CN112299433B - Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application - Google Patents

Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application Download PDF

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CN112299433B
CN112299433B CN201910693676.6A CN201910693676A CN112299433B CN 112299433 B CN112299433 B CN 112299433B CN 201910693676 A CN201910693676 A CN 201910693676A CN 112299433 B CN112299433 B CN 112299433B
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zeolite
zsm
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catalyst
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CN112299433A (en
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张上
桂鹏
胡长禄
潘晖华
吕雉
韩晓琳
张鹏
崔佳
李知春
龚奇菡
常玉红
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Petrochina Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/40—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

Abstract

The invention relates to hydrogen type ZSM-5/EU-1 eutectic zeolite, an aromatic isomerization catalyst containing the eutectic zeolite, a preparation method and application, wherein the ZSM-5/EU-1 eutectic zeolite is prepared by the following method: step 1): adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring; step 2): and transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing with water to be neutral, performing suction filtration, and drying to obtain the ZSM-5/EU-1 eutectic zeolite. The aromatic isomerization catalyst comprises the following components in parts by weight: 10.0-80.0 w% of hydrogen type ZSM-5/EU-1 eutectic zeolite, 15.0-90.0 w% of binder and 0.1-5.0 w% of metal rhenium in the VIIB group of the periodic table. The catalyst can be applied to the ethylbenzene dealkylation type C8 arene isomerization catalytic reaction process, and can effectively reduce the hydrogenation side reaction after the ethylbenzene dealkylation.

Description

Hydrogen type ZSM-5/EU-1 eutectic zeolite, aromatic isomerization catalyst, preparation method and application
Technical Field
The invention relates to hydrogen type ZSM-5/EU-1 eutectic zeolite and an aromatic hydrocarbon isomerization catalyst containing the eutectic zeolite. The aromatic hydrocarbon isomerization catalyst can be applied to a xylene isomerization unit of an aromatic hydrocarbon combination device, raffinate oil after separation of a target product, namely p-xylene (or o-xylene), is isomerized into a product with xylene close to thermodynamic equilibrium, and meanwhile, part of ethylbenzene in a raw material is converted into benzene, and belongs to the technical field of catalysts.
Background
Since ethylbenzene has a boiling point that is only 2.2 ℃ different from PX, separation of ethylbenzene from xylenes by rectification is difficult and uneconomical, and therefore ethylbenzene must be converted during xylene isomerization. The commercial isomerization technology of C8 aromatics can be classified into ethylbenzene conversion type and ethylbenzene dealkylation type according to the ethylbenzene conversion route. The ethylbenzene dealkylation type C8 aromatics isomerization technology has attracted considerable attention because it can reduce the investment scale of the plant and the consumption of utilities in operation, and enrich the product types of the plant. For ethylbenzene dealkylation type C8 aromatics isomerization catalysts, the indexes for characterizing the performance of the catalysts are generally as follows: equilibrium concentration of p-xylene (PX/. sigma.X), ethylbenzene conversion (EBc) and Xylene Yield (XY).
The general process of an aromatic hydrocarbon combined device is to send benzene components generated by ethylbenzene dealkylation in a xylene isomerization unit to a subsequent unit for separation and refining to produce a pure benzene product. The purity of benzene in low boiling azeotropes (mainly cyclohexane and methylcyclopentane) has a large impact on the energy consumption of the subsequent separation and refining processes. When the purity of benzene in the low-boiling-point azeotrope is higher (not less than 99.3%), the benzene component can be directly sent to the rectifying section of the aromatic extraction unit, and qualified pure benzene product (not less than 99.9%) is directly extracted from the side line of the benzene tower; when the purity of benzene in the low boiling point azeotrope is lower (less than 99.3%), benzene can not be separated from other azeotropes directly by rectification, and the material needs to be sent into an aromatic extraction unit to produce a pure benzene product, so that the load of the extraction unit and the production energy consumption are increased. Thus, for commercial ethylbenzene dealkylation type C8 aromatics isomerization catalysts, the purity of the product benzene in the low boiling azeotrope is also an important indicator.
The patent CN1233531A, CN101293805A and CN1327945A disclose EU-1 zeolite and a technology for C8 aromatic hydrocarbon isomerization reaction, and relate to the synthesis of EU-1 molecular sieve, the dealumination of EU-1 molecular sieve by acid, the modification of catalyst by tin and indium and the like. Patents CN1102360A and CN1887423A disclose that ZSM-5 zeolite and mordenite are used as ethylbenzene dealkylation type C8 aromatics isomerization catalysts, and group viii metal is added, so that the catalyst has higher ethylbenzene removal capability. Patent CN102039161 discloses a catalyst using EUO and ZSM-5 molecular sieves and at least one noble metal of group viii and antimony oxide, having high ethylbenzene conversion activity and xylene selectivity. However, the above patent technologies do not relate to the product distribution study after ethylbenzene dealkylation.
