. 4 is the catalyst XRD spectrogram that preparation example II-1 prepares
- Fig. 5 is the infrared absorption spectrogram of the catalyst prepared by Preparation Example II-1;
- Fig. 6 is the catalyst XRD spectrogram that preparation example II-3 prepares.
- Figure 7 is the XRD spectrum of the catalyst prepared in Preparation Example III-1.
- silicon-aluminum ratio or “silicon-aluminum molar ratio” refers to the molar ratio between silicon calculated as SiO2 and aluminum calculated as Al2O3 in the molecular sieve.
- w, m, s, vs, wm, ms and s-vs, etc. represent the diffraction at the corresponding 2 ⁇ angle calculated based on the diffraction peak intensity (in peak height)
- the relative intensity I/I 0 of the peak relative to the strongest diffraction peak that is, the highest intensity diffraction peak
- I represents the peak intensity of the corresponding diffraction peak
- I 0 represents the peak intensity of the strongest diffraction peak
- w represents weak
- m represents Medium
- wm for weak to medium ms for medium to strong
- s-vs for strong to very strong are well known to those skilled in the art.
- pore volume refers to the volume of pores per unit mass of the catalyst.
- total pore volume refers to the volume of all pores per unit mass of the catalyst.
- micropore volume refers to the volume of all micropores (generally referring to pores with a channel diameter less than 2 nanometers) possessed by the catalyst per unit mass.
- the so-called “specific surface area” refers to the total area of a sample per unit mass, including the inner surface area and the outer surface area.
- Non-porous samples only have an external surface area, such as Portland cement, some clay mineral powders, etc.; porous and porous samples have both external and internal surface areas, such as asbestos fibers, diatomaceous earth, and molecular sieves.
- the surface area in micropores with a pore diameter less than 2 nanometers is the internal surface area, and the surface area after deducting the internal surface area is called the external surface area.
- the external surface area of a unit mass sample is the external specific surface area.
- the "catalyst outer surface” mentioned in this application refers to the surface of the catalyst except the inner surface of micropores with a pore diameter less than 2 nanometers.
- H-type silica-alumina molecular sieve has the meaning generally understood in the art, especially refers to a silica-alumina molecular sieve with active acid sites. It can usually be directly prepared by using an acidic system, or obtained by subjecting a basic metal-type silica-alumina molecular sieve such as Na-type silica-alumina molecular sieve to ammonium ion exchange and roasting.
- the amount and content of the metal component having hydrogenation activity are calculated by metal.
- any matters or matters not mentioned are directly applicable to those known in the art without any change.
- any of the implementations described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas are regarded as a part of the original disclosure or original record of the application, and should not be It is regarded as a new content that has not been disclosed or expected in this paper, unless those skilled in the art think that the combination is obviously unreasonable.
- the present application provides a hydrogenation-acid catalytic dual-functional catalyst, based on the quality of the catalyst, comprising 80-99.8% of the silica-alumina molecular sieve component, 0.2-2% of the The metal component with hydrogenation activity on the molecular sieve, and 0-20% of the hydrocarbyl modification component.
- the hydrocarbon-based modification component is connected to the surface of the molecular sieve through a covalent bond, for example, a hydrocarbon-Si-O-molecular sieve.
- a silylating agent can be used as a raw material to link the hydrocarbon-based modification component on the surface of the molecular sieve through the reaction of the silicon-oxygen bond connected to silicon with the active hydroxyl group on the surface of the molecular sieve.
- the hydrogenation active metal is selected from ruthenium, platinum, palladium, copper, nickel, or a combination thereof, more preferably ruthenium, palladium, or a combination thereof.
- the hydrocarbon group modification component is a C 1-20 hydrocarbon group, preferably a C 1-10 hydrocarbon group, more preferably selected from methyl, ethyl, propyl, isopropyl, butyl, benzene phenylmethyl, phenethyl, or combinations thereof.
- the mass content of the silica-alumina molecular sieve is 90-99.8%, such as 91%, 92%, 93%, 94%, 95%, 96% %, 97%, 98%, 99%, 99.5%, etc. Further preferably, the mass content of the silica-alumina molecular sieve is 90-98%.
- the mass content of the hydrogenation active metal is 0.2-1.5%, preferably 0.2-1.2%, more preferably 0.3-1.0%, for example 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% and so on.
- the silica-alumina molecular sieve is selected from molecular sieves with MWW, FAU, MOR, BEA or ATS structures, or a combination thereof, preferably molecular sieves with ATS structures.
- molecular sieves with MWW structure SCM-1 molecular sieves, MCM-22 molecular sieves, etc.
- the silica-alumina molecular sieve is H-type silica-alumina molecular sieve.
- the silica-alumina ratio of the molecular sieve in the silica-alumina catalyst is 2-50, preferably 2-40, more preferably 2-20.
- the molecular sieve is a silica-alumina molecular sieve with an ATS structure
- the X-ray diffraction spectrum of the catalyst shows the relative intensity characteristics of the diffraction peaks as shown in the following table :
- the X-ray diffraction spectrum of the catalyst shows the relative intensity characteristics of the diffraction peaks shown in any row in the following table:
- the crystals have a strip-like or rod-like morphology, the length of the crystals is 0.3-3 ⁇ m, and the aspect ratio is 2-20, preferably 5-20.
- the catalyst can optionally undergo one or both of hydrocarbylation treatment and reduction treatment, wherein the hydrocarbylation treatment and reduction treatment can be used in the hydrogenation active metal during the preparation of the catalyst After the loading step, it can also be carried out before the catalyst is used; and, when both hydrocarbylation treatment and reduction treatment are carried out, the reduction treatment can be carried out before or after the hydrocarbylation treatment, preferably after the hydrocarbylation treatment Afterwards.
- the catalyst is reduced.
- the silica-alumina molecular sieve is a molecular sieve having a structure of MWW, FAU, MOR or BEA
- the catalyst is preferably hydrocarbylated.
- the hydrogenation active metal in the catalyst, may exist in various forms, for example, in a form selected from metal element, oxide, chloride, nitrate, or a combination thereof.
- the hydrogenation active metal mainly exists in the form of simple metal, such as when the catalyst has been reduced.
- the particle size of the hydrogenation active metal particles is 0.5-10 nm, preferably 1-5 nm.
- the silica-alumina molecular sieve is a molecular sieve with an ATS structure, especially an ATS molecular sieve with the above-mentioned XRD spectrum characteristics, and based on the quality of the catalyst, the silicon
- the mass content of the aluminum molecular sieve is 80-99.8%, preferably 90-99.8%
- the mass content of the hydrogenation active metal is 0.2-2%, preferably 0.2-1.5%
- the catalyst does not contain the hydrocarbyl modified sex component.
- the mass of the silica-alumina molecular sieve is based on the quality of the catalyst
- the content is 80-98%, preferably 90-98%
- the mass content of the hydrogenation active metal is 0.2-1.5%, preferably 0.2-1.2%, more preferably 0.3-1.0%
- the hydrocarbyl modified The mass content of the components is 1-20%, preferably 1-10%, more preferably 2-10%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% wait.
