WO2022063266A1 - 歧化与烷基转移催化剂及其制备和应用 - Google Patents

歧化与烷基转移催化剂及其制备和应用 Download PDF

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WO2022063266A1
WO2022063266A1 PCT/CN2021/120641 CN2021120641W WO2022063266A1 WO 2022063266 A1 WO2022063266 A1 WO 2022063266A1 CN 2021120641 W CN2021120641 W CN 2021120641W WO 2022063266 A1 WO2022063266 A1 WO 2022063266A1
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catalyst
metal
molecular sieve
weight
hours
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PCT/CN2021/120641
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English (en)
French (fr)
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李经球
丁健
吴雅楠
孔德金
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority claimed from CN202011036008.5A external-priority patent/CN114425425A/zh
Priority claimed from CN202011034477.3A external-priority patent/CN114425404B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to KR1020237013600A priority Critical patent/KR20230079115A/ko
Priority to EP21871635.5A priority patent/EP4219005A4/en
Priority to US18/246,713 priority patent/US20230364593A1/en
Priority to JP2023519203A priority patent/JP2023542418A/ja
Publication of WO2022063266A1 publication Critical patent/WO2022063266A1/zh

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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Definitions

  • the present application relates to the technical field of catalysts, in particular to a disproportionation and transalkylation catalyst and its preparation and application.
  • toluene and carbon 9 and above heavy aromatic hydrocarbons (C 9 + A) to increase the production of xylene is a method for effectively utilizing heavy aromatics to increase the production of xylene, and is widely used.
  • the reaction network between toluene and C 9 + A is complex, involving dealkylation and lightening of heavy aromatics, disproportionation and transalkylation, and hydrocracking of benzene rings.
  • the above reactions are acid-catalyzed reactions, which can be carried out under the action of the acid center of the molecular sieve.
  • certain metal components can be introduced into the catalyst.
  • Metal components can promote the rapid hydrogenation and saturation of olefin intermediates, accelerate reactions such as dealkylation, and improve the conversion efficiency of heavy aromatics, but at the same time, metal components can also aggravate the hydrogenation and saturation of aromatics.
  • Metals such as platinum, palladium, rhenium, and molybdenum are often used as hydrogenation metal components. Different metals have different effects on the reaction. Too strong metal hydrogenation function will lead to an increase in the side reaction of aromatic hydrocarbon hydrogenation and an increase in the loss rate of aromatic rings; Metals with too weak hydrogenation function have little effect on promoting the main reaction. The selection of suitable metal promoters is the key to catalyst synthesis.
  • CN102688770A discloses an aromatic hydrocarbon hydrogenation catalyst, which is composed of mesoporous zeolite and precious metal, and the precious metal is selected from platinum, palladium, rhodium, silver, ruthenium, gold, etc., and is prepared by post-processing, soft template or hard template.
  • the obtained mesoporous zeolite is calcined by ammonium nitrate ion exchange to obtain a catalyst carrier, and then impregnated and loaded with precious metal components, thereby improving the hydrodearomatization activity and sulfur resistance of the catalyst.
  • CN1259930A discloses a double-layer catalyst reaction process.
  • the upper layer catalyst contains a metal of Group VIIIB and is selected from MCM-22, ZSM-12, Beta, PSH-3, SSZ-25 zeolite molecular sieve, and the lower layer catalyst is ZSM-5 molecular sieve , the reactants first pass through the upper catalyst to produce xylene and benzene intermediate, and then pass through the second catalyst bed to purify the benzene product.
  • CN1122571 discloses a noble metal-containing molecular sieve catalyst suitable for processing high C 9 + A feedstock, the catalyst is composed of 10-80% by weight mordenite or beta zeolite and 0-70% by weight ZSM-5,5 -90% by weight of ⁇ -Al 2 O 3 as a carrier, loading 0.001-0.5 parts by weight of platinum and 0.01-10.0 parts by weight of tin or 0.01-7.0 parts by weight of lead.
  • the purpose of the present application is to provide a novel disproportionation and transalkylation catalyst and its preparation and application, which are suitable for the catalytic conversion of alkyl aromatic hydrocarbons, such as disproportionation and transalkylation of alkyl aromatic hydrocarbons, especially in the form of
  • the reaction for producing xylene from toluene and/or C 9 + alkyl aromatic hydrocarbons as raw materials has the advantages of high conversion efficiency, low aromatic hydrocarbon hydrogenation side reactions and high product selectivity.
  • the present application provides a disproportionation and transalkylation catalyst, comprising an acidic molecular sieve, a first metal component immobilized on the acidic molecular sieve, and an oxide assistant, the first metal
  • the first metal contained in the component is selected from at least one of VB group metals, VIB group metals and VIIB group metals, and the amount of medium and strong acid in the catalyst is 0.05-2mmol/g catalyst, and the amount of medium and strong acid accounts for the total.
  • the proportion of acid content is 60-99%.
  • the first metal is at least one selected from Mo, W and Re, more preferably a combination of at least two of Mo, Re and W, particularly preferably a combination of Mo, Re and W .
  • the catalyst further comprises a second metal component different from the first metal component, the second metal component preferably being supported on the oxide promoter.
  • the second metal in the second metal component is selected from at least one of Group IA, Group IIA, Group IIIA, Group IVA, Group VA, Group IVB and Lanthanide metals.
  • the application of the disproportionation and transalkylation catalyst according to the present application in the catalytic conversion of alkyl aromatic hydrocarbons includes disproportionation reaction of alkyl aromatic hydrocarbons, transalkylation of alkyl aromatic hydrocarbons reaction, or a combination of the two.
  • a process for the catalytic conversion of alkyl aromatic hydrocarbons comprising the step of contacting and reacting a feedstock comprising alkyl aromatic hydrocarbons with a disproportionation and transalkylation catalyst according to the present application in the presence of hydrogen.
  • the catalyst of the present application uses active metal components comprising VB, VIB and/or VIIB group metals, and is immobilized on the acidic molecular sieve, based on the hydrogen migration effect on the metal surface and the synergistic effect with the acid site of the molecular sieve, and is loaded on the acidic molecular sieve.
  • the metal components on the surface of the acidic molecular sieve can preferentially cover or weaken some of the strong acid centers, and synergize with the nearby acidic sites of the molecular sieve to promote the conversion efficiency of aromatic hydrocarbons and reduce the side reactions of hydrogenation, with high reactivity and low aromatics loss.
  • the catalyst of the present application uses two metal components, and based on the influence of different metal components on the aromatic hydrocarbon conversion reaction process, the supported metal distribution on the catalyst is regulated, wherein the higher hydrogenation function is.
  • the first metal component is supported on the surface of the acidic molecular sieve to promote the conversion efficiency of aromatics, while the second metal component is preferably supported on the oxide auxiliary to inhibit the side reaction of aromatics hydrogenation and saturation on the surface of the oxide auxiliary. .
  • Figure 1A and Figure 1B show the NH 3 -TPD spectra of the catalysts obtained in Example I-1 and Comparative Example I-1 of the present application, respectively;
  • Fig. 2 shows the TEM image of the catalyst obtained in Example I-1 of the present application
  • Figure 3 shows the TEM image of the catalyst obtained in Example II-1 of the present application.
  • any specific numerical value disclosed herein, including the endpoints of a numerical range, is not limited to the precise value of the numerical value, but is to be understood to encompass values approximating the precise value, such as within ⁇ 5% of the precise value. all possible values. And, for the disclosed numerical range, between the endpoint values of the range, between the endpoint values and the specific point values in the range, and between the specific point values, one or more new values can be obtained in any combination. Numerical ranges, these new numerical ranges should also be considered to be specifically disclosed herein.
  • acidic molecular sieve has the meaning commonly understood in the art and refers to a molecular sieve having B acid and/or L acid sites.
  • C 8 aromatics (or C 8 A) refers to aromatic hydrocarbons having 8 carbon atoms or mixtures thereof, such as xylene; similarly the term “C 9 aromatics (or C 9 A)” refers to Aromatic hydrocarbons with 9 carbon atoms or mixtures thereof, such as propylbenzene, ethyl toluene, mesitylene, etc.
  • C 9 + aromatic hydrocarbons refers to aromatic hydrocarbons or mixtures thereof having 9 or more carbon atoms
  • C 10 + aromatic hydrocarbons (or C 10 + A) refers to aromatic hydrocarbons or mixtures thereof having 10 or more carbon atoms.
  • C10 + alkyl aromatic hydrocarbons include, but are not limited to, diethylbenzene, dimethylethylbenzene, methpropylbenzene, tetratoluene, methylnaphthalene, dimethylnaphthalene, and the like.
  • the medium and strong acid content of the catalyst is calculated according to the peak area of the NH 3 -TPD spectrum in the range of 200-400°C ; The ratio of the peak area in the °C interval to the total peak area in the 100-600 °C interval.
  • any matter or matter not mentioned is directly applicable to those known in the art without any change.
  • any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are regarded as part of the original disclosure or original record of this application, and should not be It is considered to be new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.
  • the present application provides a disproportionation and transalkylation catalyst, comprising an acidic molecular sieve, a first metal component and an oxide auxiliary agent immobilized on the acidic molecular sieve, the first
  • the first metal contained in the metal component is selected from at least one of VB group metals, VIB group metals and VIIB group metals, and the medium and strong acid amount of the catalyst is 0.05-2mmol/g catalyst, and the medium and strong acid amount accounts for 0.05-2mmol/g catalyst.
  • the proportion of total acid content is 60-99%.
  • the metal components supported on the surface of the molecular sieve can preferentially cover or weaken part of the strong acid centers, and synergize with the acid sites of the nearby molecular sieve to play a role in It can promote the conversion efficiency of aromatic hydrocarbons and reduce the side reactions of hydrogenation.
  • the amount of medium and strong acid in the catalyst is 0.1-1 mmol/g, and the proportion of medium and strong acid in the total acid amount is 70-90%.
  • the ammonia desorption of the acidic molecular sieve after immobilizing the first metal component at 200-400 °C The percentage increase in volume is 0.5-20%.
  • the increase in the ammonia desorption amount of the acidic molecular sieve at 200-400 °C indicates that the amount of medium and strong acid required in the catalyst of the present application increases, which is beneficial to improve the reaction efficiency and xylene selectivity.
  • the first metal is present in the catalyst in the form of a metal element, a metal oxide, or a combination of both.
  • the first metal component is immobilized on the acidic molecular sieve by physical mixing and/or chemical bonding.
  • the catalyst of the present application can be obtained by the following method: after the first metal component is supported on the acidic molecular sieve, it is kneaded and shaped with an oxide assistant. In this embodiment, after the first metal component is supported on the molecular sieve, it is kneaded and formed with an oxide auxiliary agent, based on the synergistic effect of the metal and the acid center of the molecular sieve and the modulation effect of the metal on the acidity, through the catalyst on the catalyst.
