WO2023045105A1 - 一种制备对二甲苯的方法 - Google Patents

一种制备对二甲苯的方法 Download PDF

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WO2023045105A1
WO2023045105A1 PCT/CN2021/137211 CN2021137211W WO2023045105A1 WO 2023045105 A1 WO2023045105 A1 WO 2023045105A1 CN 2021137211 W CN2021137211 W CN 2021137211W WO 2023045105 A1 WO2023045105 A1 WO 2023045105A1
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naphtha
reaction
methanol
hzsm
molecular sieve
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French (fr)
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于政锡
刘中民
杨越
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to JP2024516705A priority patent/JP7688231B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
    • C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/02—Monocyclic hydrocarbons
    • C07C15/067—C8H10 hydrocarbons
    • C07C15/08—Xylenes
    • 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
    • B01J29/40—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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • 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

Definitions

  • the present application relates to a method for preparing p-xylene, in particular to a method for preparing p-xylene by coupled conversion of methanol, naphtha and CO2 on a zeolite molecular sieve-based catalyst, which belongs to the field of petrochemical industry.
  • CO 2 carbon dioxide
  • CO 2 carbon dioxide
  • its concentration in the atmosphere is increasing day by day, which leads to the increasingly prominent greenhouse effect.
  • global CO2 emissions have reached 34 billion tons, and China's CO2 emissions have exceeded 10 billion tons.
  • China proposed that CO 2 emissions should peak before 2030 and strive to achieve carbon neutrality before 2060. Therefore, the recovery, fixation and resource utilization of CO2 have become a problem that countries all over the world pay close attention to. From the perspective of resources, CO 2 is the cheapest carbon resource in the world.
  • Aromatics represented by triphenyls are basic chemical raw materials. Among them, p-xylene is the most concerned product among aromatics. The market is huge and heavily dependent on imports. In 2019, the output of p-xylene was 13.46 million tons, the import volume reached 15.94 million tons, and the foreign dependence was 52%. Industrially, p-xylene is mainly produced from naphtha through catalytic reforming and aromatics combined unit. There are many steps, complicated process, and huge investment. Therefore, a huge part of aromatics comes from naphtha-to-aromatics technology.
  • CN108160104A discloses a catalyst for hydrogenation of carbon dioxide to produce aromatics and its preparation method and application. It adopts the nano metal oxide & ZSM-5 molecular sieve catalyst mixed by mechanical mixing, grinding mixing or ball milling, and the C5 + content in the carbon dioxide hydrogenation product reaches 80 %, and the selectivity of aromatics reaches over 70%.
  • CN107840778A discloses a method for preparing aromatics by hydrogenation of carbon dioxide under the action of a composite catalyst.
  • the composite catalyst is composed of an iron-based catalyst for hydrogenation of carbon dioxide to produce low-carbon olefins as the first component, and mainly plays the role of olefin aromatization Metal-modified or non-modified molecular sieves are mixed.
  • the conversion rate of CO 2 is 33%, and the selectivity of C 5+ hydrocarbons can reach 65%, of which aromatics account for 63% of C 5+ hydrocarbons.
  • CO2 is first activated under the action of metal oxides, and then reacts with hydrogen to form intermediate components that undergo carbon chain growth, transfer, and ring formation under the action of molecular sieves to generate aromatic hydrocarbons.
  • the above researches are all about CO2 hydrogenation to produce liquid hydrocarbons or aromatics.
  • the source of hydrogen is also a key issue restricting its industrial application.
  • This application provides a new technical route for producing aromatics by using CO 2 , that is, using naphtha as a raw material and coupling with CO 2 to produce aromatics, which provides a new way for the production of aromatics and large-scale utilization of CO 2 .
  • a method for preparing p-xylene is provided.
  • the method can not only prepare xylene, but also can obtain benzene and toluene simultaneously, and the benzene and toluene can be recycled as reaction raw materials.
  • a method for preparing p-xylene the raw materials containing methanol, naphtha and CO2 are passed through a reactor equipped with a catalyst to react to generate p-xylene.
  • reaction conditions reaction temperature 450-650°C, reaction pressure 0.1-3.5MPa, naphtha weight space velocity 0.1-5h -1 , CO 2 weight space velocity 0.1-3h -1 , methanol weight space velocity Speed 0.1 ⁇ 5h -1 .
  • reaction conditions reaction temperature 500-600°C, reaction pressure 0.1-3MPa, naphtha weight space velocity 0.5-2h -1 , CO 2 weight space velocity 0.5-2h -1 , methanol weight space velocity 0.5 ⁇ 2h -1 .
  • the reaction temperature is 500-600°C
  • the reaction pressure is 0.1-1MPa
  • the naphtha weight space velocity is 0.5-2h -1
  • the CO 2 weight space velocity is 0.5-2h -1
  • the methanol weight space velocity is 0.5-2h -1 .