- the mass content of the hydrogenation active metal on the outer surface of the catalyst to the elements on the outer surface is less than 0.5%, preferably less than 0.4%, more preferably 0.01% -0.35%, such as 0.01-0.2%.
- the distribution coefficient of the hydrogenation active metal on the outer surface of the catalyst is 1-20%, preferably 1.5-18%, more preferably 1.5-12%, eg 1.5-10%.
- the hydrogenation active metal distribution coefficient on the outer surface of the catalyst is calculated by the following formula:
- the distribution coefficient of the hydrogenation active metal on the outer surface (the mass content of the hydrogenation active metal on the outer surface of the catalyst to the elements on the outer surface * the external specific surface area of the catalyst) / (the total mass content of the hydrogenation active metal in the catalyst * the specific surface area of the catalyst) * 100 %,
- the mass content of hydrogenation active metals on the outer surface of the catalyst accounting for the outer surface elements is obtained by X-ray photoelectron spectroscopy (XPS) test, and the total mass content of hydrogenation active metals in the catalyst can be obtained by inductively coupled plasma atomic emission spectroscopy (ICP) analysis.
- XPS X-ray photoelectron spectroscopy
- ICP inductively coupled plasma atomic emission spectroscopy
- the distribution coefficient of the hydrogenation active metal on the outer surface of the catalyst can be used to characterize the ratio of the hydrogenation active metal content on the outer surface of the catalyst to the total hydrogenation active metal content. Specifically, when the hydrogenation active metals in the catalyst are loaded on the inner and outer surfaces of molecular sieves by a simple impregnation method, the ratio of the hydrogenation active metal content on the outer surface to the total hydrogenation active metal content is divided by the relative distribution of hydrogenation active metals on the outer surface In addition to being directly proportional, it is also directly proportional to the proportion of the external surface area of the catalyst.
- the specific surface area of the catalyst is 200-800m 2 /g, preferably 250-700m 2 /g, such as 300m 2 /g, 380m 2 /g, 385m 2 /g, 410m 2 / g g, 490m 2 /g or 500m 2 /g.
- the total pore volume of the catalyst is not less than 0.15 cm 3 /g, preferably 0.18-1.0 cm 3 /g, more preferably 0.2-1.0 cm 3 /g, for example 0.2-0.9 cm 3 /g.
- the micropore volume of the catalyst is 0.05-0.30 cm 3 /g, preferably 0.10-0.25 cm 3 /g.
- the total acid content of the catalyst is 400-1500 ⁇ mol ⁇ g -1 , preferably 600-1500 ⁇ mol ⁇ g -1 , such as 800 ⁇ mol ⁇ g -1 , 1250 ⁇ mol ⁇ g -1 , 1300 ⁇ mol ⁇ g -1 or 1500 ⁇ mol ⁇ g -1 .
- the catalyst when the catalyst is hydrocarbylated (i.e., the hydrocarbyl modification component content in the catalyst is in the range of 1-20%, preferably 1-10%), the catalyst's The relative acid equivalent of the outer surface is 15-50%, preferably 15-40%, for example 20%, 30% or 35%.
- the acid amount ratio of B acid/L acid of the catalyst is 0.2-8.0, preferably 0.4-6.0, more preferably 3.0- 6.0, for example 5.0 or 5.5.
- the ratio of acid amount of B acid/L acid of the catalyst is 3-10, preferably 5-7.
- the metal H 2 -TPR test reduction temperature of the catalyst is 470-500°C, preferably 480-500°C, in the case of hydrocarbylation treatment but no reduction treatment.
- a method for preparing the catalyst of the present application comprising the steps of:
- the H-type silica-alumina molecular sieve is selected from molecular sieves having a structure of MWW, FAU, MOR, BEA or ATS, or a combination thereof, preferably a molecular sieve having an ATS structure.
- the step (1) includes subjecting the raw material of the silica-alumina molecular sieve to ammonium ion exchange and calcining to obtain the H-type silica-alumina molecular sieve.
- the raw material of the silica-alumina molecular sieve is selected from a silica-alumina molecular sieve having a structure of MWW, FAU, MOR or BEA, or a combination thereof.
- the ammonium ion exchange is to exchange the alkali metal or alkaline earth metal cations such as Na + and K + in the basic metal type molecular sieve into NH 4 + , at 20- Exchange at 60°C for 0.5-4h, one or more times, the ammonium salt in the ammonium ion exchange is selected from one or more of ammonia water, ammonium chloride, ammonium nitrate, and ammonium carbonate. The concentration of the ammonium salt is 0.1-1.0mol/L.
- After the ammonium ion exchange dry at 60-120°C for 4-24h, and then roast. The roasting temperature is 400-650°C, the roasting time is 1-12 hours, and the roasting atmosphere is oxygen or air to obtain the H-type silica-alumina molecular sieve.
- the step (1) includes mixing the silicon source, the aluminum source, the fluorine source, the organic structure directing agent and water, and after pre-heating, crystallization treatment and roasting are carried out to obtain the H-type ATS Silica-alumina molecular sieve.
- the added silicon source is calculated as SiO 2
- the aluminum source is calculated as Al 2 O 3
- the fluorine source is calculated as F-
- the molar ratio of organic structure directing agent and water is The ratio is 1:(0.02-0.2):(0.5-2):(0.25-1.5):(3-15), preferably 1:(0.05-0.15):(0.5-1):(0.5-1): (5-10).
- the silicon source is selected from silicic acid, silica gel, silica sol, tetraethyl silicate, water glass, or a combination thereof
- the aluminum source is selected from pseudo Boehmite, aluminum isopropoxide, or their combination
- the fluorine source is hydrofluoric acid
- the organic structure directing agent is 4-pyrrolidinylpyridine.
- 4-pyrrolidinylpyridine is used as the organic structure directing agent, no alkali is needed during the reaction, and the obtained molecular sieve can be used as a catalyst without ammonium ion exchange.
- the heating pretreatment method is rotary evaporation or open heating to remove water, and the treatment condition of open heating is heating and stirring at 50-100°C, It is preferably heated and stirred at 70-90°C.
- step (1) after the raw material mixture is heated and pretreated, the molar ratio of the silicon source to water in terms of SiO2 during crystallization is 1: (1-10), preferably 1: (1.5-6.5).
- the crystallization conditions include: the crystallization temperature is 120-200°C, preferably 150-200°C, and the crystallization time is 7-21 days, preferably 7 -15 days.
- the crystallization in step (1), can be carried out in any manner conventionally known in the art, such as making the silicon source, aluminum source, fluorine source, and organic structure-oriented It is a method in which the agent and water are mixed according to a predetermined ratio, and the obtained mixture is heated and crystallized under crystallization conditions.
- the product in step (1), after the crystallization step is completed, can be obtained from the obtained mixture by any conventionally known separation method and calcination treatment.
- the separation means for example, a method of filtering, washing and drying the obtained mixture can be mentioned.
- the filtering, washing and drying can be performed in any manner conventionally known in the art.
- the filtering for example, the obtained product mixture can be simply suction filtered.
- the washing for example, washing with deionized water and/or ethanol is mentioned.