  • the supported metals are specifically distributed, which effectively reduces the strong acid center of the molecular sieve and increases the medium and strong acid center, thereby promoting the conversion efficiency of aromatics, improving the selectivity of products such as xylene, and inhibiting the side reactions of aromatics hydrocracking.
  • the catalyst comprises 40-90 wt % of the acidic molecular sieve and 5-40 wt % of the oxide promoter, based on the total weight of the catalyst, calculated as metal elements , the catalyst comprises 0.01-20% by weight of the first metal component.
  • the first metal contained in the first metal component is selected from at least one of VB, VIB and VIIB metals, preferably at least one of Mo, W and Re, more preferably Mo At least two of , Re and W, and the mixed weight ratio of the two in terms of metal elements is 0.1-10:1; particularly preferably a combination of Mo, Re and W, and in terms of metal elements Mo, Re and The weight ratio of W is 1:0.1-0.4:0.1-0.6.
  • the combination of at least two of Mo, Re, and W can further stabilize the metal component and reduce the adverse effect of the migration of the metal oxide during the heat treatment on the molecular sieve structure.
  • the acidic molecular sieves can be selected from a wide range, and commonly used acidic molecular sieves can be used in the present application.
  • the acidic molecular sieve is selected from acidic molecular sieves with eight-membered ring, ten-membered ring or twelve-membered ring pore structure, or a combination thereof, more preferably selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12, Y molecular sieve, or a combination thereof, particularly preferably selected from ZSM-5, MCM-22, MOR, ZSM-12 molecular sieve, or a combination thereof.
  • the oxide assistants can be selected in a wide range, and commonly used oxide assistants can be used in the catalyst of the present application, preferably selected from alumina, silicon oxide, magnesium oxide, titanium oxide, Zirconium, kaolin, or various combinations thereof.
  • the catalyst further comprises phosphorus, preferably immobilized on the acidic molecular sieve by physical mixing and/or chemical bonding, more preferably in terms of P 2 O 5 and in terms of the catalyst's Based on the total weight, the content of the phosphorus is 0.1-5% by weight.
  • the phosphorus-containing compound can further optimize the surface acidity of the molecular sieve on the one hand, and can inhibit the strong interaction between the metal component and the molecular sieve on the other hand, and improve the reducibility of the metal component.
  • the catalyst of the present application further comprises a second metal component different from the first metal component, the second metal being present in all of the metal elements, metal oxides, or a combination of the two in the catalyst mentioned above.
  • the second metal component is immobilized on the oxide auxiliary agent, for example, by physical mixing and/or chemical bonding.
  • the first metal component with higher hydrogenation function (such as VB, VIB, VIIB group metals) is supported on the surface of the acidic molecular sieve, which plays a role in promoting the conversion efficiency of aromatics, while the second metal component is supported on the oxide On the auxiliary agent to inhibit the side reaction of aromatic hydrocarbon hydrogenation and saturation on the surface of the oxide auxiliary agent.
  • the conversion efficiency and target product selectivity of the catalyst of the present application in the aromatic hydrocarbon conversion reaction can be greatly improved.
  • the type of the second metal can be selected from a wide range.
  • the second metal in the second metal component is selected from Group IA, Group IIA, Group IIIA, At least one of Group IVA, Group VA, Group IVB and Lanthanide metals, more preferably at least one selected from the group consisting of Sr, Bi, Ce, Zr and Ge.
  • the catalyst based on the total weight of the catalyst, the catalyst comprises 40-90 wt% acidic molecular sieve and 5-40 wt% oxide promoter, and based on the metal element, the catalyst comprises 0.01-20% by weight of the first metal component and 0.01-20% by weight of the second metal component.
  • the catalyst comprises 50-80% by weight of acidic molecular sieves and 10-30% by weight of oxide promoters, and based on metal elements, the catalyst 0.05-18 wt% of the first metal component and 0.05-18 wt% of the second metal component are included.
  • the catalyst has a molar ratio (B/L) of Bronsted acid to Lewis acid of 10:1 to 0.5:1, more preferably 9:1 to 2:1.
  • the loading of step 1) can be carried out by various conventional loading methods, including but not limited to dipping, direct mixing, precipitation, spraying and the like.
  • the loading of step 1) comprises impregnating the acidic molecular sieve source with a solution comprising a first metal source and optionally a phosphorus source.
  • the impregnation may be an equal volume impregnation or a supersaturated impregnation, preferably a supersaturated impregnation.
  • the first heat treatment of step 1) includes roasting or a combination of drying and roasting.
  • drying conditions can be selected from a wide range, and common drying conditions can be used in this application. 30h.
  • the calcination conditions can be selected within a wide range, and common calcination conditions can be used in this application.
  • the preferred calcination temperature is 300-700° C. 30 hours.
  • the firing is performed in an oxygen-containing atmosphere, which may be, for example, an air atmosphere.
  • the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the two is 5-100:1.
  • the type of the first metal source can be selected from a wide range, for example, it can be a soluble compound of the first metal, and the specific selection of the first metal is as described above, and commonly used types of soluble compounds All can be used in this application, and will not be repeated here.
  • the phosphorus source can be selected from a wide range, and is preferably a phosphorus-containing soluble compound such as phosphoric acid and soluble phosphate. There is no special requirement for the type of the soluble compound, which will not be repeated here.
  • the acidic molecular sieve source can be selected from a wide range, preferably the acidic molecular sieve source is selected from acidic molecular sieves with eight-membered ring, ten-membered ring or twelve-membered ring pore structure characteristics, or their combination, more preferably selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM-12, Y molecular sieve, or a combination thereof, particularly preferably selected from ZSM-5, MCM-22, MOR, ZSM- 12 molecular sieves, or a combination thereof.
  • the oxide auxiliary source may be selected, for example, from alumina, silica, magnesia, titania, zirconia, kaolin, or a combination thereof.
  • the method of the present application further comprises, before step 2), loading a second metal source on the oxide auxiliary agent source, and optionally performing a second heat treatment to obtain a modified oxide auxiliary agent agent source.
  • the loading of step 2) can be carried out by various conventional loading methods, including but not limited to dipping, direct mixing, precipitation, spraying, and the like.
  • the loading of the second metal source on the oxide aid source comprises impregnating the oxide aid source with a solution comprising the second metal source.
  • the type of the second metal source can be selected in a wide range, for example, it can be a soluble compound of the second metal, the specific selection of the second metal is as described above, and the commonly used types of soluble compounds All can be used in this application, and will not be repeated here.
  • the second heat treatment comprises firing or a combination of drying and firing.
  • the drying conditions can be selected in a wide range, and common drying conditions can be used.
  • the calcination conditions can also be selected within a wide range, and common calcination conditions can be used.
  • the firing is performed in an oxygen-containing atmosphere, which may be, for example, an air atmosphere.
  • the oxygen-containing atmosphere is a mixed gas of air and water vapor, and the volume ratio of the two is 5-100:1.
  • the post-treatment of step 2) includes calcining at 300-600° C. for 1-30 hours in an oxygen-containing atmosphere.
  • the post-treatment of step 2) may further include a reduction step.
  • the present application has no special requirements for the reduction step, which can be operated in a conventional manner, and will not be described in detail here.
  • the application of the disproportionation and transalkylation catalyst according to the present application in the catalytic conversion of alkyl aromatic hydrocarbons, wherein the catalytic conversion of alkyl aromatic hydrocarbons includes disproportionation reaction of alkyl aromatic hydrocarbons, transalkylation of alkyl aromatic hydrocarbons reaction, or a combination of the two.
  • a method for the catalytic conversion of alkyl aromatic hydrocarbons comprising the step of contacting and reacting a feedstock comprising alkyl aromatic hydrocarbons with a disproportionation and transalkylation catalyst according to the present application in the presence of hydrogen.
  • the alkylaromatics preferably include toluene, C9 + alkylaromatics, or a combination thereof.
  • the conditions of the contact reaction include: the reaction temperature is 250-500° C., the reaction pressure is 1.5-6.5 MPa, the molar ratio of hydrogen to hydrocarbon is 1-10, and the feed weight space velocity is 0.5-5.
  • the application provides the following technical solutions:
  • a disproportionation and transalkylation catalyst characterized in that the catalyst contains an acidic molecular sieve component, an oxide promoter, a first metal and/or a first metal oxide, and a second metal and/or a second metal oxide compound, wherein the first metal is selected from one or more of Group VB, VIB and VIIB metals, and the second metal is a metal component different from the first metal; the first metal and/or the first metal A metal oxide is immobilized on the acidic molecular sieve component.
  • the first metal and/or the first metal oxide is immobilized on the acidic molecular sieve component by physical mixing and/or chemical bonding; and the second metal and/or the second metal oxide is supported by physical mixing and/or chemical bonding; / or chemical bonds are immobilized on the oxide auxiliary.
  • the preparation step of the catalyst includes: immobilizing the first metal and/or the first metal oxide on the acidic molecular sieve, and immobilizing the second metal and/or the second metal oxide on the oxide auxiliary; Then the two are kneaded and molded.
  • the content of the acidic molecular sieve component is 40-90% by weight
  • the content of the oxide auxiliary agent is 5-40% by weight
  • the content of the first metal and/or the first metal oxide is 0.01-20% by weight
  • the content of the second metal and/or the second metal oxide is 0.01-20% by weight.
  • the content of the acidic molecular sieve component is 50-80% by weight
  • the content of the oxide auxiliary agent is 10-30% by weight
  • the content of the first metal and/or the first metal oxide is 0.05-18% by weight
  • the content of the second metal and/or the second metal oxide is 0.05-18% by weight.
  • the second metal is selected from one or more of IA, IIA, IIIA, IVA, Group VA and lanthanide metals, preferably one or more of Sr, Bi, Ce, Zr and Ge.
  • the first metal is selected from one or more of Mo, Re and W, preferably the first metal is at least two of Mo, Re and W, and the mixing weight ratio of the two is 0.1-10:1 ; more preferably a combination of the three, and the weight ratio of Mo, Re and W is 1:0.1-0.4:0.1-0.6.
  • the acidic molecular sieve component is selected from the acidic molecular sieve components with eight-membered ring, ten-membered ring or twelve-membered ring pore structure characteristics; preferably selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, ZSM -At least one of 12 and Y molecular sieves.
  • the oxide auxiliary agent is selected from one or more of alumina, silica, magnesia, titania and kaolin.