Patent CN108273546A discloses a preparation method of a catalyst for preparing propylene by catalytic cracking of naphtha, which comprises the following steps: firstly, preparing EU-1/ZSM-5 composite molecular sieve by adopting a hydrothermal synthesis method, and then adding gamma-Al2O3Uniformly mixing, and loading perrhenic acid and tetrabutyl ammonium perrhenate by adopting an impregnation method after molding to obtain the catalyst for preparing propylene by catalytic pyrolysis of naphtha. The patent discloses: the catalyst for preparing propylene by catalytic cracking of naphtha prepared by the method can be used for catalytically cracking naphtha to produce more propylene products. The technology utilizes the cracking function of the EU-1/ZSM-5 composite molecular sieve to treat naphtha (mainly straight-chain paraffin of C5-C7) and crack the naphtha into micromolecular (C2-C4) olefin. The technology is not suitable for processing the C8 aromatic hydrocarbon isomerization process, otherwise, the technology can cause the C8 aromatic hydrocarbon raw material to be largely cracked, the liquid yield is reduced, and the economic benefit is not high. The C8 aromatic hydrocarbon isomerization catalyst which adopts ZSM-5, EU-1 zeolite as an acidic component and a VIII group noble metal as a metal component has been realized to be industrially applied, shows good catalytic performance, but still has the problem that an acidic active center is not matched with a metal active center. In the ethylbenzene dealkylation type C8 aromatics isomerization catalyst, even if the content of the group VIII noble metal is controlled below 0.05 percent, the catalyst can still be usedThe problem of higher non-aromatic hydrocarbon content azeotropic with benzene occurs, the purity of the benzene in the low boiling point azeotrope is reduced, and the yield and the energy consumption of the aromatic hydrocarbon combination device are influenced.
Disclosure of Invention
The method takes ZSM-5/EU-1 eutectic zeolite as an acid center, takes non-noble metal rhenium as a metal center, and the acid center is better matched with the metal center, so that the method can realize xylene isomerization and ethylbenzene dealkylation, can quickly hydrogenate an ethyl intermediate generated by ethylbenzene dealkylation to generate ethane, and can effectively control a hydrogenation side reaction of the ethylbenzene dealkylation to generate benzene, thereby improving the purity of the benzene in a low-boiling-point azeotrope. The specific invention content is as follows:
firstly, the invention provides hydrogen type ZSM-5/EU-1 eutectic zeolite, which simultaneously contains a ZSM-5 zeolite crystal phase and an EU-1 zeolite crystal phase and is prepared by the following method:
step 1): adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring;
step 2): transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing with water to be neutral, performing suction filtration, and drying to obtain ZSM-5/EU-1 eutectic zeolite;
wherein the template agent is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide and triethylamine;
the silicon source is one or more of silica sol, water glass, white carbon black and silicic acid.
Preferably, the hydrogen type ZSM-5/EU-1 eutectic zeolite provided by the invention is prepared by the steps of preparing a template agent, wherein the template agent is tetraethylammonium hydroxide; the silicon source is a mixture of silica sol and white carbon black.
The invention provides hydrogen type ZSM-5/EU-1 eutectic zeolite, wherein the mass content of a ZSM-5 zeolite crystalline phase is 60-95% by taking the mass of the eutectic zeolite as a hundred percent.
Preferably, the hydrogen type ZSM-5/EU-1 eutectic zeolite provided by the invention is characterized in that the mass content of the ZSM-5 zeolite crystalline phase is 70-90% by taking the mass of the eutectic zeolite as a hundred percent.
The invention provides hydrogen type ZSM-5/EU-1 eutectic zeolite, wherein the silicon-aluminum ratio of the eutectic zeolite is 1: 20 to 160.
Generally, EU-1 zeolite is added into NaOH solution for treatment, the EU-1 molecular sieve is primarily decomposed in alkali solution to form an EU-1 molecular sieve primary structural unit, the EU-1 molecular sieve primary structural unit plays a role in structure guidance for synthesis of the eutectic molecular sieve, crystallization of the eutectic molecular sieve is accelerated to form an EU-1 zeolite precursor, then a template agent, a silicon source and water are added to form a reactant mixed solution, and then the solution is transferred to a stainless steel kettle for crystallization.
In the step 1), firstly, adding the EU-1 zeolite into a NaOH solution, wherein the EU-1 zeolite is primarily decomposed in an alkali solution to form a primary EU-1 molecular sieve structural unit, so that the EU-1 molecular sieve structural unit plays a role in structure guidance for the synthesis of the eutectic molecular sieve and accelerates the crystallization of the eutectic molecular sieve. In this process, stirring, preferably continuous stirring, may be carried out. And adding the template agent, the silicon source and the water after uniformly stirring, and uniformly stirring to form a reactant mixed solution. Wherein the template agent is one or more of tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide and triethylamine; preferably tetraethylammonium hydroxide. The silicon source is one or more of silica sol, water glass, white carbon black and silicic acid, and preferably, the silicon source is a mixture of the silica sol and the white carbon black.
The step 2) is a crystallization process, and the reactant mixed solution in the step 1) is transferred to a stainless steel kettle for crystallization, wherein the crystallization temperature is 100-300 ℃, and the crystallization time is 12-36 hours.
And taking out the product, and cooling to room temperature, wherein the process can be carried out under natural conditions or by adopting a freezing method for rapidly cooling. The product is then washed with water to neutrality, which is for the unreacted templating agent, the silicon source.
And (3) carrying out suction filtration on the product, and drying to obtain the ZSM-35/EU-1 eutectic zeolite.
The invention also provides an aromatic hydrocarbon isomerization catalyst which contains the hydrogen type ZSM-5/EU-1 eutectic zeolite; and the catalyst comprises the following components in percentage by total mass:
10.0-80.0% of hydrogen type ZSM-5/EU-1 eutectic zeolite;
0.1-5.0% of metal rhenium;
the balance being binder.