- the drying temperature is, for example, 40-250°C, preferably 60-150°C
- the drying time is, for example, 8-30 hours, preferably 10-20 hours. This drying may be performed under normal pressure or under reduced pressure.
- the calcination in step (1), can be carried out in any manner conventionally known in the art, for example, the calcination temperature is generally 300-800°C, preferably 400-650°C, and the calcination time Generally 1-12 hours, preferably 2-6 hours.
- the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen atmosphere.
- the hydrogenation active metal in step (2), can be loaded on the H-type silica-alumina molecular sieve by conventional means (such as impregnation).
- the step (2) loads the hydrogenation active metal on the H-type silicon aluminum molecular sieve by adding a solution of the hydrogenation active metal source to the H-type silica-alumina molecular sieve and drying it. on aluminum molecular sieves.
- the hydrogenation active metal source is selected from soluble compounds of the metal, preferably chlorides, nitrates of the metal, or combinations thereof.
- the solution of the hydrogenation active metal source may be a solution containing ruthenium prepared from ruthenium nitrate or ruthenium chloride.
- the concentration of the solution of the hydrogenation active metal source is 1.5-50 g/L, preferably 2-45 g/L.
- step (2) the solution of the hydrogenation active metal source is added dropwise to the H-type silica-alumina molecular sieve in step (1).
- the present application has no special limitation on the conditions of the dropwise addition, for example, it can be mixed for 1-10 hours after the dropwise addition at room temperature.
- the mass ratio of the mass of the hydrogenation active metal in the solution of the hydrogenation active metal source to the H-type silicon aluminum molecular sieve in step (1) is 0.002- 0.015:1, for example 0.005-0.02:1.
- the drying in step (2), can be performed in a conventional manner, such as oven drying, and the drying conditions preferably include: a drying temperature of 40-90° C., and a drying time of 4-12 hours.
- step (2) after the hydrogenation active metal is loaded on the H-type silica-alumina molecular sieve, one or both of hydrocarbylation treatment and reduction treatment can be optionally performed on the obtained product treatment, and when both hydrocarbylation treatment and reduction treatment are carried out, said reduction treatment may be performed before or after said hydrocarbylation treatment, preferably after hydrocarbylation treatment.
- step (2) includes reducing the product after loading the hydrogenation active metal.
- the reduction can be reduced with a reducing gas, preferably hydrogen reduction, and the reduction conditions preferably include: the reduction temperature is 300-550°C, the reduction time is 3-6 hours, and the volume space velocity of the reducing gas is 40-200h- 1 .
- step (2) includes hydrocarbylating the product after loading the hydrogenation active metal, Preferably, the product after loading the hydrogenation active metal is firstly subjected to the reduction treatment and then the hydrocarbylation treatment.
- the hydrocarbylating treatment in step (2) includes mixing and reacting the product loaded with hydrogenation active metal, preferably after reduction, with a hydrocarbylating agent in a solvent.
- the hydrocarbylating agent is selected from methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, propyltrimethoxysilane Oxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, tolylsilanetriol, diphenylsilanediol, or combinations thereof, Preferably selected from dimethyldimethoxysilane, diethyldimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, toluene silanetriols, or combinations thereof.
- the solvent used in the hydrocarbylation treatment is selected from methyltrimethoxysilane
- the mass ratio of the product loaded with hydrogenation active metal, the hydrocarbylating agent to the solvent is 1: (0.05-0.45): (5-55), Preferably it is 1:(0.06-0.40):(6-50), for example 1:(0.10-0.33):(8-50) or 1:(0.12-0.35):(7.5-52).
- the reaction conditions include: the reaction temperature is 40-110°C, preferably 70-110°C, and the reaction time is 6-48h, preferably 8-24h Hour.
- the resulting reaction product is separated (eg filtered), washed and dried.
- the separation, washing and drying can be carried out in any manner conventionally known in the art.
- the resulting product mixture can, for example, be simply suction-filtered as the filtration.
- washing for example, washing with deionized water and/or ethanol is mentioned.
- the drying temperature is, for example, 40-250°C, preferably 60-150°C; the drying time is, for example, 8-30 hours, preferably 10-20 hours. This drying may be performed under normal pressure or under reduced pressure.
- the hydrogenation-acid catalysis bifunctional catalyst prepared by the method of the present application is provided.
- the characteristics of the hydrogenation-acid catalysis dual-function catalyst obtained by the method of the present application are as described in the first aspect of the present application, and will not be repeated here.
- the application of the catalyst of the present application in hydrocarbon hydroconversion reaction including the step of contacting and reacting hydrocarbon feedstock with the catalyst in the presence of hydrogen.
- the hydrocarbon hydroconversion reaction is selected from benzene hydroalkylation reaction and alkane hydroisomerization reaction.
- the present application provides a one-step method for preparing cyclohexylbenzene by hydrogenating benzene, comprising contacting and reacting benzene with the catalyst described in the present application in the presence of hydrogen to obtain cyclohexylbenzene.
- the conditions of the reaction include: the mass ratio of benzene to the catalyst is 8-40, preferably 10-40; the reaction temperature is 100-220°C, preferably 120-200°C; the reaction time is 2 -8 hours, preferably 2.5-6 hours; the reaction hydrogen pressure is 0.8-2.5MPa, preferably 1.0-2.5MPa.
- the present application provides a method for hydroisomerization of alkanes, comprising contacting and reacting linear alkanes with the catalyst of the present application in the presence of hydrogen to obtain isomerized products, wherein the linear alkanes It is a C8 or higher straight-chain alkane, preferably a C8-C20 straight-chain alkane, more preferably a C8-C12 straight-chain alkane, such as n-heptane, n-decane, and the like.
- the reaction conditions include: the mass ratio of linear alkane to catalyst is 10-100, preferably 10-50; the reaction temperature is 250-400°C, preferably 300-400°C; the reaction time is 3 -10 hours, preferably 4-10 hours; the reaction hydrogen pressure is 2.5-5.0MPa, preferably 3.0-4.0MPa.
- a catalyst for producing cyclohexylbenzene said catalyst having a schematic chemical composition as shown in the formula "xM ⁇ ySiO 2 ⁇ zAl 2 O 3 ";
- M is a metal element, selected from one or more of ruthenium, platinum, palladium, copper and nickel metals;
- the catalyst according to item A1 characterized in that, in the catalyst, based on the mass of the catalyst, the mass content of the metal M is 0.2%-2%.
- the catalyst according to item A1 characterized in that, the catalyst has an X-ray diffraction spectrum as shown in the table below,
- the catalyst according to item A1 characterized in that the total acid content of the catalyst is 500-1500 ⁇ mol ⁇ g -1 , preferably 800-1500 ⁇ mol ⁇ g -1 , the ratio of the acid content of B acid/L acid 3-10, preferably 5-7.
- the catalyst according to item A1 characterized in that, in the catalyst, the crystals have elongated or rod-shaped morphology, the length of the crystals is 0.3-3 ⁇ m, and the aspect ratio is 2-20.
- the catalyst according to item A1 characterized in that, the specific surface area of the catalyst is 200-600 m2 /g, preferably 250-500 m2 /g; the micropore volume of the catalyst is 0.05-0.30 cm3 /g, preferably 0.10-0.25 cm3 /g.