  • the second metal source solution is impregnated with the oxide auxiliary agent source, and the second heat treatment is performed to obtain a second solid;
  • step 1) the steps of the first heat treatment and the second heat treatment each comprise: roasting or drying and roasting,
  • the drying conditions include: the temperature is 50-200°C, and the time is 1-30h;
  • the firing conditions include: heat treatment at 300-700° C. for 1-30 hours in an oxygen-containing atmosphere.
  • the first metal source is a soluble compound containing Group VB, VIB and VIIB metals; and/or
  • the second metal source is a second metal-containing soluble compound
  • the source of the acidic molecular sieve component is selected from the acidic molecular sieve component with eight-membered ring, ten-membered ring or twelve-membered ring pore structure characteristics; preferably selected from ZSM-5, SAPO-11, MCM-22, MOR, Beta, at least one of ZSM-12 and Y molecular sieves; and/or
  • the oxide auxiliary source is selected from one or more of alumina, silica, magnesia, titania and kaolin.
  • a method for disproportionation and transalkylation comprising: using benzene, toluene and/or heavy aromatic hydrocarbons of carbon 9 and above as raw materials, in the presence of hydrogen, contacting and reacting with a catalyst to generate light aromatic components, It is characterized in that, the catalyst is the catalyst described in any one of items 1-9.
  • the reagents and raw materials used are all commercially available materials, and the purity is reagent pure.
  • the amount of ammonia desorption was measured by the NH 3 -TPD method.
  • the specific method was as follows: Weigh 50 mg of the sample, purge it for 30 minutes under flowing helium (30 ml/min) and 500° C., and cool to Adsorb NH 3 gas at 100°C for 10 minutes to the adsorption equilibrium, then switch to helium (30ml/min) for purging for 1 hour, program the temperature to 600°C at a heating rate of 10°C/min, and detect the NH 3 signal in the effluent by TCD .
  • the medium and strong acid content of the obtained catalyst is calculated according to the peak area of the NH 3 -TPD spectrum in the range of 200-400°C.
  • the ratio of the medium and strong acid to the total acid is the ratio of the peak area of the NH 3 -TPD spectrum in the range of 200-400°C to the total peak area in the range of 100-600°C.
  • the B acid content and L acid content of the obtained catalyst were obtained by pyridine infrared spectroscopy, and the specific test process was as follows: the sample was pressed into a tablet, vacuumed to 10 -4 Pa, and heated to 400 ° C for 2h heat treatment. , and then cooled to 200 °C, statically adsorbed pyridine for 5 minutes and equilibrated for 5 minutes, then vacuumed for 40 minutes, and then heated up to 300 °C for 10 minutes and equilibrated for 5 minutes before performing IR scanning . Calculation of absorption peak areas around 1 and 1450 cm -1 .
  • the TEM pictures of the obtained catalysts were characterized by the Tecnai G2 F20 S-TWIN type high-resolution field emission transmission electron microscope of FEI Company, and the working voltage was 200kV. Elemental analysis was performed using an energy dispersive X-ray analyzer equipped with a transmission electron microscope.
  • the I series of examples illustrate the preparation and use of catalysts according to the present application comprising only a first metal component supported on an acidic molecular sieve.
  • Fig. 2 The TEM elemental analysis of the obtained catalyst is shown in Fig. 2, in which the upper left image shows the phase diagram of molecular sieve and alumina in the catalyst, the upper right image shows the distribution of supported Mo elements, the lower left image shows the Si element distribution, and the lower right image shows the distribution of Si element. Al element distribution.
  • the silicon-rich part corresponds to the mordenite
  • the aluminum-rich part corresponds to the alumina promoter.
  • Mo element see the upper right figure
  • Beta molecular sieve Take 20g of Beta molecular sieve, supersaturate and impregnate ammonium molybdate solution, and then pre-calcinate at 400 ° C for 3 hours in an air atmosphere to obtain a modified molecular sieve.
  • the modified molecular sieve was kneaded with 7.7 grams of kaolin to form, and calcined at 550° C. for 2 hours in an air atmosphere to obtain a catalyst with a molybdenum content of 1 wt%.
  • the composition and properties of the obtained catalyst are shown in Table I-1.
  • Example I-1 Prepared according to the method of Example I-1, the difference is that a certain amount of mordenite is impregnated with ammonium molybdate and ammonium tungstate solution, and all other conditions are the same, and the obtained catalyst composition and properties are shown in Table I-1.
  • Example 1 Prepare according to the method described in Example 1, the difference is that getting a certain amount of mordenite and immersing the ammonium molybdate solution to obtain the modified molecular sieve powder that the molybdenum content is 3wt%, the modified molecular sieve is in the mixed atmosphere of air and water vapor ( The volume ratio of air to water vapor was 20:1) pre-baked at 400°C for 3 hours.
  • the preparation conditions of the remaining catalysts are all the same, and the composition and properties of the obtained catalysts are shown in Table I-1.
  • Example 2 Prepare according to the method described in Example 1, the difference is that getting a certain amount of mordenite and immersing the ammonium molybdate solution to obtain the modified molecular sieve powder that the molybdenum content is 3wt%, the modified molecular sieve is in the mixed atmosphere of air and water vapor ( The volume ratio of air and water vapor was 5:1) and calcined at 400° C. for 3 hours, and the preparation conditions of the remaining catalysts were all the same. The composition and properties of the obtained catalysts were shown in Table I-1.
  • Example 2 Prepared according to the method described in Example 1, except that a certain amount of mordenite was impregnated with ammonium molybdate solution to obtain modified molecular sieve powder with molybdenum content of 3wt%, and the modified molecular sieve was obtained after drying at 120°C. 20 grams of modified molecular sieves were kneaded with 7.7 grams of alumina to form a catalyst, and calcined at 550° C. for 2 hours to obtain a catalyst. The composition and properties of the obtained catalyst are shown in Table I-1.
  • Example I-1 Prepared according to the method of Example I-1, the difference is that a certain amount of mordenite is impregnated with a certain amount of ammonium tungstate solution, all other conditions are the same, and the obtained catalyst composition and properties are shown in Table I-1.
  • Example I-1 Prepared according to the method of Example I-1, the difference is that a certain amount of mordenite is impregnated with a certain amount of ammonium tungstate and ammonium perrhenate solution, all other conditions are the same, and the obtained catalyst composition and properties are shown in Table I-1.
  • the reaction conditions are as follows: the total weight space velocity is 4.0 h -1 , the reaction temperature is 370° C., the reaction pressure is 2.5 MPa, and the hydrogen-hydrocarbon molecular ratio is 3.0.
  • the weight composition of C 9 A raw materials is: 4.2% of propylbenzene, 31.0% of methylethylbenzene, 59.6% of trimethylbenzene, 5.2% of indane, and the weight composition of C 10 + A is: 3.6% of diethylbenzene, 26.9% of dimethylethylbenzene, 2.3% of methylpropylbenzene, 28.8% of tetratoluene, 14.4% of methylnaphthalene, 11.1% of dimethylnaphthalene, and 12.9% of others. Test conditions and results are shown in Table I-2.
  • the conversion rate can be improved while reducing the loss rate of aromatic rings compared to the comparative example.
  • the conversion efficiency can be further improved to 48.2%, and the loss rate of aromatic rings can be reduced to 0.8%.
  • the conversion rate can also be increased to 48.5%, and the loss rate of aromatic rings can be reduced to 0.7%.
  • the II series of examples illustrate the preparation and use of catalysts according to the present application comprising a first metal component supported on an acidic molecular sieve and a second metal component supported on an oxide promoter.
  • modified molecular sieve powder Take 20 grams of mordenite, immerse it in a certain ammonium molybdate solution with supersaturation, spray dry it at 150 °C, and then roast it in an air atmosphere at 400 °C for 3 hours to obtain modified molecular sieve powder.
  • An equal volume of 7.7 grams of alumina was impregnated with a certain amount of strontium nitrate, and then dried at 150°C to obtain modified alumina.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 550°C for 2 hours to obtain a catalyst with a molybdenum content of 1 wt% and a strontium content of 1.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the TEM elemental analysis of the obtained catalyst is shown in Fig. 3, in which the upper left image shows the phase diagram of the combination of molecular sieve and alumina in the catalyst, the upper middle image shows the Al element distribution, the upper right image shows the Si element distribution, and the lower left image shows the Mo elemental distribution Elemental distribution, the lower middle panel shows the Sr elemental distribution.
  • the silicon-rich part corresponds to the mordenite
  • the aluminum-rich part corresponds to the alumina promoter.
  • the lower left picture is mainly distributed on the surface of the mordenite
  • the Sr element see the lower middle picture
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • Beta zeolite Take 20 grams of Beta zeolite, supersaturate it with a certain ammonium molybdate solution, spray-dry it at 150 °C, and then roast it in an air atmosphere at 400 °C for 3 hours to obtain modified molecular sieve powder.
  • An equal volume of 7.7 grams of alumina was impregnated with a certain amount of strontium nitrate, and then dried at 150°C to obtain modified alumina.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 550°C for 2 hours to obtain a catalyst with a molybdenum content of 1 wt% and a strontium content of 1.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. Test conditions and results are shown in Table II-2.
  • modified molecular sieve powder After mixing 15 grams of mordenite molecular sieve with 5 grams of ZSM-5 molecular sieve, supersaturated and impregnated a certain ammonium molybdate solution, dried at 120 ° C for 10 hours, and then roasted in air atmosphere and 450 ° C for 3 hours to obtain modified molecular sieve powder . An equal volume of 7.7 grams of alumina was impregnated with a certain amount of bismuth nitrate, and the modified alumina was obtained by drying at 120°C.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 500°C for 6 hours to obtain a catalyst with a molybdenum content of 3wt% and a bismuth content of 5wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the modified molecular sieve and modified alumina were kneaded into molding and calcined at 550°C for 2 hours to obtain a catalyst with a molybdenum content of 13 wt% and a cerium content of 8.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the reaction conditions are as follows: the total weight space velocity is 4.0 h -1 , the reaction temperature is 370° C., the reaction pressure is 3.5 MPa, and the hydrogen-hydrocarbon molecular ratio is 3.0.
  • the reaction starting material was 100% reformed C9 + A.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 500°C for 6 hours to obtain a catalyst with a molybdenum content of 3wt% and a bismuth content of 5wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the modified molecular sieve powder was obtained by supersaturated immersion in a certain ammonium molybdate solution, and calcined at 500°C for 3 hours.
  • An equal volume of 7.7 grams of alumina was impregnated with a certain amount of bismuth nitrate, and the modified alumina was obtained by calcining at 500°C for 3 hours.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 550°C for 3 hours to obtain a catalyst with a molybdenum content of 3 wt% and a bismuth content of 5 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • Beta molecular sieve Take 15 grams of Beta molecular sieve and 5 grams of ZSM-5 molecular sieve and mix them evenly, supersaturate and impregnate a certain amount of ammonium perrhenate solution, dry at 120 °C for 10 hours, and then bake in air atmosphere and 500 °C for 3 hours to obtain modified molecular sieves pink.