Preferably, the content of the hydrogen type ZSM-5/EU-1 eutectic zeolite in the aromatic hydrocarbon isomerization catalyst provided by the invention is 40-70% by weight of the total catalyst.
Preferably, the aromatic hydrocarbon isomerization catalyst provided by the invention has the metal rhenium content of 0.5-3.0% by weight of the total catalyst.
More preferably, the aromatic hydrocarbon isomerization catalyst provided by the invention has a metal rhenium content of 1.0-2.0% by weight of the total catalyst.
Preferably, the aromatic hydrocarbon isomerization catalyst provided by the invention has a binder selected from one or more of alumina, titanium oxide, silicon oxide, boron oxide, magnesium oxide and clay
More preferably, the present invention provides the aromatic hydrocarbon isomerization catalyst, wherein the binder site is alumina and/or titania.
In the aromatic hydrocarbon isomerization catalyst provided by the invention, the content of the hydrogen type ZSM-5/EU-1 eutectic zeolite is 10-80% by weight of the total mass of the catalyst. In the aromatic hydrocarbon isomerization catalyst provided by the invention, the content of the metal rhenium is 0.1-5.0%, preferably 0.5-3.0%, and more preferably 1.0-2.0% in percentage by total mass of the catalyst. In the aromatic hydrocarbon isomerization catalyst provided by the invention, a binder is not particularly limited, the binder is one or more selected from alumina, titanium oxide, silica, boron oxide, magnesium oxide and clay, and the binder is preferably alumina and/or titanium oxide.
The invention also provides a preparation method of the aromatic hydrocarbon isomerization catalyst, which comprises the following specific steps:
step 1): roasting ZSM-5/EU-1 eutectic zeolite in a low-oxygen-concentration atmosphere at the roasting temperature of 200-500 ℃ for 3-8 h;
step 2): uniformly mixing, molding and roasting the roasted eutectic zeolite and a binder, wherein the roasting temperature is 200-600 ℃, and the roasting time is 3-6 hours;
step 3): 0.1-0.5 g/mL of the product roasted in the step 2)-1Performing ion exchange for 2-4 hours in the ammonium salt solution at the exchange temperature of 40-95 ℃, then washing with deionized water, and filtering;
step 4): dipping the product exchanged in the step 3) in a rhenium salt solution with a liquid-solid ratio of 1.0-3.0 for 2-24 hours at a dipping temperature of 25-95 ℃, and then filtering and drying;
step 5): activating the product dried in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; and then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst.
The preparation method of the aromatic hydrocarbon isomerization catalyst provided by the invention is characterized in that the roasting temperature in the step 1) is 300-400 ℃; the roasting temperature in the step 2) is 350-450 ℃; in the step 3), the ammonium salt solution is ammonium chloride and/or ammonium nitrate, and the exchange temperature is 60-80 ℃. In the step 4), the liquid-solid ratio is 1.2-2.0, the dipping temperature is 40-60 ℃, and the dipping time is 6-16 hours; in the step 5), the activation temperature is 300-400 ℃; the reduction temperature is 300-400 ℃.
Generally, in the step 1), the ZSM-5/EU-1 eutectic zeolite is firstly calcined in the low-oxygen concentration atmosphere, and the calcination temperature and the calcination time are not particularly limited, wherein the calcination temperature can be 200-500 ℃, and if the calcination temperature is lower than 200 ℃, the temperature is lower. If the calcination temperature is higher than 500 ℃, the temperature is higher. The calcination time is generally 3 to 8 hours, and if the calcination time is less than 3 hours, the time is too short. If the calcination time is more than 8 hours, the time is too long.
In the step 2), uniformly mixing, molding and roasting the roasted eutectic zeolite and the binder, wherein the roasting temperature and the roasting time are not particularly limited, preferably the roasting temperature is 200-600 ℃, and the roasting time is 3-6 hours; if the roasting temperature is lower than 200 ℃, the temperature is lower; if the roasting temperature is higher than 600 ℃, the temperature is higher; the roasting time is generally 3-8h, and if the roasting time is less than 3 h, the roasting time is too short; if the calcination time is more than 6 hours, the time is too long.
In the step 3), the roasted product obtained in the step 2) is added in an amount of 0.1-0.5 g/mL-1Performing ion exchange for 2-4 hours at the exchange temperature of 40-95 ℃ in the ammonium salt solution, washing with deionized water, and filtering; the concentration of the ammonium salt solution in this step is not particularly limited, but is preferably 0.1 to 0.5 g/mL-1If the concentration is lower than this value, the concentration is lower. If it is higher than this value, the concentration is higher. The exchange temperature in this step is not particularly limited, but is preferably 40 to 95 ℃ and if the temperature is lower than 40 ℃, the temperature is lower. If it is higher than 95 deg.C, the temperature is too high.
In the step 4), the product exchanged in the step 3) is immersed in a rhenium salt solution with a liquid-solid ratio of 1.0-3.0 for 2-24 hours at a temperature of 25-95 ℃, and then filtered and dried, wherein an immersion method is adopted to load metal rhenium on a catalyst carrier. In this process, the dipping time is not particularly limited, but is generally 2 to 24 hours, and if the dipping time is less than 2 hours, the time is too short; if the dipping time is longer than 24 hours, the time is too long. The dipping temperature is not particularly limited, and is generally 25-95 ℃, and if the temperature is lower than 25 ℃, the temperature is lower; if it is higher than 95 deg.C, the temperature is too high.