  • reaction temperature is independently selected from any value among 450°C, 480°C, 500°C, 520°C, 550°C, 570°C, 600°C, 620°C, 650°C or any range between them.
  • reaction pressure is independently selected from any value among 0.1MPa, 0.15MPa, 0.2MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3MPa or any range between them.
  • the naphtha weight space velocity is independently selected from 0.1h ⁇ 1 , 0.2h ⁇ 1 , 0.5h ⁇ 1 , 0.7h ⁇ 1 , 1h ⁇ 1 , 1.2h ⁇ 1 , 1.5h ⁇ 1 , 2h ⁇ 1 Any value among 1 , 2.5h -1 , 3h -1 , 3.5h -1 , 4h -1 , 4.5h -1 , 5h -1 or any range value between them.
  • the CO gravimetric space velocity is independently selected from 0.1h ⁇ 1 , 0.2h ⁇ 1 , 0.5h ⁇ 1 , 0.7h ⁇ 1 , 1h ⁇ 1 , 1.2h ⁇ 1 , 1.5h ⁇ 1 , 2h ⁇ 1 , 2.5h -1 , any value in 3h -1 or any range value between them.
  • the methanol weight space velocity is independently selected from 0.1h ⁇ 1 , 0.2h ⁇ 1 , 0.5h ⁇ 1 , 0.7h ⁇ 1 , 1h ⁇ 1 , 1.2h ⁇ 1 , 1.5h ⁇ 1 , 2h ⁇ 1 , Any value among 2.5h -1 , 3h -1 , 3.5h -1 , 4h -1 , 4.5h -1 , 5h -1 or any value in the range between the two.
  • the usage ratio of CO 2 , naphtha and methanol is 0.3-2:1:0.3-2.
  • the usage ratio of CO 2 , naphtha and methanol is 0.3-1.5:1:0.3-1.5.
  • the usage ratio of CO 2 , naphtha and methanol is 0.5-1.0:1:0.5-1.0.
  • the usage ratio of CO 2 , naphtha and methanol is 1:3:2.
  • the usage ratio of CO 2 , naphtha and methanol is 0.8:1:0.6.
  • the usage ratio of CO 2 , naphtha and methanol is 0.8:1:1.2.
  • the usage ratio of CO 2 , naphtha and methanol is 1.5:1:1.5.
  • the components containing benzene and toluene in the mixture obtained from the reaction are separated from the obtained mixture, returned to the reaction system, and co-feed with the raw material on the catalyst to generate p-xylene.
  • the recycling of raw materials is realized by separating the components containing benzene and toluene in the mixture obtained from the reaction, that is, returning the components containing benzene and toluene in the by-products to the reaction system.
  • the catalyst is an acidic molecular sieve.
  • the acidic molecular sieve is HZSM-5 zeolite molecular sieve.
  • the silicon-aluminum ratio of the HZSM-5 zeolite molecular sieve is not the main factor affecting the catalytic activity, and the commonly used silicon-aluminum ratio Si/Al is sufficient.
  • the HZSM-5 zeolite molecular sieve is a metal-modified HZSM-5 zeolite molecular sieve.
  • the metal used for metal modification is selected from at least one of La, Zn, Ga, Fe, Mo, and Cr.
  • the HZSM-5 zeolite molecular sieve is HZSM-5 zeolite molecular sieve modified by metal and silylating agent.
  • the HZSM-5 zeolite molecular sieve modified by metal modification and silylating agent means that the HZSM-5 zeolite molecular sieve is modified by metal and then modified by silylating agent.
  • the silylating agent used for modification of the silylating agent is selected from at least one of the compounds having the following chemical formula:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from at least one of C 1-10 alkyl and C 1-10 alkoxy.
  • At least one of R 1 , R 2 , R 3 and R 4 is selected from C 1-10 alkoxy groups.
  • the silylating agent is selected from tetraethyl silicate and/or tetramethyl silicate.
  • the preparation step of the catalyst is also included:
  • the HZSM-5 zeolite molecular sieve is placed in the metal salt solution, impregnated, dried and calcined to obtain the metal-modified HZSM-5 zeolite molecular sieve.
  • the metal modification method includes: placing the HZSM-5 zeolite molecular sieve in a metal salt solution, impregnating, drying, and calcining to obtain the metal-modified HZSM-5 zeolite molecular sieve.
  • the impregnation conditions an immersion temperature of 60-100° C., and an immersion time of 2-10 hours.
  • the impregnation conditions an immersion temperature of 70-90° C., and an immersion time of 4-8 hours.
  • the immersion temperature is independently selected from any value among 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C or any range between them.