  • An equal volume of 7.7 grams of alumina was impregnated with a certain amount of germanium chloride, and the modified alumina was obtained by drying at 120° C. for 10 hours.
  • the modified molecular sieve and modified alumina were kneaded into molding and calcined at 550°C for 2 hours to obtain a catalyst with a rhenium content of 1 wt% and a germanium content of 3.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • reaction conditions are as follows: the total weight space velocity is 4.0 hours -1 , the reaction temperature is 360° C., the reaction pressure is 3.0 MPa, and the hydrogen-hydrocarbon molecular ratio is 3.0.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the modified molecular sieve Take 15 grams of ZSM-12 molecular sieve and 5 grams of ZSM-5 molecular sieve, mix them evenly, and immerse them in a certain ammonium molybdate solution in equal volume. After drying at 120 °C for 10 hours, the modified molecular sieve is prepared by calcining at 400 °C for 3 hours in an air atmosphere. pink. 4 grams of alumina and 3.5 grams of magnesia were mixed uniformly, and then immersed in an equal volume of zirconium chloride, and dried at 120° C. for 10 hours to obtain a modified oxide.
  • the modified molecular sieve and the modified oxide were kneaded to form, and calcined at 500°C for 4 hours to obtain a catalyst with a molybdenum content of 8 wt% and a zirconium content of 5.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method of Example II-1, the difference is that after 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve are mixed uniformly, a certain ammonium molybdate and ammonium tungstate solution are supersaturated and impregnated, and other conditions are the same, the obtained
  • the catalyst composition and properties are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method of Example II-1, the difference is that after 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve are mixed uniformly, a certain ammonium molybdate and ammonium perrhenate solution are supersaturated and impregnated, and other conditions are the same, The composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method of Example II-1, the difference is that after mixing 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve evenly, a certain ammonium tungstate and ammonium perrhenate solution are supersaturated and impregnated, and the other conditions are the same, The composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method of Example II-1, the difference is that after mixing 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve uniformly, supersaturated immersion in certain solutions of ammonium molybdate, ammonium tungstate and ammonium perrhenate, and the rest The conditions are the same, the composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method described in Example II-1, except that 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve were mixed uniformly, and then supersaturated and immersed in a certain ammonium molybdate solution, and after drying at 120 ° C for 10 hours,
  • the modified molecular sieve powder was obtained by calcining at 400°C for 3 hours in a mixed atmosphere of air and water vapor (volume ratio of air and water vapor: 20:1), and the other catalyst preparation and reduction conditions and reaction conditions were the same.
  • Table II-1 The composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method described in Example II-1, except that 18 grams of mordenite molecular sieve and 2 grams of ZSM-5 molecular sieve were mixed uniformly, sprayed with a certain ammonium molybdate solution, dried at 120 ° C for 10 hours, and then The modified molecular sieve powder was obtained by calcining at 400°C for 3 hours in a mixed atmosphere of air and water vapor (volume ratio of air and water vapor: 5:1), and other catalyst preparation and reduction conditions and reaction conditions were the same.
  • Table II-1 The composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-1 Prepared according to the method described in Example II-1, the difference is that after mixing 18 grams of mordenite and 2 grams of ZSM-5 molecular sieve uniformly, immersed in an equal volume of a certain ammonium molybdate solution, and dried at 120 ° C to obtain a modified Molecular sieve powder, take an equal volume of 7.7 grams of alumina, impregnate a certain amount of strontium nitrate, and dry at 150 °C to obtain modified alumina. The modified molecular sieve and modified alumina were kneaded into shape, and calcined at 550° C. for 2 hours to obtain a catalyst. The other catalyst preparation and reduction conditions and reaction conditions were the same. The composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • Example II-9 Prepared according to the method described in Example II-9, the difference is that after the modified molecular sieve was dried at 120 ° C for 10 hours, it was then dried in a mixed atmosphere of air and water vapor (volume ratio of air to water vapor 5:1) and 400 After calcination at °C for 3 hours, the other catalyst preparation and reduction conditions and reaction conditions are the same.
  • the composition and properties of the obtained catalyst are shown in Table II-1, and the test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the modified molecular sieve and modified alumina were kneaded into molding and calcined at 550°C for 2 hours to obtain a catalyst with a platinum content of 0.1 wt% and a strontium content of 2.0 wt%.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • Beta molecular sieve 20 grams was supersaturated and immersed in a certain ammonium dichloroplatinum solution, spray-dried at 200°C, and roasted at 500°C for 2 hours in an air atmosphere to obtain modified molecular sieve powder.
  • An equal volume of 7.7 grams of alumina was impregnated with a certain amount of stannous chloride, and the modified alumina was obtained by drying at 200°C.
  • the modified molecular sieve and modified alumina were kneaded into molding, and calcined at 550°C for 2 hours to obtain a catalyst with a platinum content of 0.05 wt % and a tin content of 2.0 wt %.