Step 5): activating the product dried in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; and then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst.
The invention also provides another preparation method of the aromatic hydrocarbon isomerization catalyst, which comprises the following specific steps:
step 1): roasting ZSM-5/EU-1 eutectic zeolite in a low-oxygen-concentration atmosphere at the roasting temperature of 200-500 ℃ for 3-8 h;
step 2): uniformly mixing, molding and roasting the roasted eutectic zeolite and a binder, wherein the roasting temperature is 200-600 ℃, and the roasting time is 3-8 hours;
step 3): uniformly mixing, molding and roasting the roasted eutectic zeolite, the oxide of rhenium and a binder, wherein the roasting temperature is 200-600 ℃;
step 4): 0.1-0.5 g/mL of the catalyst calcined in the step 3)-1Performing ion exchange for 2-4 hours in the ammonium salt solution at the exchange temperature of 40-95 ℃, then washing with deionized water, and filtering;
step 5): activating the dried catalyst in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; and then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst.
The preparation method of the aromatic hydrocarbon isomerization catalyst provided by the invention is characterized in that the roasting temperature in the step 1) is 300-400 ℃; the roasting temperature in the step 2) is 350-450 ℃; the rhenium oxide in the step 3) is one or more of rhenium heptoxide, rhenium dioxide and rhenium trioxide; the roasting temperature is 350-450 ℃. The rhenium oxide is rhenium heptoxide. The ammonium salt solution in the step 4) is ammonium chloride and/or ammonium nitrate, and the exchange temperature is 60-80 ℃; in the step 5), the activation temperature is 300-400 ℃, and the reduction temperature is 300-400 ℃.
Generally, in the step 1), firstly, roasting the ZSM-5/EU-1 eutectic zeolite in a low-oxygen-concentration atmosphere, wherein the roasting temperature and the roasting time are not particularly limited, the roasting temperature can be 200-500 ℃, and if the roasting temperature is lower than 200 ℃, the temperature is lower; if the calcination temperature is higher than 500 ℃, the temperature is higher. The roasting time is generally 3-8h, and if the roasting time is less than 3 h, the roasting time is too short; if the calcination time is more than 8 hours, the time is too long.
In the step 2), uniformly mixing, molding and roasting the roasted eutectic zeolite and the binder, wherein the roasting temperature and the roasting time are not particularly limited, preferably the roasting temperature is 200-600 ℃, and the roasting time is 3-8 h; if the calcination temperature is lower than 200 ℃, the temperature is lower. If the calcination temperature is higher than 600 ℃, the temperature is higher. The roasting time is generally 3-8h, and if the roasting time is less than 3 h, the roasting time is too short; if the calcination time is more than 8 hours, the time is too long.
In the step 3), uniformly mixing, molding and roasting the roasted eutectic zeolite, the oxide of rhenium and the binder, wherein the roasting temperature is 200-600 ℃, the roasting temperature and the roasting time are not particularly limited, the roasting temperature is preferably 200-600 ℃, and if the roasting temperature is lower than 200 ℃, the temperature is lower; if the calcination temperature is higher than 600 ℃, the temperature is higher.
In the step 4), the calcined catalyst in the step 3) is added in an amount of 0.1-0.5 g/mL-1Performing ion exchange for 2-4 hours in the ammonium salt solution at the exchange temperature of 40-95 ℃, then washing with deionized water, and filtering; the purpose of this step is. . . In this process, the dipping time is not particularly limited, but is generally 2 to 4 hours, and if the dipping time is less than 2 hours, the time is too short; if the dipping time is more than 4 hours, the time is too long. The dipping temperature is not particularly limited, but is generally 40-95 ℃, and if the temperature is lower than 40 ℃, the temperature is lower; if it is higher than 95 deg.C, the temperature is too high.
Step 5): activating the dried catalyst in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; and then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst.
The application of the aromatic hydrocarbon isomerization catalyst provided by the invention is characterized in that raffinate oil of an aromatic hydrocarbon combination device is used as a raw material to carry out dealkylation type C8 aromatic hydrocarbon isomerization reaction, and the reaction conditions are as follows: the reaction temperature is 300-400 ℃, the hydrogen partial pressure is 0.70-1.5 MPa, and the volume ratio of hydrogen to oil is 100-500 v.v-1And the feeding weight hourly space velocity is 5-15 h-1。
The invention can also be stated in detail as follows:
an aromatic isomerization catalyst comprising by weight: 10.0-80.0 w% of hydrogen type ZSM-5/EU-1 eutectic zeolite, 15.0-90.0 w% of binder and 0.1-5.0 w% of metal rhenium in the VIIB group of the periodic table.
The preparation method of the hydrogen type ZSM-5/EU-1 eutectic zeolite comprises the following steps: adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring. And transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing to be neutral with water, performing suction filtration, and drying at 100 ℃ to obtain the ZSM-5/EU-1 eutectic zeolite. The template agent is one or more of tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetraethyl ammonium bromide, tetrapropyl ammonium bromide and triethylamine, and tetraethyl ammonium hydroxide is preferred. The silicon source is one or more of silica sol, water glass, white carbon black and silicic acid, and the mixture of silica sol and white carbon black is preferred.