- A8 a method for preparing a catalyst for the production of cyclohexylbenzene described in any one of item A1-7, comprising the steps:
- step (2) Add the solution containing metal M to the sample B in step (1), dry and reduce to prepare the catalyst.
- step (1) the added silicon source is calculated as SiO 2
- the aluminum source is calculated as Al 2 O 3
- the fluorine source is calculated as F -
- the molar ratio of organic structure directing agent a and water is 1: (0.02-0.2): (0.5-2): (0.25-1.5): (3-15), preferably 1: (0.05-0.15): ( 0.5-1):(0.5-1):(5-10).
- A10 according to the preparation method described in item A8 or A9, it is characterized in that, in step (1), the silicon source is selected from at least one of silicic acid, silica gel, silica sol, tetraethyl silicate, and water glass
- the aluminum source is selected from at least one of pseudo-boehmite and aluminum isopropoxide
- the fluorine source is selected from hydrofluoric acid
- the organic structure-directing agent is selected from 4-pyrrole Alkylpyridine.
- step (1) after the raw material mixture is preheated and pretreated, the molar ratio of silicon source to water in terms of SiO2 during crystallization It is 1:(1-10), preferably 1:(1.5-6.5).
- step (1) the crystallization conditions: the temperature is 120-200 ° C, the time is 7-21 days, preferably, the temperature is 150- 200°C, the time is 7-15 days.
- step (2) The preparation method according to item A8 or A9, characterized in that, in step (2), the concentration of the solution containing metal M is 2-50 g/L.
- the catalyst described in any one of items A1-A7 is used in a method for producing cyclohexylbenzene by one-step hydrogenation of benzene.
- A15 according to the method described in item A14, it is characterized in that, described method comprises raw material benzene and described catalyst contact reaction, makes cyclohexylbenzene with hydrogen as hydrogen source; Wherein, the mass ratio of raw material benzene and catalyst is 8 -40; the reaction temperature is 100-220°C, the reaction time is 2-8 hours, and the reaction hydrogen pressure is 0.8-2.5MPa.
- a catalyst for producing cyclohexylbenzene is characterized in that, said catalyst comprises molecular sieve, active metal M and hydrocarbyl modifying group;
- the active metal M is selected from one or more of ruthenium, platinum, palladium, copper and nickel;
- hydrocarbyl modifying group is selected from at least one of C1-C4 alkanyl groups
- the mass content of the active metal M is 0.2%-1.5%; the mass content of the metal M on the outer surface of the catalyst in the outer surface elements is less than 0.4%; the metal M distribution on the outer surface The coefficient is 1.2%-20%.
- the catalyst according to item B1 characterized in that, in the catalyst, based on the mass of the catalyst, the mass content of the metal M is 0.2%-1.2%.
- the catalyst according to item B1 characterized in that, in the catalyst, based on the mass of the catalyst, the mass content of the hydrocarbon-based modifying group is 1%-10%.
- molecular sieve in described catalyst is selected from at least one in MWW, FAU, MOR, BEA, ATS molecular sieve; Molecular sieve accounts for 90%-98% of catalyst mass in described catalyst %, the ratio of silicon to aluminum is 2-50, preferably 4-40.
- the catalyst according to item B1 characterized in that the specific surface area of the catalyst is 380-800m 2 /g, preferably 400-700m 2 /g; the total pore volume of the catalyst is not less than 0.15cm 3 / g, preferably 0.2-0.9 cm 3 /g.
- step (i) The preparation method according to item B6, characterized in that, in step (i), the concentration of the solution containing metal M is 2-50 g/L.
- step (ii) the alkylating agent is selected from methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane One or more of base silane, diethyldimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, preferably dimethyldimethoxysilane, diethyldimethylsilane One or more of oxysilane and isopropyltrimethoxysilane; the solvent is at least one of ethanol or toluene.
- step (iii) the mass ratio of the added catalyst precursor, alkylating agent and solvent is 1: (0.05-0.40): (5- 50).
- the catalyst described in any one of project B1-B5 is used for the method for benzene hydrogenation one-step system cyclohexylbenzene.
- C1 a method for preparing cyclohexylbenzene by one-step hydrogenation of benzene, comprising contacting reaction of raw material benzene and a catalyst, using hydrogen as a hydrogen source to prepare cyclohexylbenzene;
- the catalyst includes molecular sieves, active metal M and a hydrocarbon modification group;
- the active metal M is selected from one or more of ruthenium, platinum, palladium, copper and nickel;
- the hydrocarbyl modifying group is selected from at least one of phenyl, benzyl, and phenethyl;
- the total acid content of the catalyst is 400-1500 ⁇ mol ⁇ g -1
- the relative acid equivalent of the outer surface of the catalyst is 15%-35%.
- molecular sieve in described catalyst is at least one in MWW, FAU, MOR, BEA, ATS molecular sieve;
- Molecular sieve accounts for 80%-95% of catalyst mass in described catalyst %, the molar ratio of silicon to aluminum is 2-50, preferably 4-40.
- the preparation method of described catalyst comprises the following steps:
- step (A) characterized in that, in step (A), the concentration of the solution containing metal M is 1.5-45 g/L.
- step (B) the arylation reagent is selected from the group consisting of, phenyltrimethoxysilane, tolyltrimethoxysilane, phenylsilanetriol, One or more of tolylsilanetriol and diphenylsilanediol; the solvent is at least one of ethanol or toluene.
- step (B) the mass ratio of the added catalyst precursor, arylation reagent and solvent is 1: (0.06-0.45): (6-55 ).
- C10 according to the method described in item C1, it is characterized in that, in described reaction, the mass ratio of raw material benzene and catalyst is 8-40, and reaction temperature is 100-220 °C, and reaction time is 2-8 hour, and hydrogen pressure is 0.8-2.5MPa.
- the reagents and raw materials used are all commercially available products, and the purity is analytically pure.
- the structure of the sample is determined by the X-ray diffraction spectrum (XRD), and the XRD spectrum is determined by the X-ray powder diffractometer, and the X-ray used
- the model of the powder diffractometer is Panalytical X PERPRO X-ray powder diffractometer, and the following conditions are used to analyze the phase of the sample: CuK ⁇ ray source Nickel filter, 2 ⁇ scanning range 2-50°, operating voltage 40kV, current 40mA, scanning rate 10°/min.
- the model of the scanning electron microscope (SEM) used is S-4800II field emission scanning electron microscope.
- the method of measuring the crystal particle size of the sample is: use the scanning electron microscope to observe the molecular sieve at a magnification of 10,000 times, randomly select an observation field of view, calculate the average value of the sum of the particle diameters of all crystals in the observation field of view, and repeat the operation A total of 10 times. The average value of the sum of the average values of 10 times was used as the crystal grain size.
- the measuring method of sample size is: use transmission electron microscope (Netherlands FEI company G2F30 transmission electron microscope, operating voltage 300kV) to observe molecular sieve under 100,000 times of magnification , randomly select an observation field of view, calculate the average value of the sum of the sizes of all particles in the observation field of view, repeat this operation a total of 10 times, and take the average value of the sum of the average values of the 10 times as the particle size.