  • the composition and properties of the obtained catalyst are shown in Table II-1.
  • the weight composition of the C 9 A raw material is: 4.2% of propylbenzene, 32.0% of methylethylbenzene, 59.6% of trimethylbenzene, and 4.2% of indane.
  • the weight composition of C 10 A was: 15.3% of diethylbenzene, 36.9% of dimethylethylbenzene, 22.3% of methylpropylbenzene, 24.0% of tetratoluene, and 1.5% of methylnaphthalene. . Test conditions and results are shown in Table II-2.
  • the catalyst of the present application can further improve the conversion rate and reduce the loss of aromatic rings by immobilizing the first and second metals on the molecular sieve and the oxide auxiliary, respectively.

Abstract

公开了一种歧化与烷基转移催化剂及其制备和应用，所述催化剂包含酸性分子筛、固载在所述酸性分子筛上的第一金属组分和氧化物助剂，所述第一金属组分中所含的第一金属选自VB族金属、VIB族金属和VIIB族金属中的至少一种，所述催化剂的中强酸酸量为0.05-2.0mmol/g催化剂，中强酸酸量占总酸量的比例为60-99％。所述催化剂用在烷基芳烃的催化转化中时，具有反应活性高、芳烃损失率低等优点。

Description

歧化与烷基转移催化剂及其制备和应用 技术领域
本申请涉及催化剂的技术领域，具体涉及一种歧化与烷基转移催化剂及其制备和应用。
背景技术
利用甲苯与碳九及其以上重芳烃(C 9 +A)烷基转移反应增产二甲苯是有效利用重芳烃来增产二甲苯的方法，被广泛应用。甲苯与C 9 +A间的反应网络复杂，涉及重芳烃脱烷基轻质化、歧化与烷基转移、苯环加氢裂解等。上述各反应为酸催化反应，需在分子筛酸中心作用下方能进行。此外，研究发现，为提高催化剂转化效率，改善催化剂抗积炭性能，可在催化剂中引入一定的金属组分。金属组分可促进烯烃中间物的快速加氢饱和，加快脱烷基等反应的进行，提高重芳烃转化效率，但同时金属组分也会加剧芳烃的加氢饱和。金属铂、钯、铼、钼等金属常用作加氢金属组分，不同金属对反应的影响结果不同，金属加氢功能过强会导致芳烃加氢副反应加大，芳环损失率增加；而加氢功能过弱的金属对主反应促进作用不明显。选择合适的金属助剂是催化剂合成的关键。
CN102688770A公开了一种芳烃加氢催化剂，其以介孔沸石及贵金属为组成，贵金属选自铂、钯、铑、银、钌、金等，使用后处理发，软模板或硬模板制备具有介孔材料特性的介孔沸石，将得到的介孔沸石经硝酸铵离子交换焙烧得到催化剂载体，然后浸渍负载贵金属组分，由此来提高催化剂的加氢脱芳烃活性及抗硫性能。
CN1259930A公布了一种双层催化剂反应工艺，上层催化剂为含有一种VIIIB族金属及选自MCM-22、ZSM-12、Beta、PSH-3、SSZ-25沸石分子筛，下层催化剂为ZSM-5分子筛，反应物先经上层催化剂生产二甲苯及苯中间物，再通过第二催化剂床进行苯产物的提纯。
CN1122571公开了一种适用于处理高C 9 +A原料的含贵金属的分子筛催化剂，该催化剂以10-80％(重量)丝光沸石或β沸石和0-70％(重量)的ZSM-5，5-90％(重量)的γ-Al 2O 3为载体，负载0.001-0.5重量份铂及0.01-10.0重量份锡或0.01-7.0重量份铅。
然而，现有技术中已知的芳烃转化催化剂存在转化效率低，加氢 副产物较高等问题，因此仍然需要一种能够至少部分克服上述问题的新型催化剂。
发明内容
本申请的目的是提供一种新型的歧化和烷基转移催化剂及其制备和应用，所述催化剂适用于烷基芳烃的催化转化，例如烷基芳烃的歧化反应和烷基转移反应，特别是以甲苯和/或C 9 +烷基芳烃为原料生产二甲苯的反应，具有转化效率高、芳烃加氢副反应低、产物选择性高的优点。
为了实现上述目的，一方面，本申请提供了一种歧化与烷基转移催化剂，包含酸性分子筛、固载在所述酸性分子筛上的第一金属组分和氧化物助剂，所述第一金属组分中所含的第一金属选自VB族金属、VIB族金属和VIIB族金属中的至少一种，所述催化剂的中强酸酸量为0.05-2mmol/g催化剂，中强酸酸量占总酸量的比例为60-99％。
优选地，所述第一金属为选自Mo、W和Re中的至少一种，更优选为Mo、Re和W中的至少两种的组合，特别优选为Mo、Re和W三者的组合。
优选地，所述催化剂进一步包含不同于所述第一金属组分的第二金属组分，所述第二金属组分优选固载在所述氧化物助剂上。
进一步优选地，所述第二金属组分中的第二金属选自IA族、IIA族、IIIA族、IVA族、VA族、IVB族及镧系金属中的至少一种。
另一方面，提供了制备根据本申请的歧化与烷基转移催化剂的方法，包括如下步骤：
1)在酸性分子筛源上装载第一金属源和任选的磷源，并进行第一热处理得到改性分子筛；以及
2)将所述改性分子筛与氧化物助剂源成型，并任选进行后处理，得到所述催化剂。
又一方面，提供了根据本申请的歧化与烷基转移催化剂在烷基芳烃的催化转化中的应用，所述烷基芳烃的催化转化包括烷基芳烃的歧化反应、烷基芳烃的烷基转移反应，或者两者的组合。
再一方面，提供了一种烷基芳烃的催化转化方法，包括在氢气存在下，使包含烷基芳烃的原料与根据本申请的歧化与烷基转移催化剂接触反应的步骤。
本申请的催化剂具有一个或多个以下的特点：
1)本申请的催化剂使用包含VB、VIB和/或VIIB族金属的活性金属组分，并将其固载在酸性分子筛上，基于金属表面氢迁移作用及与分子筛酸性位的协同作用，负载在酸性分子筛表面的金属组分能优先覆盖或弱化部分强酸中心，并与附近分子筛酸性位进行协同作用，起到促进芳烃转化效率、降低加氢副反应的作用，具有反应活性高、芳烃损失低等优势；
2)在优选的实施方式中，本申请的催化剂使用了两种金属组分，且基于不同金属组分对芳烃转化反应过程的影响，调控了催化剂上的负载金属分布，其中较高加氢功能的第一金属组分负载在酸性分子筛表面，起到促进芳烃转化效率的作用，而第二金属组分优选负载在氧化物助剂上以抑制氧化物助剂表面上发生芳烃加氢饱和副反应。由此大大提高了催化剂用于芳烃转化反应的转化效率和目标产物选择性；以及
3)本申请的催化剂用于甲苯、C 9 +芳烃生产二甲苯和苯的反应中时，具有芳烃加氢副反应低、二甲苯选择性高的优点。
本申请的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本申请的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本申请，但并不构成对本申请的限制。在附图中：
图1A和图1B分别显示了本申请实施例I-1和对比例I-1所得催化剂的NH 3-TPD谱图；
图2显示了本申请实施例I-1所得催化剂的TEM图；
图3显示了本申请实施例II-1所得催化剂的TEM图。
具体实施方式
以下结合附图对本申请的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本申请，并不用于限制本申请。
在本文中所披露的任何具体数值(包括数值范围的端点)都不限于该数值的精确值，而应当理解为还涵盖了接近该精确值的值，例如 在该精确值±5％范围内的所有可能的数值。并且，对于所披露的数值范围而言，在该范围的端点值之间、端点值与范围内的具体点值之间，以及各具体点值之间可以任意组合而得到一个或多个新的数值范围，这些新的数值范围也应被视为在本文中具体公开。
除非另有说明，本文所用的术语具有与本领域技术人员通常所理解的相同的含义，如果术语在本文中有定义，且其定义与本领域的通常理解不同，则以本文的定义为准。
在本申请中，术语“酸性分子筛”具有本领域通常理解的含义，指具有B酸和/或L酸性位点的分子筛。
在本申请中，术语“C 8芳烃(或C 8A)”是指具有8个碳原子的芳烃或其混合物，例如二甲苯；类似地术语“C 9芳烃(或C 9A)”是指具有9个碳原子的芳烃或其混合物，例如丙苯、甲乙苯、三甲苯等。
在本申请中，术语“C 9 +芳烃(或C 9 +A)”是指具有9个及以上碳原子的芳烃或其混合物，类似地术语“C 10 +芳烃(或C 10 +A)”是指具有10个及以上碳原子的芳烃或其混合物。例如，C 10 +烷基芳烃包括但不限于二乙苯、二甲基乙苯、甲基丙苯、四甲苯、甲基萘、二甲基萘等。
在本申请中，催化剂的中强酸量按照NH 3-TPD谱图在200-400℃区间内的峰面积计算得到；中强酸量占总酸量的比例为NH 3-TPD谱图在200-400℃区间的峰面积与100-600℃区间内的总峰面积的比值。
本申请中，除了明确说明的内容之外，未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且，本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合，由此形成的技术方案或技术思想均视为本申请原始公开或原始记载的一部分，而不应被视为是本文未曾披露或预期过的新内容，除非本领域技术人员认为该结合明显不合理。
在本文中提及的所有专利和非专利文献，包括但不限于教科书和期刊文章等，均通过引用方式全文并入本文。
如上所述，在第一方面，本申请提供了一种歧化与烷基转移催化剂，包含酸性分子筛、固载在所述酸性分子筛上的第一金属组分和氧化物助剂，所述第一金属组分中所含的第一金属选自VB族金属、VIB族金属和VIIB族金属中的至少一种，所述催化剂的中强酸酸量为0.05-2mmol/g催化剂，中强酸酸量占总酸量的比例为60-99％。
在本申请的催化剂中，基于金属表面氢迁移作用及与分子筛酸性位的协同作用，负载在分子筛表面的金属组分能优先覆盖或弱化部分强酸中心，并与附近分子筛酸性位进行协同作用，起到促进芳烃转化效率、降低加氢副反应的作用。
在优选的实施方式中，所述催化剂的中强酸酸量为0.1-1mmol/g，中强酸酸量占总酸量的比例为70-90％。
在优选的实施方式中，以常压下，酸性分子筛于200-400℃下氨脱附量为基准，固载第一金属组分后的所述酸性分子筛于200-400℃下的氨脱附量增加百分比为0.5-20％。本申请中，酸性分子筛在200-400℃下氨脱附量的增加，说明了本申请的催化剂中所需的中强酸酸量增加了，有利于提高反应效率及二甲苯选择性。
在本申请的催化剂中，所述第一金属以金属元素、金属氧化物或两者组合的形式存在于所述催化剂中。在优选的实施方式中，所述第一金属组分通过物理混合和/或化学键作用固载在所述酸性分子筛上。
在优选的实施方式中，本申请的催化剂可通过如下方式得到：将第一金属组分负载在酸性分子筛上后，与氧化物助剂捏合成型。在该实施方式中，通过将第一金属组分负载在分子筛上之后再与氧化物助剂捏合成型，基于金属与分子筛酸中心的协同作用及金属对酸性的调变作用，通过对催化剂上的负载金属进行了特定分布，有效减少分子筛强酸中心而增加中强酸中心，从而起到促进芳烃转化效率、提高产物如二甲苯选择性及抑制芳烃加氢裂解副反应的作用。
在优选的实施方式中，以所述催化剂的总重量为基准，所述催化剂包含40-90重量％的所述酸性分子筛和5-40重量％的所述氧化物助剂，并且以金属元素计，所述催化剂包含0.01-20重量％的所述第一金属组分。
根据本申请，所述第一金属组分中所含的第一金属选自VB、VIB和VIIB族金属中的至少一种，优选为Mo、W和Re中的至少一种，更优选为Mo、Re和W中的至少两种，且以金属元素计二者的混合重量比例为0.1-10∶1；特别优选为Mo、Re和W三者的组合，且以金属元素计Mo、Re与W的重量比为1∶0.1-0.4∶0.1-0.6。在本申请的优选实施方式中，Mo、Re、W中至少两者组合能进一步稳定金属组分，减少金属氧化物热处理过程中的迁移对分子筛结构的不利影响。
根据本申请，所述酸性分子筛可以在较宽的范围内进行选择，常用的酸性分子筛均可以用于本申请。在优选的实施方式中，所述酸性分子筛选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛，或者它们的组合，更优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12、Y分子筛，或者它们的组合，特别优选选自ZSM-5、MCM-22、MOR、ZSM-12分子筛，或者它们的组合。
根据本申请，所述氧化物助剂可在较宽的范围内进行选择，常用的氧化物助剂均可用于本申请的催化剂，优选选自氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、高岭土，或者它们的各种组合。
在优选的实施方式中，所述催化剂进一步包含磷，所述磷优选通过物理混合和/或化学键作用固载在所述酸性分子筛上，更优选地以P 2O 5计并以所述催化剂的总重量为基准，所述磷的含量为0.1-5重量％。在该优选实施方式中，含磷化合物一方面可进一步优化分子筛表面酸性，另一方面能抑制金属组分与分子筛的强相互作用，提高金属组分的可还原性。
在优选的实施方式中，本申请的催化剂进一步包含不同于所述第一金属组分的第二金属组分，所述第二金属以金属元素、金属氧化物或两者组合的形式存在于所述催化剂中。进一步优选地，所述第二金属组分固载在所述氧化物助剂上，例如通过物理混合和/或化学键作用固载在氧化物助剂上。
本申请中，首次发现基于不同加氢金属组分对芳烃转化反应过程的影响，通过优化金属组分在催化剂上的微观分布，组合不同金属的优点，可达到更优的催化效果，一方面可实现芳烃的高效转化，同时也可降低芳烃的加氢饱和。具体而言，较高加氢功能的第一金属组分(如VB、VIB、VIIB族金属)负载在酸性分子筛表面，起到促进芳烃转化效率的作用，而第二金属组分负载在氧化物助剂上以抑制氧化物助剂表面上发生芳烃加氢饱和副反应。由此，可以大大提高本申请催化剂用于芳烃转化反应的转化效率和目标产物选择性。