The hydrogen type ZSM-5/EU-1 eutectic zeolite contains ZSM-5 zeolite crystal phase and EU-1 zeolite crystal phase at the same time, and the weight content of the ZSM-5 zeolite in the eutectic zeolite is 60-95 w%, preferably 70-90 w%. Silicon to aluminum ratio (SiO)2/Al2O3) More than 20, preferably in the range of 20-160, and the content of the hydrogen type ZSM-5/EU-1 eutectic zeolite is preferably 40-70 w%.
The binder is selected from one or more of alumina, titanium oxide, silicon oxide, boron oxide, magnesium oxide and clay, preferably from alumina, titanium oxide or a mixture of the two.
The content of rhenium (Re) in the VIIB group metal of the periodic Table is 0.1 to 5.0 w%, preferably 1.0 to 3.0 w%, more preferably 0.5 to 2.0 w%.
The preparation method of the catalyst comprises the following steps: and roasting the ZSM-5/EU-1 eutectic zeolite in a low-oxygen-concentration atmosphere at the roasting temperature of 200-500 ℃, preferably 300-400 ℃ for 3-8 h. Uniformly mixing and molding the sintered eutectic zeolite and the binder, and roasting at the temperature of 200-600 ℃, preferably 350-450 ℃, wherein the roasting time is 3-8 h. The calcined catalyst is added in an amount of 0.1 to 0.5 g/mL-1The ammonium salt solution is subjected to ion exchange for 2-4 hours, the ammonium salt solution is preferably selected from ammonium chloride and ammonium nitrate, the exchange temperature is 40-95 ℃, the exchange temperature is preferably 60-80 ℃, and then deionized water is usedWashing and filtering. And (3) soaking the exchanged catalyst in a rhenium salt solution with the liquid-solid ratio of 1.0-3.0, preferably 1.2-2.0 at 25-95 ℃, preferably 40-60 ℃ for 2-24 hours, preferably 6-16 hours, preferably ammonium perrhenate, filtering and drying. Activating the dried catalyst for 2-8 hours at 200-550 ℃, preferably 300-400 ℃ in an air atmosphere, and then reducing for 2-8 hours at 200-550 ℃, preferably 300-400 ℃ in a hydrogen atmosphere to obtain the catalyst.
The preparation method of the catalyst comprises the following steps: roasting ZSM-5/EU-1 eutectic zeolite in a low-oxygen-concentration atmosphere, wherein the roasting temperature is 200-500 ℃, and preferably 300-400 ℃. Uniformly mixing and molding the sintered eutectic zeolite, rhenium oxide and a binder, and roasting at the temperature of 200-600 ℃, preferably 350-450 ℃; the rhenium oxide is one or more of rhenium heptoxide, rhenium dioxide and rhenium trioxide, and preferably rhenium heptoxide. The calcined catalyst is added in an amount of 0.1 to 0.5 g/mL-1And carrying out ion exchange in the ammonium salt solution for 2-4 hours, wherein the ammonium salt solution is preferably selected from ammonium chloride and ammonium nitrate, the exchange temperature is 40-95 ℃, preferably 60-80 ℃, and then washing with deionized water, filtering and drying. Activating the dried catalyst for 2-8 hours at 200-550 ℃, preferably 300-400 ℃ in an air atmosphere, and then reducing for 2-8 hours at 200-550 ℃, preferably 300-400 ℃ in a hydrogen atmosphere to obtain the catalyst.
The invention also relates to application of the catalyst, which is characterized in that raffinate oil of an aromatic hydrocarbon combination device is used as a raw material to carry out dealkylation type C8 aromatic hydrocarbon isomerization reaction at the reaction temperature of 300-400 ℃, the hydrogen partial pressure of 0.70-1.5 MPa and the hydrogen-oil volume ratio of 100-500 v.v.v-1And the feeding weight hourly space velocity is 5-15 h-1Under the condition, xylene isomerization and ethylbenzene dealkylation can be realized, and the hydrogenation side reaction of generating benzene by ethylbenzene dealkylation can be effectively controlled, so that the purity of benzene in the low-boiling-point azeotrope is improved. The purity of benzene in the azeotrope of benzene, methyl cyclopentane and cyclohexane is not less than 99.5%.
Detailed Description
The following examples illustrate the invention without in any way limiting its scope.
Preparation of ZSM-5/EU-1 eutectic zeolite
Example 1
Adding EU-1 zeolite into NaOH solution, stirring uniformly, adding tetraethylammonium hydroxide, silica sol, white carbon black and water, and stirring uniformly. Transferring the solution to a stainless steel kettle, crystallizing at 200 ℃ for 30 hours, taking out, cooling to room temperature, washing to neutrality with water, filtering, and drying at 100 ℃ to obtain different SiO2/Al2O3ZSM-5/EU-1 eutectic zeolite.
Example 2
Adding EU-1 zeolite into NaOH solution, stirring uniformly, adding tetraethylammonium bromide, tetrapropylammonium bromide, silica sol and water, and stirring uniformly. Transferring the solution to a stainless steel kettle, crystallizing at 160 ℃ for 36 hours, taking out, cooling to room temperature, washing to neutrality with water, filtering, and drying at 100 ℃ to obtain different SiO2/Al2O3ZSM-5/EU-1 eutectic zeolite of (1).
Preparation of the catalyst
Example 3
Containing 70.0 w% ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O3100), 3.0 w% Re, 27.0 w% alumina, catalyst C3.