- transmission electron microscope Netherlands FEI company G2F30 transmission electron microscope, operating voltage 300kV
- the acid content and the acid species of the sample are measured using the pyridine adsorption infrared method (Nicolet Model 710 spectrometer).
- the specific operation steps are as follows: a. Sample pretreatment. The sample (about 30 mg) was compressed into a thin disc with a diameter of 13 mm, and loaded into an infrared sample cell. Afterwards, the samples were pretreated at 400 °C for 1 h under vacuum cell conditions. After the sample tank is cooled to room temperature, scan the infrared data of the sample as the background.
- the pyridine vapor was passed into the original position until the adsorption reached equilibrium, and the adsorption time was 1 h. c, pyridine desorption. After the adsorption is completed, vacuumize at 100°C until the internal pressure does not change. The desorption time is 40 minutes, and the infrared absorption spectra are scanned and recorded respectively. The difference spectrum before and after pyridine adsorption is the obtained pyridine adsorption-infrared absorption spectrum. Calculate the acid content of the sample according to the spectrum:
- r and w are the diameter (cm) and mass (g) of the thin catalyst disc
- A is the absorbance integral value at the specified wavenumber peak according to the scanning pyridine adsorption-infrared absorption spectrum.
- IMEC is the integral molar extinction coefficient
- IMEC L is 2.22
- IMEC B is 1.67.
- the peak near 1545cm -1 is B acid
- the peak near 1455cm -1 is L acid.
- the characterization of the relative acid equivalent of the outer surface of the catalyst is determined by "probe reaction” tricumene cracking, and its specific operation is to prepare 50 mg of catalyst and 100 mg of quartz Sand-mixed column samples were then passed through gas chromatography (GC, Agilent 7890B) at 250 °C with 1 ⁇ L of tricumene liquid per injection, followed by comparison with unhydrocarbylated “metal- Molecular sieve structure, to evaluate the relative acidity and activity of the outer surface of the catalyst, the specific calculation method is as follows:
- Relative acid equivalent of the outer surface (propene output of the alkylation group/(3 ⁇ tricumene addition amount of the alkylation group))/(propylene output of the non-hydrocarbylation group/(3 ⁇ tricumene addition amount of the non-hydrocarbylation group) ) ⁇ 100%.
- the total pore volume, micropore pore volume, total specific surface area and external specific surface area of the sample are measured by nitrogen physical adsorption-desorption method (BET method): Use a physical adsorption instrument (such as Micromeretic ASAP2020M physical adsorption instrument) to measure the nitrogen physical adsorption-desorption isotherm of the molecular sieve, and then calculate it by BET equation and t-plot equation.
- BET method nitrogen physical adsorption-desorption method
- the used Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP) model is Varian 725-ES, and the analysis sample is dissolved with hydrofluoric acid to detect the content of the element (in the form of mole), including the hydrogenation active metal in the sample (hereinafter referred to as "metal M”), and then obtain the mass content by conversion.
- ICP Inductively Coupled Plasma Atomic Emission Spectroscopy
- X-ray photoelectron spectroscopy test catalyst surface element state to determine catalyst outer surface metal M accounts for the mass content of outer surface elements.
- the metal M distribution coefficient on the outer surface of the catalyst is calculated by the following formula:
- Metal M distribution coefficient (mass content of metal M on the outer surface of the catalyst in elements on the outer surface * specific surface area of the catalyst) / (total mass content of metal M in the catalyst * specific surface area of the catalyst) * 100%.
- the metal reduction temperature is obtained by using H 2 -TPR test (hydrogen temperature programmed reduction).
- the TPR tester is an AMI-3300 temperature-programmed adsorption instrument from Altamira Instruments.
- the test method is to purge the sample with argon at 300°C for 1h, then cool down to 50°C, and then inject 10 %H 2 -Ar mixed gas, then the temperature was raised to 900°C at 10°C/min, the H 2 consumption curve was measured, and the peak temperature of the curve was recorded as the sample reduction temperature.
- the mass content of the hydrocarbon-based modified component is determined by means of mass loss ratio under thermogravimetric-mass spectrometry (TG-MS), and confirmed by mass spectrometry Types of modified hydrocarbon groups.
- TG-MS thermogravimetric-mass spectrometry
- the analyzer is the STA449F3-QMS403 model of Netzsch Company. The thermogravimetric results of the samples at 25-1000°C were measured at a heating rate of 10°C/min.
- FTIR Fourier transform infrared spectrometer
- the reaction product cyclohexylbenzene is qualitatively analyzed by gas chromatography-mass chromatography (GC-MS), and the product cyclohexylbenzene yield and reaction substrate are analyzed by gas chromatography (GC) conversion rate.
- the gas spectrometer is Agilent 7890A of Agilent Corporation of the United States
- the chromatographic column is a HP-5 non-polar capillary column (30m, 0.53mm)
- the gas chromatograph is Agilent 7890B
- the detector is a hydrogen flame ionization detector (FID).
- the chromatographic column is SE-54 capillary column (30m, 0.53mm).
- the yield % of the product cyclohexylbenzene (the molar amount of cyclohexylbenzene generated by the reaction ⁇ 2)/(the molar amount of the reaction substrate benzene) ⁇ 100%.
- the selectivity % of the product cyclohexylbenzene (the molar amount of cyclohexylbenzene produced by the reaction ⁇ 2)/(the molar amount of benzene reacted) ⁇ 100%.
- Isomerization product yield% (the molar weight of the isomerized product generated by the reaction)/(the molar weight of the reaction substrate n-decane) ⁇ 100%
- Isomerization product selectivity % (the molar amount of the isomerized product generated by the reaction)/(the molar amount of n-decane reacted) ⁇ 100%.
- the XRD spectrum data of the catalyst are shown in Table I-1, the XRD spectrum is shown in Figure 1, and the TEM photos and SEM photos are shown in Figures 2 and 3, respectively.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Ru is 0.3%
- the properties of the resulting catalysts are listed in Table 1-13.
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-2, and the XRD spectrum is similar to that shown in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Ru is 0.6%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-3, and the XRD spectrum is similar to that shown in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Ru is 1.5%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-4, and the XRD spectrum is similar to that shown in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Ru is 0.3%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-2.0 ⁇ m, and the aspect ratio is 2-15.
- the XRD spectrogram data of the catalyst are shown in Table I-5, and the XRD spectrogram is similar to that shown in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Ru is 0.3%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.5-2.5 ⁇ m, and the aspect ratio is 3-20.
- the XRD spectrum data of the catalyst are shown in Table I-6, and the XRD spectrum is similar to that in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 10
- the mass fraction of Pd is 0.3%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-7, and the XRD spectrum is similar to that in Figure 1.
- n(SiO 2 ):n(Al 2 O 3 ) 20
- the mass fraction of Ru is 0.3%
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-12.
- the XRD spectrum data of the catalyst are shown in Table I-8, and the XRD spectrum is similar to that in Figure 1.
- the properties of the resulting catalysts are listed in Table 1-13.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-12.