根据本申请，所述第二金属的种类可在较宽的范围内选择，在优选的实施方式中，所述第二金属组分中的第二金属选自IA族、IIA族、IIIA族、IVA族、VA族、IVB族及镧系金属中的至少一种，更优选选自Sr、Bi、Ce、Zr和Ge中至少一种。
在进一步优选的实施方式中，以催化剂的总重量为基准，所述催化剂包含40-90重量％的酸性分子筛和5-40重量％的氧化物助剂，并且以金属元素计，所述催化剂包含0.01-20重量％的第一金属组分和0.01-20重量％的第二金属组分。
在更进一步优选的实施方式中，以催化剂的总重量为基准，所述催化剂包含50-80重量％的酸性分子筛和10-30重量％的氧化物助剂，并且以金属元素计，所述催化剂包含0.05-18重量％的第一金属组分和0.05-18重量％的第二金属组分。
在某些优选实施方式中，所述催化剂的Bronsted酸量与Lewis酸量的摩尔比(B/L)值为10∶1-0.5∶1，更优选为9∶1-2∶1。
在第二方面，提供了一种制备根据本申请的歧化与烷基转移催化剂的方法，包括如下步骤：
1)在酸性分子筛源上装载第一金属源和任选的磷源，并进行第一热处理得到改性分子筛；以及
2)将所述改性分子筛与氧化物助剂源成型，并任选进行后处理，得到所述催化剂。
在本申请中，步骤1)的所述装载可以通过各种常规装载方式进行，包括但不限于浸渍、直接混合、沉淀、喷涂等。在优选的实施方式中，步骤1)的所述装载包括用包含第一金属源的溶液和任选的磷源浸渍所述酸性分子筛源。在本申请中，所述浸渍可以是等体积浸渍或过饱和浸渍，优选为过饱和浸渍。
在优选的实施方式中，步骤1)的所述第一热处理包括焙烧或者干燥与焙烧的组合。
本申请中，所述干燥的条件可在较宽的范围内选择，常用干燥条件均可用于本申请，优选的干燥温度可为50-200℃，干燥时间可以依据温度进行调整，优选为1-30h。
本申请中，所述焙烧的条件可在较宽的范围内选择，常用焙烧条件均可以用于本申请，优选的焙烧温度为300-700℃，焙烧时间可以依据温度进行调整，优选为1-30小时。
在优选的实施方式中，所述焙烧在含氧气氛中进行，所述含氧气氛可以为例如空气气氛。在进一步优选的实施方式中，所述含氧气氛为空气与水蒸气的混合气体，二者体积比为5-100∶1。
根据本申请，所述第一金属源的种类可在较宽的范围内选择，例如可以为第一金属的可溶性化合物，所述第一金属的具体选择如上文所述，并且常用类型的可溶性化合物均可以用于本申请，在此不再赘述。
根据本申请，所述磷源可以在较宽的范围内选择，优选为含磷的可溶性化合物，例如磷酸和可溶性磷酸盐，所述可溶性化合物的种类无特殊要求，在此不再赘述。
根据本申请，所述酸性分子筛源可以在较宽的范围内选择，优选地所述酸性分子筛源选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛，或者它们的组合，更优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12、Y分子筛，或者它们的组合，特别优选选自ZSM-5、MCM-22、MOR、ZSM-12分子筛，或者它们的组合。
根据本申请，所述氧化物助剂源例如可以选自氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、高岭土，或者它们的组合。
在优选的实施方式中，本申请的方法进一步包括，在步骤2)之前，在所述氧化物助剂源上装载第二金属源，并任选进行第二热处理，得到改性的氧化物助剂源。在本申请中，步骤2)的所述装载可以通过各种常规装载方式进行，包括但不限于浸渍、直接混合、沉淀、喷涂等。进一步优选地，所述在氧化物助剂源上装载第二金属源包括用包含第二金属源的溶液浸渍所述氧化物助剂源。
根据本申请，所述第二金属源的种类可在较宽的范围内选择，例如可以为第二金属的可溶性化合物，所述第二金属的具体选择如上文所述，并且常用类型的可溶性化合物均可以用于本申请，在此不再赘述。
在优选的实施方式中，所述第二热处理包括焙烧或者干燥与焙烧的组合。所述干燥的条件可在较宽的范围内选择，常用干燥条件均可使用，优选的干燥温度可为50-200℃，干燥时间可以依据温度进行调整，优选为1-30h。所述焙烧的条件也可在较宽的范围内选择，常用焙烧条件均可使用，优选的焙烧温度为300-700℃，焙烧时间可以依据温度进行调整，优选为1-30小时。在进一步优选的实施方式中，所述焙烧在含氧气氛中进行，所述含氧气氛可以为例如空气气氛。在更进一步优选的实施方式中，所述含氧气氛为空气与水蒸气的混合气体，二 者体积比为5-100∶1。
在优选的实施方式中，步骤2)的所述后处理包括在含氧气氛下在300-600℃焙烧1-30小时。
本申请的催化剂，在进行使用前，可根据需要进行还原。因此，在某些优选实施方式中，步骤2)的后处理还可以进一步包括还原步骤。本申请对所述还原步骤无特殊要求，可按照常规方式操作，在此不进行详细描述。
第三方面，提供了根据本申请的歧化与烷基转移催化剂在烷基芳烃的催化转化中的应用，所述烷基芳烃的催化转化包括烷基芳烃的歧化反应、烷基芳烃的烷基转移反应，或者两者的组合。
第四方面，提供了一种烷基芳烃的催化转化方法，包括在氢气存在下，使包含烷基芳烃的原料与根据本申请的歧化与烷基转移催化剂接触反应的步骤。
在本申请中，所述烷基芳烃优选包括甲苯、C 9 +烷基芳烃，或者它们的组合。
在优选的实施方式中，所述接触反应的条件包括：反应温度为250-500℃，反应压力为1.5-6.5MPa，氢烃摩尔比为1-10，进料重量空速为0.5-5。
在某些优选的实施方式中，本申请提供了如下的技术方案：
1、一种歧化与烷基转移催化剂，其特征在于，该催化剂含有酸性分子筛组分、氧化物助剂、第一金属和/或第一金属氧化物，第二金属和/或第二金属氧化物，其中所述第一金属选自VB、VIB和VIIB族金属中的一种或多种，所述第二金属为与第一金属不同的金属组分；所述第一金属和/或第一金属氧化物固载在所述酸性分子筛组分上。
2、根据项目1所述的催化剂，其中，
所述第一金属和/或第一金属氧化物通过物理混合和/或化学键作用固载在所述酸性分子筛组分上；且所述第二金属和/或第二金属氧化物通过物理混合和/或化学键作用固载在氧化物助剂上。
3、根据项目1或2所述的催化剂，其中，
所述催化剂的制备步骤包括：将第一金属和/或第一金属氧化物固载在所述酸性分子筛上，将第二金属和/或第二金属氧化物固载在氧化物助剂上；然后将二者进行捏合成型。
4、根据项目1-3中任一项所述的催化剂，其中，
以催化剂的100重量％计，所述酸性分子筛组分的含量为40-90重量％，氧化物助剂的含量为5-40重量％，第一金属和/或第一金属氧化物的含量为0.01-20重量％，第二金属和/或第二金属氧化物的含量为0.01-20重量％。
5、根据项目4所述的催化剂，其中，
以催化剂的100重量％计，所述酸性分子筛组分的含量为50-80重量％，氧化物助剂的含量为10-30重量％，第一金属和/或第一金属氧化物的含量为0.05-18重量％，第二金属和/或第二金属氧化物的含量为0.05-18重量％。
6、根据项目1-5中任一项所述的催化剂，其中，
所述第二金属选自IA、IIA、IIIA、IVA、VA族及镧系金属中的一种或多种，优选选自Sr、Bi、Ce、Zr和Ge中的一种或多种。
7、根据项目1-6中任一项所述的催化剂，其中，
所述第一金属选自Mo、Re和W中的一种或多种，优选所述第一金属为Mo、Re和W中的至少两种，二者的混合重量比例为0.1-10∶1；更优选为三者的组合，且Mo、Re与W的重量比为1∶0.1-0.4∶0.1-0.6。
8、根据项目1-7中任一项所述的催化剂，其中，
所述酸性分子筛组分选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛组分；优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12和Y分子筛中的至少一种。
9、根据项目1-8中任一项所述的催化剂，其中，
所述氧化物助剂选自氧化铝、氧化硅、氧化镁、氧化钛和高岭土中的一种或多种。
10、一种制备项目1-9中任一项所述催化剂的方法，该方法包括：
1)将第一金属源溶液浸渍所述酸性分子筛组分源，第一热处理得到第一固体；
将第二金属源溶液浸渍氧化物助剂源，第二热处理得到第二固体；
2)将所述第一固体与第二固体捏合、成型。
11、根据项目10所述的方法，其中，步骤1)中，第一热处理和第二热处理的步骤各自包括：焙烧或者，干燥和焙烧，
其中，干燥的条件包括：温度为50-200℃，时间为1-30h；
其中，焙烧的条件包括：在含氧气氛下于300-700℃下热处理1-30小时。
12、根据项目11所述的方法，其中，所述含氧气氛为空气与水蒸气的混合气体，二者体积比为5-100∶1。
13、根据项目10-12中任一项所述的方法，其中，
所述第一金属源为含VB、VIB和VIIB族金属可溶性化合物；和/或
所述第二金属源为含第二金属的可溶性化合物；和/或
所述酸性分子筛组分源选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛组分；优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12和Y分子筛中的至少一种；和/或
所述氧化物助剂源选自氧化铝、氧化硅、氧化镁、氧化钛和高岭土中的一种或多种。
14、一种歧化与烷基转移的方法，该方法包括：以苯、甲苯和/或碳九及以上重芳烃为原料，在氢气存在条件下，与催化剂接触反应，生成轻质芳烃组分，其特征在于，所述催化剂为项目1-9中任一项所述的催化剂。
实施例
下面结合实施例对本申请予以进一步说明，但并不因此而限制本申请。
以下实施例和对比例中，如无特殊表示，所用试剂和原料均为市售材料，纯度为试剂纯。
以下实施例和对比例中，氨脱附量采用NH 3-TPD方法测量，具体方法如下：称取50mg样品，在流通氦气下(30ml/min)及500℃下吹扫30分钟，降温至100℃吸附NH 3气10分钟至吸附平衡，再切换至氦气(30ml/min)吹扫1小时后，以10℃/min升温速率程序升温至600℃，用TCD检测流出物中NH 3信号。
以下实施例和对比例中，所得催化剂的中强酸量按照NH 3-TPD谱图在200-400℃区间内的峰面积计算而得。中强酸量占总酸量的比例为NH 3-TPD谱图在200-400℃区间峰面积与100-600℃区间内的总峰面积的比值。
以下实施例和对比例中，所得催化剂的B酸量和L酸量通过吡啶 红外光谱得到，具体测试过程为：将试样压片成型，抽真空至10 -4Pa，升温至400℃热处理2h，然后降温至200℃后静态吸附吡啶5min并平衡5min，随后抽真空40分钟，再10分钟升温到300℃并平衡5分钟后进行IR扫描，B酸量和L酸量分别按照样品在1540cm -1和1450cm -1附近的吸收峰面积计算。
以下实施例和对比例中，所得催化剂的TEM照片通过FEI公司的Tecnai G2 F20 S-TWIN型高分辨场发射透射电子显微镜表征，工作电压为200kV。元素分析利用透射电镜装备的能量散射X射线分析仪进行检测。
以下实施例和对比例中，原料转化率及产物选择性的计算方法如下：
Figure PCTCN2021120641-appb-000001
Figure PCTCN2021120641-appb-000002
Figure PCTCN2021120641-appb-000003
Figure PCTCN2021120641-appb-000004
Figure PCTCN2021120641-appb-000005
其中：
1)当反应原料为C 9 +芳烃时，总选择性定义为(B+T+C 8A)选择性；
2)当反应原料为(甲苯+C 9 +芳烃)混合料时，总选择性定义为(B+C 8A)选择性。
实施例I系列
第I系列的实施例说明了根据本申请的仅包含固载在酸性分子筛上的第一金属组分的催化剂的制备和应用。
实施例I-1
取20g丝光沸石，过饱和浸渍钼酸铵溶液，然后于空气气氛下经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
所得催化剂的NH 3-TPD谱图如图1A所示，与图1B所示的对比例I-1的NH 3-TPD谱图相比，其在200-400℃区间内的峰面积相对于100-600℃区间内的总峰面积的比例显著增大。
所得催化剂的TEM元素分析如图2所示，其中左上图显示了催化剂中分子筛和氧化铝的相图，右上图显示了负载Mo元素的分布，左下图显示了Si元素分布，右下图显示了Al元素分布。根据所得催化剂的组成可知，富含硅的部分(见左下图)对应丝光沸石，而富含铝的部分(见右下图)对应氧化铝助剂，从Mo元素的分布(见右上图)可知，Mo元素主要分布于催化剂中的丝光沸石表面。
实施例I-2
取20g丝光沸石，过饱和浸渍高铼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得铼含量为0.5wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-3
取20g Beta分子筛，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克高岭土捏合成型，空气气氛下550℃焙烧2小时制得钼含量为1wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-4
取20g ZSM-12分子筛，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-5
取20g MCM-22分子筛，过饱和浸渍钼酸铵溶液，然后于空气气氛再经400℃预焙烧3小时。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为4wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-6
取20g丝光沸石，过饱和浸渍含磷酸二氢铵及钼酸铵的溶液，然后于空气气氛再经400℃预焙烧3小时。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得磷含量为0.5wt％的、钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-7
取20g USY分子筛，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-8