SiO synthesized in example 12/Al2O3100 of ZSM-5/EU-1 eutectic zeolite is fully mixed with pseudo-boehmite powder, 3.0w percent of nitric acid solution is added and uniformly mixed, and a cylindrical orifice plate is used for extrusion molding; standing the cylindrical strip at room temperature for 4 hours, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ in air for 4 hours to prepare a catalyst carrier; the catalyst carrier was adjusted to 0.2 g/mL-1Exchanging the ammonium chloride solution for 2 hours at the temperature of 60-90 ℃, washing the ammonium chloride solution by deionized water, and filtering; the obtained carrier after exchange is immersed in a solution containing ammonium perrhenate at normal temperature for 12 hours, dried at 120 ℃ for 2 hours, calcined at 500 ℃ for 4 hours, and reduced in hydrogen at 500 ℃ for 4 hours to obtain the catalyst C3.
Example 4
Containing 50.0 w% ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O3＝20)、1.0w％Re、49.0w% alumina, catalyst C4.
SiO synthesized in example 22/Al2O3ZSM-5/EU-1 eutectic zeolite 20 was subjected to extrusion, drying, calcination, ammonium exchange, impregnation, drying, calcination and reduction by the method in example 3 to obtain catalyst C4.
Example 5
Containing 80.0 w% of ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O360), 4.5 w% Re, 15.5 w% alumina catalyst C5.
SiO synthesized in example 12/Al2O3The 60 ZSM-5/EU-1 eutectic zeolite is fully mixed with rhenium heptoxide and pseudo-boehmite powder, 3.0 w% nitric acid solution is added and uniformly mixed, and a cylindrical orifice plate is used for extrusion molding; standing the cylindrical strip at room temperature for 4 hours, drying at 120 ℃ for 2 hours, and roasting at 500 ℃ in air for 4 hours to prepare a catalyst carrier; the catalyst carrier was adjusted to 0.2 g/mL-1Exchanging the ammonium nitrate solution for 2 hours at the temperature of 60-90 ℃, washing with deionized water, and filtering; drying at 120 deg.C for 2 hr, calcining at 500 deg.C for 4 hr, and reducing at 500 deg.C in hydrogen for 4 hr to obtain catalyst C5.
Example 6
Containing 40.0 w% of ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O380), 0.5 w% Re, 59.5 w% alumina catalyst C6.
SiO synthesized in example 22/Al2O3ZSM-5/EU-1 eutectic zeolite and rhenium dioxide 80 were subjected to extrusion, drying, calcination, ammonium exchange, drying, calcination and reduction by the method described in example 5 to obtain catalyst C6.
Example 7
Containing 60.0 w% ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O340), 2.0 w% Re, 38.0 w% alumina catalyst C7.
SiO synthesized in example 12/Al2O340 ZSM-5/EU-1 eutectic zeolite, extruded, dried and calcined as described in example 3And (3) sintering, ammonium exchange, impregnation, drying, roasting and reduction to obtain the catalyst C7.
Comparative example 1
Containing 60.0 w% ZSM-5/EU-1 eutectic zeolite (SiO)2/Al2O340), 0.2 w% Pt, 38.0 w% alumina catalyst C8.
SiO synthesized in example 12/Al2O3Adopting the method in the embodiment 2 to carry out extrusion, drying, roasting and ammonium exchange on 40 ZSM-5/EU-1 eutectic zeolite; the obtained exchanged carrier was immersed in a solution containing chloroplatinic acid at normal temperature for 12 hours, dried at 120 ℃ for 2 hours, calcined at 500 ℃ for 4 hours, and reduced in hydrogen at 500 ℃ for 4 hours to obtain catalyst C8.
Comparative example 2
Taking ZSM-5 zeolite, EU-1 zeolite and gamma-Al2O3Weighing and uniformly mixing the materials according to the weight ratio of 45:15:40, kneading the mixed powder in dilute nitric acid with the concentration of 2%, extruding and forming, drying at 115 ℃, and roasting in the air at 600 ℃ for 2 hours to obtain the carrier. 5% NH for the support4And exchanging the Cl aqueous solution for 2 hours at 95 ℃, filtering, washing with deionized water, and drying to obtain the ammonium carrier. The ammonium type carrier is immersed in chloroplatinic acid with the concentration of 0.35mg/ml for 20 hours at the room temperature and the liquid-solid weight ratio of 1.4, diffused at the temperature of 60 ℃ for 4 hours after filtration, dried at the temperature of 120 ℃ for 4 hours, activated in the air at the temperature of 500 ℃ for 4 hours, and reduced in hydrogen for 4 hours, thus obtaining the catalyst C9 with platinum loading of 0.1 w%.
Evaluation of catalyst Effect
Example 8
The performance of the catalysts C3-C9 was evaluated using a 100mL fixed bed unit, the feedstock was raffinate oil from an aromatics complex, the composition of which is shown in Table 1, and the feedstock contained no cyclohexane or methylcyclopentane.
TABLE 1 raffinate oil composition for evaluation
Figure BDA0002147239210000151
Figure BDA0002147239210000161
Wherein C7N + P means C7And below cycloalkanes and alkanes, C8N + P meaning C8Cycloalkanes and alkanes, B means benzene, T means toluene, EB means ethylbenzene, PX means p-xylene, MX means m-xylene, OX means o-xylene, C9+ A means C9And the above aromatic hydrocarbons.