- the XRD spectrum data of the catalyst are shown in Table I-9, and the XRD spectrum is similar to that shown in Figure 1.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-10, and the XRD spectrum is similar to that shown in Figure 1.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.5-2.5 ⁇ m, and the aspect ratio is 3-20.
- the XRD spectrum data of the catalyst are shown in Table I-11, and the XRD spectrum is similar to that shown in Figure 1.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-10.
- the XRD spectrum data of the catalyst are shown in Table I-12, and the XRD spectrum is similar to that shown in Figure 1.
- the SEM of the catalyst is similar to that shown in FIG. 3 .
- the crystals have a strip shape, the length of the crystals is 0.4-1.5 ⁇ m, and the aspect ratio is 2-12.
- Example I-1 The catalyst evaluation method is shown in Example I-1, and the composition and evaluation results of the catalyst are listed in Table I-15.
- Example I-1 The catalyst evaluation method is shown in Example I-1, and the composition and evaluation results of the catalyst are listed in Table I-15.
- Example I-1 The catalyst evaluation method is shown in Example I-1, and the composition and evaluation results of the catalyst are listed in Table I-15.
- Example I-1 The catalyst evaluation method is shown in Example I-1, and the composition and evaluation results of the catalyst are listed in Table I-15.
- the catalyst prepared in Preparation Example I-1 was washed, dried, and put into the next reaction, and a total of 6 reactions were circulated.
- the catalyst evaluation retains the reaction conditions in Example I-1, that is, 8 g of benzene is added into the autoclave, and hydrogen is charged to make the system pressure reach 1.2 MPa. Then the temperature of the system was raised to 150° C., and the reaction ended after 4 hours.
- the catalyst evaluation results are listed in Table I-16.
- catalyst evaluation retains the reaction condition among the embodiment I-12, promptly adds 8g benzene in autoclave, and fills with hydrogen to make system pressure reach 1.2MPa. Then the temperature of the system was raised to 150° C., and the reaction ended after 4 hours. Catalyst evaluation results are listed in Table I-17.
- the Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 25:1 (with MWW structure) and 0.2mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, Then centrifuge and wash, repeat the ammonium ion exchange twice, dry the sample obtained at 100°C overnight, and roast in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieve.
- the hydrocarbylated molecular sieve was reduced in a fixed-bed reactor at 450° C. and a hydrogen volume space velocity of 50 h ⁇ 1 for 3 h to prepare the target catalyst.
- the XRD spectrum of the obtained catalyst is shown in Figure 4. According to XRD, it can be known that the catalyst retains the MWW molecular sieve structure as a whole.
- the infrared absorption spectrum of the obtained catalyst is shown in Fig. 5, and the Si-C absorption peak appears near the visible wavenumber 2950 cm ⁇ 1 .
- the hydrocarbyl group was determined to be methyl by TG-MS test, and the content is shown in Table II-1. Catalyst specific surface area, pore volume, acidic properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content are shown in Table II-1.
- the Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 25:1 (with MWW structure) and 0.2mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, Then centrifuge and wash, repeat the ammonium ion exchange twice, dry the sample obtained at 100°C overnight, and roast in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieve.
- Gained catalyst XRD spectrogram is the same as Fig. 1. Catalyst specific surface area, pore volume, acidic properties (including total acid content and external surface acid content), metal M content and external surface metal M content are shown in Table II-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD spectrum of the obtained catalyst is shown in Figure 6, and the catalyst as a whole retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table II-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 5:1 and 0.2 mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table II-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 5:1 and 0.2 mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table II-1.
- H-type ATS molecular sieve precursor Take 1.5 mL of 3.2 g/L ruthenium chloride solution and add dropwise on 1 g of the obtained H-type ATS molecular sieve precursor. After drying at 80°C for 2h, it was reduced for 3h in a fixed-bed reactor at 450°C and a hydrogen volume space velocity of 50h -1 to obtain a catalyst precursor. Take 0.2g of isopropyltrimethoxysilane, mix with 1g of catalyst precursor and 10mL of toluene solvent, reflux at 110°C for 24h, centrifuge with water, wash, and dry at 80°C for 12h to obtain the catalyst.
- the obtained catalyst XRD as a whole retains the ATS molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table II-1.
- the catalyst was prepared with reference to Preparation Example II-1, except that the raw material was changed to Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 50:1, and the remaining steps remained unchanged. Catalyst properties are shown in Table II-1.
- the obtained catalyst XRD pattern is similar to that shown in Figure 1. Catalyst specific surface area, pore volume, acidic properties (including total acid content and external surface acid content), metal M content and external surface metal M content are shown in Table II-1.
- the catalyst was prepared with reference to Preparation Example II-1, except that the step of treating with methyltrimethoxysilane was omitted.
- the properties of the obtained catalyst are shown in Table II-1.
- the catalyst evaluation method is the same as in Example II-5, and the catalyst evaluation results are listed in Table II-2.
- the catalyst was prepared with reference to Preparation Example II-1, except that the amount of the added ruthenium chloride solution of the same concentration was increased to 8mL, that is, only the metal content in the catalyst was increased. Catalyst properties are shown in Table II-1.
- the catalyst evaluation method is the same as in Example II-5, and the catalyst evaluation results are listed in Table II-2.
- the catalyst evaluation method is the same as in Example II-5, and the catalyst evaluation results are listed in Table II-2.
- the catalyst prepared in Preparation Example II-1 was washed, dried, and put into the next reaction, and a total of 6 reactions were circulated.
- the evaluation of the catalyst is to add 8 g of benzene into the autoclave, and fill in hydrogen to make the system pressure reach 1.2 MPa. Then the temperature of the system was raised to 150° C., and the reaction ended after 4 hours.
- the catalyst evaluation results are shown in Table II-3.
- MCM-22 molecular sieves (with MWW structure) with a silicon-aluminum molar ratio of 20:1 and 0.2 mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD spectrum of the obtained catalyst is shown in Figure 7, and the catalyst as a whole retains the MWW molecular sieve structure unchanged.
- Catalyst specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content are shown in Table III-1.
- the preparation process is the same as that of Preparation Example III-1, except that the Na-type MCM-22 molecular sieve with a silicon-aluminum molar ratio of 25:1 is selected.
- the XRD pattern of the catalyst obtained is the same as in Figure 7. Catalyst specific surface area, pore volume, acidic properties (including total acid content and external surface acid content), metal M content and external surface metal M content are shown in Table III-1.
- the preparation process is the same as that of Preparation Example III-1, except that Na-type mordenite (with a MOR structure) with a silicon-aluminum molar ratio of 10:1 is selected.
- the obtained catalyst retains the MOR molecular sieve structure as a whole.
- the specific surface area, pore volume, acidic properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table III-1.
- the preparation process is the same as that of Preparation Example III-1, except that the Na-type mordenite (having a MOR structure) with a silicon-aluminum molar ratio of 15:1 is selected.
- the obtained catalyst retains the MOR molecular sieve structure as a whole.
- the specific surface area, pore volume, acidic properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table III-1.
- the obtained catalyst retains the ATS molecular sieve structure as a whole.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table III-1.