取20g SAPO-11分子筛，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-9
取20g丝光沸石，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与20克硅溶胶(含氧化硅7.7克)捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-10
取20g丝光沸石，过饱和浸渍钼酸铵溶液，然后于空气气氛经400℃预焙烧3小时得到改性分子筛。取改性分子筛与6.7克氧化铝及1克氧化镁捏合成型，空气气氛下550℃焙烧2小时制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-11
取20g ZSM-12与ZSM-5分子筛(重量比为7∶3)的混合物，过饱和浸渍钼酸铵溶液，然后于空气气氛再经300℃预焙烧3小时。取改性分 子筛与7.7克氧化铝捏合成型，空气气氛下550℃焙烧2小时制得钼含量为4wt％的催化剂，所得催化剂组成和性质见表I-1。
实施例I-12
按照实施例I-1的方法制备，不同的是，取一定量丝光沸石浸渍钼酸铵和钨酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-13
按照实施例I-1的方法制备，不同的是，取一定量丝光沸石浸渍一定钼酸铵、钨酸铵和高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-14
按照实施例1所述的方法制备，不同的是，取一定量丝光沸石浸渍钼酸铵溶液，制得钼含量为3wt％的改性分子筛粉，改性分子筛在空气和水蒸气的混合气氛(空气与水蒸气的体积比20∶1)经400℃预焙烧3小时。其余催化剂制备条件均相同，所得催化剂组成和性质见表I-1。
实施例I-15
按照实施例1所述的方法制备，不同的是，取一定量丝光沸石浸渍钼酸铵溶液，制得钼含量为3wt％的改性分子筛粉，改性分子筛在空气和水蒸气的混合气氛(空气与水蒸气的体积比5∶1)及400℃下焙烧3小时，其余催化剂制备条件均相同，所得催化剂组成和性质见表I-1。
实施例I-16
按照实施例1所述的方法制备，不同的是，取一定量丝光沸石浸渍钼酸铵溶液，制得钼含量为3wt％的改性分子筛粉，于120℃干燥后得到改性分子筛。取20克改性分子筛与7.7克氧化铝捏合成型，550℃焙烧2小时制得催化剂，所得催化剂组成和性质见表I-1。
实施例I-17
按照实施例1所述的方法制备，不同的是，取一定量丝光沸石浸渍一定钼酸铵、钨酸铵和高铼酸铵溶液，且改性分子筛在空气和水蒸气的混合气氛(空气与水蒸气的体积比20∶1)经400℃预焙烧3小时，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-18
按照实施例I-1的方法制备，不同的是，取一定量丝光沸石浸渍一定量钨酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-19
按照实施例I-1的方法制备，不同的是，取一定量丝光沸石浸渍一定量钼酸铵及高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-20
按照实施例I-1的方法制备，不同的是，取一定量丝光沸石浸渍一定量钨酸铵及高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
实施例I-21
按照实施例I-1的方法制备，不同的是，取20g丝光沸石，在搅拌过程中喷涂钼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表I-1。
对比例I-1
取7.7克氧化铝与20克丝光沸石混合成型，550℃焙烧2小时制得催化剂载体，再负载一定量钼酸铵，制得钼含量为3wt％的催化剂，所得催化剂组成和性质见表I-1。所得催化剂的NH 3-TPD如图1B所示，其中脱附温度在400℃以上的强酸峰面积相对于图1A明显更大。
Figure PCTCN2021120641-appb-000006
Figure PCTCN2021120641-appb-000007
测试例I-1
将5克上述实施例和对比例制备的催化剂分别置于反应器中，通氢气于450℃下还原3小时，再降温至370℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。
反应条件为：总重量空速为4.0小时 -1，反应温度370℃，反应压力2.5MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝50∶50(重量)。其中C 9 +A中含20％(重量)C 10 +A。C 9A原料重量组成为：丙苯4.2％、甲乙苯31.0％、三甲苯59.6％、茚满5.2％，C 10 +A重量组成为：二乙苯3.6％、二甲基乙苯26.9％、甲基丙苯2.3％、四甲苯28.8％、甲基萘14.4％、二甲基萘11.1％、其它12.9％。测试条件和结果如表I-2所示。
表I-2 测试例I-1的条件和结果
Figure PCTCN2021120641-appb-000008
Figure PCTCN2021120641-appb-000009
如表I-2的结果所示，与对比例相比，通过将金属选择性固载在分子筛上，可以提高转化率，同时减少芳环损失率。优化方案中，通过添加磷化物，可进一步提高转化效率至48.2％，芳环损失率降低至0.8％。优化方案中，通过引入Mo、Re、W三金属化合物，同样可提高转化率至48.5％，芳环损失率降低至0.7％。
实施例II系列
第II系列的实施例说明了根据本申请的包含固载在酸性分子筛上的第一金属组分和固载在氧化物助剂上的第二金属组分的催化剂的制备和应用。
实施例II-1
取20克丝光沸石，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
所得催化剂的TEM元素分析如图3所示，其中左上图显示了催化剂中分子筛和氧化铝结合的相图，中上图显示了Al元素分布，右上图显示了Si元素分布，左下图显示了Mo元素分布，中下图显示了Sr元素分布。根据所得催化剂的组成可知，富含硅的部分(见右上图)对应丝光沸石，而富含铝的部分(见中上图)对应氧化铝助剂，从金属氧化物分布可知，Mo金属(见左下图)主要分布于丝光沸石表面，而Sr元素(见中下图)主要分布于氧化铝助剂表面。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、 二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-2
取20克Beta沸石，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-3
取20克ZSM-12分子筛，过饱和浸渍一定钼酸铵溶液，，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-4
取20克ZSM-5分子筛，过饱和浸渍一定钼酸铵溶液，，经150℃喷雾 干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-5
取18克丝光沸石与2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取19.2克硅溶胶(含40％SiO 2)与一定硝酸锶混合均匀，制得改性硅溶胶。将改性分子筛与改性硅溶胶捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-6
取18克丝光沸石与2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸钾，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧 2小时制得钼含量为1wt％的、钾含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-7
取18克丝光沸石与2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸镓，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、镓含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-8
取18克丝光沸石与2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为1wt％的、锶含量为1.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。测试条件和结果如表II-2所示所示。
实施例II-9
取15克丝光沸石分子筛与5克ZSM-5分子筛混合后，过饱和浸渍一定钼酸铵溶液，经120℃干燥10小时后，再在空气气氛及450℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸铋，经120℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，500℃焙烧6小时制得钼含量为3wt％的、铋含量为5wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比2.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示所示。
实施例II-10
取15克丝光沸石分子筛及5克ZSM-5分子筛混合均匀后，等体积浸渍一定钼酸铵溶液，经120℃干燥10小时后，再在空气气氛及500℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸铈，经120℃干燥10小时后于空气气氛及400℃下焙烧3小时制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得钼含量为13wt％的，铈含量为8.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再 降温至370℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度370℃，反应压力3.5MPa，氢烃分子比3.0。反应原料为100％重整C 9 +A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示所示。
实施例II-11
取15克丝光沸石分子筛与5克ZSM-5分子筛混合后，过饱和浸渍一定钼酸铵溶液，经160℃快速喷雾干燥，然后经500℃焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸铋，经160℃烘干制得改性氧化铝，然后经500℃焙烧3小时。将改性分子筛与改性氧化铝捏合成型，500℃焙烧6小时制得钼含量为3wt％的、铋含量为5wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比4.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示所示。
实施例II-12
取15克丝光沸石分子筛与5克ZSM-5分子筛混合后，过饱和浸渍一定钼酸铵溶液，经500℃焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸铋，经500℃焙烧3小时制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧3小时制得钼含量为3wt％的、铋含量为5wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比4.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、 甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示所示。
实施例II-13
取15克Beta分子筛及5克ZSM-5分子筛混合均匀，过饱和浸渍一定量高铼酸铵溶液，经120℃干燥10小时后，再在空气气氛及500℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定氯化锗，经120℃干燥10小时制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得铼含量为1wt％的、锗含量为3.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.0MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝80∶20(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示所示。
实施例II-14
取15克ZSM-12分子筛及5克ZSM-5分子筛混合均匀后等体积浸渍一定钼酸铵溶液，经120℃干燥10小时后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取4克氧化铝及3.5克氧化镁混合均匀后等体积浸渍一定氯化锆，经120℃干燥10小时制得改性氧化物。将改性分子筛与改性氧化物捏合成型，500℃焙烧4小时制得钼含量为8wt％的、锆含量为5.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.5MPa，氢烃分子比3.0。反应原料为100％重整C 9 +A。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试 条件和结果如表II-2所示所示。
实施例II-15
按照实施例II-1的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵和钨酸铵溶液，其余条件均相同，所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-16