TABLE 2 evaluation conditions for catalyst Performance
Figure BDA0002147239210000162
Catalyst performance was evaluated in terms of equilibrium concentration of p-xylene (PX/. sigma.X), ethylbenzene conversion (EBc), Xylene Yield (XY) and benzene purity Bp in azeotropic systems (benzene, cyclohexane, methylcyclopentane).
Figure BDA0002147239210000163
Figure BDA0002147239210000164
Figure BDA0002147239210000165
Figure BDA0002147239210000166
TABLE 3 evaluation results of catalyst Properties
Figure BDA0002147239210000167
Figure BDA0002147239210000171
The evaluation results show that the catalysts C3-C7 adopting non-noble metal Re in the invention keep higher ethylbenzene conversion rate and xylene yield, and the purity of benzene in the reaction product in an azeotropic system (benzene, cyclohexane and methyl cyclopentane) is higher, and is 99.53-99.84%, which is obviously higher than that of the catalysts C8 and C9 adopting noble metal Pt.
In the catalyst C3-C7 of the invention, the benzene component of the isomerization product can be directly sent to the rectifying section of the aromatic hydrocarbon extraction unit, and qualified pure benzene products are directly extracted from the side line of the benzene tower, thus effectively reducing the production energy consumption of the aromatic hydrocarbon combination device.

Claims (18)

1. An aromatic isomerization catalyst, wherein the catalyst comprises a hydrogen form of ZSM-5/EU-1 eutectic zeolite; and the catalyst comprises the following components in percentage by total mass:
10.0-80.0% of hydrogen type ZSM-5/EU-1 eutectic zeolite;
0.1-5.0% of metal rhenium;
the balance being binder;
the hydrogen type ZSM-5/EU-1 eutectic zeolite contains a ZSM-5 zeolite crystal phase and an EU-1 zeolite crystal phase at the same time, and is prepared by the following method:
step 1): adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring;
step 2): transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing with water to be neutral, performing suction filtration, and drying to obtain ZSM-5/EU-1 eutectic zeolite;
wherein the template agent is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide and triethylamine;
the silicon source is one or more of silica sol, water glass, white carbon black and silicic acid.
2. The aromatics isomerization catalyst of claim 1 wherein the templating agent is tetraethylammonium hydroxide; the silicon source is a mixture of silica sol and white carbon black.
3. The aromatic hydrocarbon isomerization catalyst according to claim 1, wherein the content of the ZSM-5 zeolite crystal phase is 60 to 95% by mass in terms of hundred% by mass of the eutectic zeolite.
4. The aromatic hydrocarbon isomerization catalyst according to claim 3, wherein the content of the ZSM-5 zeolite crystal phase is 70 to 90% by mass in terms of hundred% by mass of the eutectic zeolite.
5. The aromatic hydrocarbon isomerization catalyst of claim 1 wherein the eutectic zeolite has a silica to alumina ratio of 1: 20 to 160.
6. The aromatic hydrocarbon isomerization catalyst according to claim 1, wherein the hydrogen type ZSM-5/EU-1 eutectic zeolite is contained in an amount of 40 to 70% by weight based on the total weight of the catalyst.
7. The aromatics isomerization catalyst of claim 1, wherein the metallic rhenium is present in an amount of 0.5 to 3.0 percent by weight of the total catalyst.
8. The aromatics isomerization catalyst of claim 1, wherein the metallic rhenium is present in an amount of 1.0 to 2.0 percent by weight of the total catalyst.
9. The aromatic hydrocarbon isomerization catalyst of claim 1, wherein the binder is one or more selected from the group consisting of alumina, titania, silica, boria, magnesia, and clay.
10. The aromatic hydrocarbon isomerization catalyst of claim 9, wherein the binder is alumina and/or titania.
11. A method for preparing an aromatic hydrocarbon isomerization catalyst, which is the method for preparing the catalyst according to any one of claims 1 to 10, and is characterized by comprising the following specific steps:
step 1): roasting hydrogen type ZSM-5/EU-1 eutectic zeolite in a low oxygen concentration atmosphere at the roasting temperature of 200-500 ℃ for 3-8 h;
step 2): uniformly mixing, molding and roasting the roasted eutectic zeolite and a binder, wherein the roasting temperature is 200-600 ℃, and the roasting time is 3-6 hours;
step 3): the roasted product in the step 2) is added in an amount of 0.1-0.5 g/mL-1Performing ion exchange for 2-4 hours in the ammonium salt solution at the exchange temperature of 40-95 ℃, then washing with deionized water, and filtering;
step 4): dipping the product exchanged in the step 3) in a rhenium salt solution with a liquid-solid ratio of 1.0-3.0 for 2-24 hours at a dipping temperature of 25-95 ℃, and then filtering and drying;
step 5): activating the dried product in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst;
the hydrogen type ZSM-5/EU-1 eutectic zeolite contains a ZSM-5 zeolite crystal phase and an EU-1 zeolite crystal phase at the same time, and is prepared by the following method:
step 1): adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring;
step 2): transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing with water to be neutral, performing suction filtration, and drying to obtain ZSM-5/EU-1 eutectic zeolite;
wherein the template agent is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide and triethylamine;
the silicon source is one or more of silica sol, water glass, white carbon black and silicic acid.
12. The method for preparing the aromatic hydrocarbon isomerization catalyst according to claim 11, wherein the calcination temperature in the step 1) is 300 to 400 ℃;
the roasting temperature in the step 2) is 350-450 ℃;
the ammonium salt solution in the step 3) is ammonium chloride and/or ammonium nitrate, and the exchange temperature is 60-80 ℃.