- the catalyst was prepared with reference to Preparation Example III-1, except that the raw material was changed to Na-type MCM-22 molecular sieve (with MWW structure) with a silicon-aluminum molar ratio of 50:1, and the remaining steps remained unchanged.
- the XRD pattern of the obtained catalyst is the same as that in Figure 7. Catalyst specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content are shown in Table III-1.
- the catalyst was prepared with reference to Preparation Example III-1, except that the part treated with phenyltrimethoxysilane was omitted.
- Catalyst evaluation method is the same as embodiment III-4, and catalyst evaluation result is listed in table III-2.
- the catalyst was prepared with reference to Preparation Example III-1, the difference being that the amount of the added ruthenium chloride solution of the same concentration was increased to 8mL, that is, only the metal content in the catalyst was increased.
- Catalyst evaluation method is the same as embodiment III-4, and catalyst evaluation result is listed in table III-2.
- the catalyst was prepared with reference to Preparation Example III-1, except that the condition of the arylation step was changed from adding 0.3 g of phenyltrimethoxysilane to adding 0.8 g of phenyltrimethoxysilane.
- Catalyst evaluation method is the same as embodiment III-4, and catalyst evaluation result is listed in table III-2.
- the catalyst obtained in Preparation Example III-1 is evaluated according to the method of Example III-4, wherein the partial pressure of hydrogen in the reaction conditions is changed to 4.0MPa, and all the other operations remain unchanged.
- the catalyst evaluation results are listed in Table III-2.
- the catalyst prepared in Preparation Example III-1 was washed, dried, and put into the next reaction, and a total of 6 reactions were circulated.
- the evaluation of the catalyst is to add 8 g of benzene into the autoclave, and fill in hydrogen to make the system pressure reach 1.2 MPa. Then the temperature of the system was raised to 150° C., and the reaction ended after 4 hours.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD spectrum pattern of the obtained catalyst is the same as that in Fig. 6.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table IV-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table IV-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table IV-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 5:1 and 0.2 mol/L NH 4 NO 3 solution (mass ratio 1:20) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table IV-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- the XRD of the obtained catalyst generally retains the FAU molecular sieve structure unchanged.
- the specific surface area, pore volume, acidity properties (including total acid content and external surface acid equivalent), metal M content and external surface metal M content of the catalyst are shown in Table IV-1.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- Example IV-1 The catalyst evaluation method is shown in Example IV-1, and the composition and evaluation results of the catalyst are listed in Table IV-2.
- the Na-type Y molecular sieve (with FAU structure) with a silicon-aluminum molar ratio of 10:1 and 0.2 mol/L NH4NO3 solution (mass ratio 1:20 ) were subjected to ammonium ion exchange at 45°C for 2 hours, and then centrifuged After washing and repeating the ammonium ion exchange twice, the sample obtained was dried overnight at 100°C and calcined in air at 550°C for 6 hours to obtain H-type silica-alumina molecular sieves.
- Example IV-1 The catalyst evaluation method is shown in Example IV-1, and the composition and evaluation results of the catalyst are listed in Table IV-2.
- any combination of various implementations of the present application can also be made, as long as they do not violate the idea of the present application, they should also be regarded as the content of the invention of the present application.
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Abstract
Description
2θ(°) | 相对强度(I/I 0×100) |
7.588-8.188 | vs |
16.286-16.886 | m-s |
18.927-19.527 | s |
20.492-21.092 | s |
22.096-22.696 | m-s |
26.983-27.583 | m-s |
2θ(°) | 相对强度(I/I 0×100) |
21.600-22.200 | m |
28.224-28.824 | w-m |
28.975-29.575 | w-m |