按照实施例II-1的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵和高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-17
按照实施例II-1的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钨酸铵和高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-18
按照实施例II-1的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵、钨酸铵和高铼酸铵溶液，其余条件均相同，所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-19
按照实施例II-1所述的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，过饱和浸渍一定钼酸铵溶液，经120℃干燥10小时后，再在空气和水蒸气的混合气氛(空气与水蒸气的体积比20∶1)及400℃下焙烧3小时制得改性分子筛粉，其余催化剂制备和还原条件以及反应条件均相同。所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-20
按照实施例II-1所述的方法制备，不同的是，取18克丝光沸石分子筛及2克ZSM-5分子筛混合均匀后，喷涂一定钼酸铵溶液，经120℃干燥10小时后，再在空气和水蒸气的混合气氛(空气与水蒸气的体积比5∶ 1)及400℃下焙烧3小时制得改性分子筛粉，其余催化剂制备和还原条件以及反应条件均相同。所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-21
按照实施例II-1所述的方法制备，不同的是，取18克丝光沸石与2克ZSM-5分子筛混合均匀后，等体积浸渍一定钼酸铵溶液，经120℃干燥后制得改性分子筛粉，取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得催化剂，其余催化剂制备和还原条件以及反应条件均相同。所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
实施例II-22
按照实施例II-9所述的方法制备，不同的是，改性分子筛经120℃干燥10小时后，再在空气和水蒸气的混合气氛(空气与水蒸气的体积比5∶1)及400℃下焙烧3小时，其余催化剂制备和还原条件以及反应条件均相同。所得催化剂组成和性质见表II-1，测试条件和结果如表II-2所示。
对比例II-1
取15克丝光沸石、5克ZSM-5与7.7克氧化铝混合成型，550℃焙烧2小时制得载体，再在载体上等体积浸渍一定量的钼酸铵溶液，500℃焙烧3小时制得钼含量为1wt％的改性催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-2
取15克丝光沸石、5克ZSM-5与7.7克氧化铝混合成型，550℃焙烧2 小时制得载体，再在载体上等体积共浸渍一定量的钼酸铵和氯化锶溶液，500℃焙烧4小时制得钼含量为1wt％的，锶含量1wt％的改性催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-3
取15克丝光沸石、5克ZSM-5与7.7克氧化铝混合，再加入一定量的含钼酸铵、硝酸镍的硝酸水溶液，捏合成型。550℃焙烧4小时制得钼含量为10wt％的，镍含量3wt％的改性催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力3.5MPa，氢烃分子比3.0。反应原料为100％重整C 9 +A。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-4
取18克丝光沸石与2克ZSM-5分子筛混合均匀，通过离子交换一定氯铂铵溶液溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定硝酸锶，经150℃喷雾干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得铂含量为0.05wt％的、锶含量为2.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再 降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比4.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-5
取18克丝光沸石与2克ZSM-5分子筛混合均匀后，通过离子交换一定亚硝基铂铵溶液溶液，经150℃喷雾干燥后，再在空气气氛及400℃下焙烧3小时制得改性分子筛粉。取7.0克氧化铝及0.7克氧化钛混合均匀后浸渍一定硝酸锶，经150℃喷雾干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得铂含量为0.1wt％的、锶含量为2.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比4.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-6
取20克丝光沸石分子筛过饱和浸渍一定二硝基铂铵溶液，经200℃喷雾干燥制得改性分子筛粉。取7.7克高岭土浸渍一定硝酸锌，经150℃干燥制得改性氧化铝。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得铂含量为0.05wt％的、锌含量为2.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为2.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重 量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
对比例II-7
取20克Beta分子筛过饱和浸渍一定二氯铂铵溶液，经200℃喷雾干燥后于空气气氛及500℃下焙烧2小时制得改性分子筛粉。取7.7克氧化铝等体积浸渍一定氯化亚锡，经200℃干燥制得改性氧化铝，。将改性分子筛与改性氧化铝捏合成型，550℃焙烧2小时制得铂含量为0.05wt％的、锡含量为2.0wt％的催化剂，所得催化剂组成和性质见表II-1。
将改性催化剂5克置于反应器中，通氢气于450℃下还原3小时，再降温至360℃，通入氢气及含有甲苯、C 9 +芳烃的物料与催化剂接触进行反应活性考察。反应条件为：总重量空速为4.0小时 -1，反应温度360℃，反应压力2.5MPa，氢烃分子比3.0。反应原料为甲苯∶C 9 +A＝43∶57(重量)。其中C 9 +A中含25％(重量)C 10A。C 9A原料重量组成为：丙苯4.2％、甲乙苯32.0％、三甲苯59.6％，茚满4.2％。C 10A重量组成为：二乙苯15.3％、二甲基乙苯36.9％、甲基丙苯22.3％、四甲苯24.0％、甲基萘1.5％。。测试条件和结果如表II-2所示。
Figure PCTCN2021120641-appb-000010
Figure PCTCN2021120641-appb-000011
表II-2 各实施例和对比例的性能测试条件和结果
Figure PCTCN2021120641-appb-000012
Figure PCTCN2021120641-appb-000013
如表II-2的结果所示，与对比催化剂相比，本申请催化剂通过将第一及第二金属分别固载于分子筛及氧化物助剂上，可进一步提高转化率、降低芳环损失。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (14)

  1. 一种歧化与烷基转移催化剂，包含酸性分子筛、固载在所述酸性分子筛上的第一金属组分和氧化物助剂，所述第一金属组分中所含的第一金属选自VB族金属、VIB族金属和VIIB族金属中的至少一种，所述催化剂的中强酸酸量为0.05-2.0mmol/g催化剂，中强酸酸量占总酸量的比例为60-99％。
  2. 根据权利要求1所述的催化剂，其中所述第一金属以金属元素、金属氧化物或两者组合的形式存在于所述催化剂中，
    优选地，所述第一金属为选自Mo、W和Re中的至少一种，更优选为Mo、Re和W中的至少两种的组合，其中以金属元素计二者的混合重量比例为0.1-10∶1，特别优选为Mo、Re和W三者的组合，且以金属元素计Mo、Re与W的重量比为1∶0.1-0.4∶0.1-0.6。
  3. 根据权利要求1或2所述的催化剂，其中所述酸性分子筛选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛，或者它们的组合，优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12、Y分子筛，或者它们的组合，更优选选自ZSM-5、MCM-22、MOR、ZSM-12分子筛，或者它们的组合。
  4. 根据权利要求1-3中任一项所述的催化剂，其中所述氧化物助剂选自氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、高岭土，或者它们的各种组合。
  5. 根据权利要求1-4中任一项所述的催化剂，其中以所述催化剂的总重量为基准，所述催化剂包含40-90重量％的所述酸性分子筛和5-40重量％的所述氧化物助剂，并且以金属元素计，所述催化剂包含0.01-20重量％的所述第一金属组分。
  6. 根据权利要求1-5中任一项所述的催化剂，其中所述催化剂进一包含磷，所述磷优选固载在所述酸性分子筛上，更优选地以P 2O 5计并以所述催化剂的总重量为基准，所述磷的含量为0.1-5重量％。
  7. 根据权利要求1-6中任一项所述的催化剂，其中所述催化剂进一步包含不同于所述第一金属组分的第二金属组分，所述第二金属组分优选固载在所述氧化物助剂上，
    优选地，所述第二金属组分中的第二金属选自IA族、IIA族、IIIA 族、IVA族、VA族、IVB族及镧系金属中的至少一种，更优选选自Sr、Bi、Ce、Zr和Ge中至少一种，所述第二金属以金属元素、金属氧化物或两者组合的形式存在于所述催化剂中。
  8. 根据权利要求7所述的催化剂，其中以催化剂的总重量为基准，所述催化剂包含40-90重量％、优选50-80重量％的酸性分子筛和5-40重量％、优选10-30重量％的氧化物助剂，并且以金属元素计，所述催化剂包含0.01-20重量％、优选0.05-18重量％的第一金属组分和0.01-20重量％、优选0.05-18重量％的第二金属组分。
  9. 制备权利要求1-8中任一项所述的歧化与烷基转移催化剂的方法，包括如下步骤：
    1)在酸性分子筛源上装载第一金属源和任选的磷源，并进行第一热处理得到改性分子筛；以及
    2)将所述改性分子筛与氧化物助剂源成型，并任选进行后处理，得到所述催化剂。
  10. 根据权利要求9所述的方法，其中所述方法具有以下特征中的至少一个：
    步骤1)的所述装载包括用包含第一金属源和任选的磷源的溶液浸渍所述酸性分子筛源；
    步骤1)的所述第一热处理包括焙烧或者干燥与焙烧的组合，优选地，所述干燥包括在50-200℃下干燥1-30h，所述焙烧包括在含氧气氛下在300-700℃焙烧1-30小时，进一步优选地，所述含氧气氛为空气与水蒸气的混合气体，二者体积比为5-100∶1：以及
    步骤2)的所述后处理包括在含氧气氛下在300-600℃焙烧1-30小时。
  11. 根据权利要求9或10所述的方法，其中所述方法具有以下特征中的至少一个：
    所述第一金属源为第一金属的可溶性化合物，所述第一金属选自VB族金属、VIB族金属和VIIB族金属中的至少一种，优选选自Mo、W和Re中的至少一种，更优选为Mo、Re和W中的至少两种的组合，其中以金属元素计二者的混合重量比例为0.1-10∶1，特别优选为Mo、Re和W三者的组合，且以金属元素计Mo、Re与W的重量比为1∶0.1-0.4∶0.1-0.6；
    所述酸性分子筛源选自具有八元环、十元环或十二元环孔结构特征的酸性分子筛，或者它们的组合，优选选自ZSM-5、SAPO-11、MCM-22、MOR、Beta、ZSM-12、Y分子筛，或者它们的组合，更优选选自ZSM-5、MCM-22、MOR、ZSM-12分子筛，或者它们的组合；和/或
    所述氧化物助剂选自氧化铝、氧化硅、氧化镁、氧化钛、氧化锆、高岭土，或者它们的组合。
  12. 根据权利要求9-11中任一项的方法，进一步包括，在步骤2)之前，在所述氧化物助剂源上装载第二金属源，并任选进行第二热处理，得到改性的氧化物助剂源，
    优选地，所述在氧化物助剂源上装载第二金属源包括用包含第二金属源的溶液浸渍所述氧化物助剂源；
    优选地，所述第二金属源为第二金属的可溶性化合物，所述第二金属选自IA族、IIA族、IIIA族、IVA族、VA族、IVB族及镧系金属中的至少一种，更优选选自Sr、Bi、Ce、Zr和Ge中的至少一种；以及
    优选地，所述第二热处理包括焙烧或者干燥与焙烧的组合，进一步优选地，所述干燥包括在50-200℃下干燥1-30h，所述焙烧包括在含氧气氛下在300-700℃焙烧1-30小时，特别优选地，所述含氧气氛为空气与水蒸气的混合气体，二者体积比为5-100∶1。
  13. 权利要求1-8中任一项所述的歧化与烷基转移催化剂在烷基芳烃的催化转化中的应用，所述烷基芳烃的催化转化包括烷基芳烃的歧化反应、烷基芳烃的烷基转移反应，或者两者的组合。
  14. 一种烷基芳烃的催化转化方法，包括在氢气存在下，使包含烷基芳烃的原料与权利要求1-8中任一项所述的歧化与烷基转移催化剂接触反应的步骤，
    优选地，所述烷基芳烃包括甲苯、C 9 +烷基芳烃，或者它们的组合；
    优选地，所述反应的条件包括：反应温度为250-500℃，反应压力为1.5-6.5MPa，氢烃摩尔比为1-10，进料重量空速为0.5-5。
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