13. The method for preparing the aromatic hydrocarbon isomerization catalyst according to claim 11 or 12, characterized in that the liquid-solid ratio in the step 4) is 1.2 to 2.0, the impregnation temperature is 40 to 60 ℃, and the impregnation time is 6 to 16 hours;
in the step 5), the activation temperature is 300-400 ℃; the reduction temperature is 300-400 ℃.
14. A method for preparing an aromatic hydrocarbon isomerization catalyst, which is the method for preparing the catalyst according to any one of claims 1 to 10, and is characterized by comprising the following specific steps:
step 1): roasting hydrogen type ZSM-5/EU-1 eutectic zeolite in a low oxygen concentration atmosphere at the roasting temperature of 200-500 ℃ for 3-8 h;
step 2): uniformly mixing, molding and roasting the roasted eutectic zeolite and a binder, wherein the roasting temperature is 200-600 ℃, and the roasting time is 3-8 hours;
step 3): uniformly mixing, molding and roasting the roasted eutectic zeolite, rhenium oxide and a binder, wherein the roasting temperature is 200-600 ℃;
step 4): 0.1-0.5 g/mL of the catalyst calcined in the step 3)-1Performing ion exchange for 2-4 hours in the ammonium salt solution at the exchange temperature of 40-95 ℃, then washing with deionized water, and filtering;
step 5): activating the dried catalyst in the step 4) in an air atmosphere, wherein the activation temperature is 200-550 ℃, and the activation time is 2-8 hours; then reducing in a hydrogen atmosphere at the temperature of 200-550 ℃ for 2-8 hours to obtain the catalyst;
the hydrogen type ZSM-5/EU-1 eutectic zeolite contains a ZSM-5 zeolite crystal phase and an EU-1 zeolite crystal phase at the same time, and is prepared by the following method:
step 1): adding a certain amount of EU-1 zeolite into NaOH solution, uniformly stirring, adding a template agent, a silicon source and water, and uniformly stirring;
step 2): transferring the solution to a stainless steel kettle, crystallizing at 100-300 ℃ for 12-36 hours, taking out, cooling to room temperature, washing with water to be neutral, performing suction filtration, and drying to obtain ZSM-5/EU-1 eutectic zeolite;
wherein the template agent is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium bromide, tetrapropylammonium bromide and triethylamine;
the silicon source is one or more of silica sol, water glass, white carbon black and silicic acid.
15. The method for preparing the aromatic hydrocarbon isomerization catalyst according to claim 14, wherein the calcination temperature in the step 1) is 300 to 400 ℃;
the roasting temperature in the step 2) is 350-450 ℃;
the rhenium oxide in the step 3) is one or more of rhenium heptoxide, rhenium dioxide and rhenium trioxide; the roasting temperature is 350-450 ℃.
16. The method of preparing an aromatic isomerization catalyst as claimed in claim 15 wherein the rhenium oxide is rhenium heptoxide.
17. The method for preparing the aromatic hydrocarbon isomerization catalyst according to any one of claims 14 to 16, wherein the ammonium salt solution in the step 4) is ammonium chloride and/or ammonium nitrate, and the exchange temperature is 60 to 80 ℃;
in the step 5), the activation temperature is 300-400 ℃, and the reduction temperature is 300-400 ℃.
18. The use of an aromatics isomerization catalyst as claimed in any one of claims 1 to 9, wherein the raffinate oil from the aromatics complex is used as the feedstock for the dealkylation C8 aromatics isomerization reaction under the following conditions: the reaction temperature is 300-400 ℃, the hydrogen partial pressure is 0.70-1.5 MPa, and the volume ratio of hydrogen to oil is 100-500 v.v-1And the feeding weight hourly space velocity is 5-15 h-1。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102909064A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Catalyst for alkylation of toluene with methanol, and preparation method and applications thereof
CN106311321A (en) * 2015-07-03 2017-01-11 中国石油天然气股份有限公司 Catalyst containing EU-1/ZSM-5 eutectic zeolite as well as preparation method and application thereof
CN108273546A (en) * 2018-02-14 2018-07-13 彭杰 A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene
CN109704358A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 The synthetic method of EU-1/ZSM-5 composite molecular screen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2895283B1 (en) * 2005-12-22 2008-02-01 Inst Francais Du Petrole CATALYST COMPRISING EUO ZEOLITHE, 10MR ZEOLITE AND 12MR ZEOLITE AND ITS USE IN ISOMERIZATION OF AROMATIC C8 COMPOUNDS

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102909064A (en) * 2011-08-01 2013-02-06 中国石油化工股份有限公司 Catalyst for alkylation of toluene with methanol, and preparation method and applications thereof
CN106311321A (en) * 2015-07-03 2017-01-11 中国石油天然气股份有限公司 Catalyst containing EU-1/ZSM-5 eutectic zeolite as well as preparation method and application thereof
CN109704358A (en) * 2017-10-26 2019-05-03 中国石油化工股份有限公司 The synthetic method of EU-1/ZSM-5 composite molecular screen
CN108273546A (en) * 2018-02-14 2018-07-13 彭杰 A kind of preparation method of naphtha catalytic cracking catalyst for preparing propene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
EU-1/ZSM-5复合分子筛的合成与表征;闫萍等;《石油炼制与化工》;20110630;第42卷(第6期);第17-22页 *

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