30.255-30.855 | w-m |
31.794-32.394 | m |
34.607-35.207 | m |
2θ(°) | 相对强度(I/I 0×100) |
7.888±0.3 | vs |
16.586±0.3 | m-s |
19.227±0.3 | s |
20.792±0.3 | s |
22.396±0.3 | m-s |
27.283±0.3 | m-s |
2θ(°) (a) | 相对强度(I/I 0×100) |
21.900±0.3 | m |
28.524±0.3 | w-m |
29.275±0.3 | w-m |
30.555±0.3 | w-m |
32.094±0.3 | m |
34.907±0.3 | m |
循环套用次数 | 环己基苯的收率(%) | 环己基苯的选择性(%) |
1 | 59 | 93.7 |
2 | 59 | 93.2 |
3 | 60 | 93.4 |
4 | 59 | 93.8 |
5 | 59 | 92.9 |
6 | 59 | 93.5 |
循环套用次数 | 环己基苯的收率(%) | 环己基苯的选择性(%) |
1 | 60 | 94.7 |
2 | 60 | 94.3 |
3 | 59 | 93.8 |
4 | 60 | 94.5 |
5 | 59 | 93.9 |
6 | 60 | 94.4 |
循环套用次数 | 环己基苯的收率(%) | 环己基苯的选择性(%) |
1 | 57 | 84.1 |
2 | 56 | 84.7 |
3 | 57 | 84.3 |
4 | 57 | 83.8 |
5 | 55 | 84.2 |
6 | 57 | 84.4 |
循环套用次数 | 环己基苯的收率(%) | 环己基苯的选择性(%) |
1 | 58 | 87.8 |
2 | 57 | 87.2 |
3 | 57 | 87.0 |
4 | 58 | 87.7 |
5 | 56 | 87.1 |
6 | 58 | 87.0 |
Claims (15)
- 一种加氢-酸催化双功能催化剂,以催化剂的质量为基准,包含80-99.8%的硅铝分子筛组分,0.2-2%的负载在所述分子筛上的具有加氢活性的金属组分,和0-20%的烃基改性组分,其中所述加氢活性金属选自钌、铂、钯、铜、镍,或者它们的组合,更优选为钌、钯或者它们的组合;所述烃基改性组分为C 1-20烃基,优选为C 1-10烃基,更优选选自甲基、乙基、丙基、异丙基、丁基、苯基、苯甲基、苯乙基,或者它们的组合。
- 根据权利要求1所述的催化剂,其中所述硅铝分子筛选自具有MWW、FAU、MOR、BEA或ATS结构的分子筛,或者它们的组合,优选为具有ATS结构的分子筛;优选地,所述硅铝分子筛的硅铝比为2-50、优选为2-40、更优选为2-20。
- 根据权利要求1或2所述的催化剂,其中所述硅铝分子筛为具有ATS结构的硅铝分子筛,并且所述催化剂的X-射线衍射谱图显示出如下表所示的衍射峰相对强度特征:
2θ(°) 相对强度(I/I 0×100) 7.588-8.188 vs 16.286-16.886 m-s 18.927-19.527 s 20.492-21.092 s 22.096-22.696 m-s 26.983-27.583 m-s - 根据权利要求3所述的催化剂,其中所述催化剂的X-射线衍射谱图显示出如下表中任一行所示的衍射峰相对强度特征:
2θ(°) 相对强度(I/I 0×100) 21.600-22.200 m 28.224-28.824 w-m 28.975-29.575 w-m 30.255-30.855 w-m 31.794-32.394 m 34.607-35.207 m - 根据权利要求1-4中任一项所述的催化剂,其中,以催化剂的质量为基准,所述催化剂包含80-98%的所述硅铝分子筛组分,0.2-2%的所述具有加氢活性的金属组分,和1-20%的所述烃基改性组分,并且根据X射线光电子能谱分析(XPS)测试,所述催化剂外表面的加氢活性金属占外表面元素的质量含量在0.5%以下、优选0.4%以下;优选地,以催化剂的质量为基准,所述催化剂包含90-98%的所述硅铝分子筛组分,0.2-1.5%的所述具有加氢活性的金属组分,和1-10%的所述烃基改性组分;进一步优选地,所述催化剂外表面的加氢活性金属分布系数为1-20%、优选1.5-18%。
- 根据权利要求1-5中任一项所述的催化剂,具有以下特征中的一个或多个:所述催化剂的比表面积为200-800m 2/g,优选250-700m 2/g;所述催化剂的总孔容不低于0.15cm 3/g,优选为0.18-1.0cm 3/g;所述催化剂的微孔孔容为0.05-0.30cm 3/g,优选为0.10-0.25cm 3/g;所述催化剂的总酸量为400-1500μmol·g -1,优选为600-1500μmol·g -1;所述催化剂的外表面相对酸当量为15-50%,优选为15-40%;所述催化剂的金属H 2-TPR测试还原温度为470-500℃,优选为480-500℃;所述催化剂的B酸/L酸的酸量之比为0.2-8.0,优选为0.4-6.0;以及所述催化剂中,晶体具有长条状或棒状形貌,晶体的长度为0.3-3μm,长宽比为2-20,优选为5-20。
- 制备权利要求1-6中任一项所述的催化剂的方法,包括如下步骤:(1)提供H型硅铝分子筛;以及(2)在所述H型硅铝分子筛上负载所述加氢活性金属,任选对所 得产物进行烃基化处理和/或还原,得到所述催化剂。
- 根据权利要求7所述的方法,其中所述步骤(1)包括将硅铝分子筛原料经过铵离子交换和焙烧,得到所述H型硅铝分子筛,优选地,所述硅铝分子筛原料选自具有MWW、FAU、MOR或BEA结构的硅铝分子筛,或者它们的组合。
- 根据权利要求7所述的方法,其中所述步骤(1)包括将硅源、铝源、氟源、有机结构导向剂和水混合,加热预处理后,再进行晶化处理和焙烧,得到H型ATS硅铝分子筛,其中所述硅源选自硅酸、硅胶、硅溶胶、硅酸四乙酯、水玻璃,或者它们的组合,所述铝源选自拟薄水铝石、异丙醇铝,或者它们的组合,所述氟源选择氢氟酸,所述有机结构导向剂为4-吡咯烷基吡啶;优选地,步骤(1)具有以下特征中的一个或多个:所加入的硅源以SiO 2计、铝源以Al 2O 3计、氟源以F-计、有机结构导向剂和水的摩尔配比为1∶(0.02-0.2)∶(0.5-2)∶(0.25-1.5)∶(3-15),优选为1∶(0.05-0.15)∶(0.5-1)∶(0.5-1)∶(5-10);所述晶化处理中,硅源以SiO 2计和水的摩尔配比为1∶(1-10),优选1∶(1.5-6.5);以及所述晶化处理的条件包括:晶化温度为120-200℃、优选150-200℃,晶化时间为7-21天、优选为7-15天。
- 根据权利要求7-9中任一项所述的方法,其中,在步骤(2)中,通过将加氢活性金属源的溶液加入到所述H型硅铝分子筛中并干燥来将所述加氢活性金属负载到所述H型硅铝分子筛上,优选地,所述步骤(2)具有以下特征中的一个或多个:所述加氢活性金属源选自所述金属的可溶性化合物,优选选自所述金属的氯化物、硝酸盐,或者它们的组合;以加氢活性金属的质量计,所述加氢活性金属源的溶液的浓度为1.5-50g/L,优选为2-45g/L;所述加氢活性金属源的溶液采用滴加的方式加入所述H型硅铝分子筛中;以及所述加氢活性金属源的溶液中所述加氢活性金属的质量与所述H型硅铝分子筛的质量比为0.002-0.015∶1,例如为0.005-0.02∶1。
- 根据权利要求7-10中任一项所述的方法,其中所述烃基化处 理包括将负载加氢活性金属后的产物与烃基化试剂在溶剂中混合反应来进行,其中所述烃基化试剂选自甲基三甲氧基硅烷、二甲基二甲氧基硅烷、乙基三甲氧基硅烷、二乙基二甲氧基硅烷、丙基三甲氧基硅烷、异丙基三甲氧基硅烷,苯基三甲氧基硅烷、甲苯基三甲氧基硅烷、苯基硅烷三醇、甲苯基硅烷三醇、二苯基硅烷二醇,或者它们的组合,优选选自二甲基二甲氧基硅烷、二乙基二甲氧基硅烷、异丙基三甲氧基硅烷、苯基三甲氧基硅烷、甲苯基三甲氧基硅烷、苯基硅烷三醇、甲苯基硅烷三醇,或者它们的组合;优选地,所述烃基化处理包括以下特征中的一个或多个:所述溶剂为乙醇、甲苯或者它们的组合;所述负载加氢活性金属后的产物、烃基化试剂与溶剂的质量比为1∶(0.05-0.45)∶(5-55)、优选为1∶(0.06-0.40)∶(6-50);以及所述烃基化处理的反应条件包括:反应温度为40-110℃、优选为70-110℃,反应时间为6-48h、优选为8-24小时。
- 根据权利要求7-11中任一项所述的方法,其中所述还原采用还原性气体、优选氢气进行,所述还原的条件优选包括:还原温度为300-450℃,还原时间3-6小时,还原气体的体积空速为40-200h -1。
- 权利要求1-6中任一项所述的加氢-酸催化双功能催化剂在烃类加氢转化反应中的应用,包括在氢气存在下,使烃类原料与所述催化剂接触反应的步骤,优选地,所述加氢转化反应选自苯加氢烷基化反应和烷烃加氢异构化反应。
- 苯加氢一步法制环己基苯的方法,包括在氢气存在下,使苯与权利要求1-6中任一项所述的加氢-酸催化双功能催化剂接触反应,得到环己基苯;优选地,所述反应的条件包括:苯与催化剂的质量比为8-40、优选为10-40;反应温度为100-220℃、优选为120-200℃;反应时间为2-8小时、优选为2.5-6小时;反应氢气压力为0.8-2.5MPa、优选为1.0-2.5MPa。
- 烷烃加氢异构化方法,包括在氢气存在下,使直链烷烃与权利要求1-6中任一项所述的加氢-酸催化双功能催化剂接触反应,得到异构化产物;其中,所述直链烷烃为C8以上的直链烷烃,优选为C8-C20直链烷烃,更优选为C8-C12直链烷烃;优选地,所述反应条件包括:直链烷烃与催化剂质量比为10-100、优选为10-50;反应温度为250-400℃、优选为300-400℃;反应时间为3-10小时、优选为4-10小时;反应氢气压力为2.5-5.0MPa,优选为3.0-4.0MPa。
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