  • the immersion time is independently selected from any value in 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or a range value between any two.
  • the solid-to-liquid ratio of the HZSM-5 zeolite molecular sieve and the metal salt solution is 1:20 ⁇ 1:1.
  • the solid-to-liquid ratio refers to a mass ratio
  • the solid-to-liquid ratio of the HZSM-5 zeolite molecular sieve and the metal salt solution is 1:10 ⁇ 1:1.
  • the solid-to-liquid ratio of the HZSM-5 zeolite molecular sieve and the metal salt solution is independently selected from 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4 , 1:3, 1:2, 1:1 any value or any range value between them.
  • the metal salt is a soluble metal salt corresponding to the metal used for metal modification.
  • the soluble metal salt may be nitrate, sulfate, etc. corresponding to the metal used for metal modification.
  • metal used for metal modification such as zinc nitrate, gallium nitrate, lanthanum nitrate, chromium nitrate, etc.
  • the drying conditions are: drying in an air atmosphere at 100-150°C.
  • the firing conditions are: firing in an air atmosphere at 500-700°C.
  • the preparation of the catalyst also includes the following steps: contacting the material containing the silylating agent with the metal-modified HZSM-5 zeolite molecular sieve, purging with inert gas, and roasting to obtain the metal Modification and silylating agent modified HZSM-5 zeolite molecular sieve.
  • the method for modifying the silylating agent includes: contacting the material containing the silylating agent with the metal-modified HZSM-5 zeolite molecular sieve, purging with inert gas, and roasting to obtain the metal-modified and HZSM-5 zeolite molecular sieve modified by silylating agent.
  • the temperature of the contact treatment is 250-450°C.
  • the temperature of the contact treatment is 300-400°C.
  • the gravimetric space velocity of the silylating agent is 0.02 ⁇ 0.5 h ⁇ 1 .
  • the gravimetric space velocity of the silylating agent is 0.05 ⁇ 0.4 h ⁇ 1 .
  • the temperature of the contact treatment is 300°C.
  • the gravimetric space velocity of the silylating agent is 0.2h -1 .
  • the inert gas is at least one selected from nitrogen, helium, and argon.
  • the temperature of the contact treatment is independently selected from any value in 250°C, 270°C, 300°C, 320°C, 350°C, 370°C, 400°C, 420°C, 450°C or any range between the two value.
  • the gravimetric space velocity of the silylating agent is independently selected from 0.02h -1 , 0.05h -1 , 0.1h -1 , 0.15h -1 , 0.2h -1 , 0.25h -1 , 0.3h -1 Any value among 1 , 0.35h -1 , 0.4h -1 , 0.45h -1 , 0.5h -1 or any range value between them.
  • the calcination condition is: calcination with air at a temperature of 400° C. to 650° C.
  • the reactor is a fixed bed reactor, a fluidized bed reactor or a moving bed reactor.
  • the naphtha is selected from at least one of hydrocracked naphtha, catalytic cracked naphtha, raffinate, top oil, and direct coal liquefaction naphtha.
  • the carbon number distribution range of the naphtha hydrocarbons is C 4 -C 12 .
  • a process flow for preparing p-xylene comprising: feeding the raw materials containing naphtha, CO and methanol to the reaction system, and contacting the catalyst to obtain the mixture A,
  • the mixture A enters the first separation system, and is separated to obtain C 5+ components
  • the C 5+ components enters the second separation system, and is separated to obtain p-xylene.
  • the C5 + component enters the second separation system, separates to obtain a component containing benzene and toluene, and co-feeds the component containing benzene and toluene to the reaction with the feedstock containing naphtha, CO2 and methanol system.
  • a kind of preparation method of the catalyst that is used for methanol, naphtha and CO Raw material prepares p-xylene, comprising:
  • the HZSM-5 zeolite molecular sieve is placed in the metal salt solution, impregnated, dried and calcined to obtain the metal-modified HZSM-5 zeolite molecular sieve.
  • a kind of preparation method of the catalyst that is used for methanol, naphtha and CO Raw material prepares p-xylene, comprising:
  • a method for preparing p-xylene comprising the steps of:
  • HZSM-5 zeolite molecular sieve placing the HZSM-5 zeolite molecular sieve in a metal salt solution, impregnating, drying, and roasting to obtain the metal-modified HZSM-5 zeolite molecular sieve;
  • step of preparing catalyst in step (s1) also includes:
  • the material containing the silylating agent is contacted with the metal-modified HZSM-5 zeolite molecular sieve, purged with an inert gas, and calcined to obtain the metal-modified and silylating agent-modified HZSM-5 zeolite molecular sieve.
  • the given data range is selected from any value in the range, and includes the endpoint value of the range.
  • C 1-10 in C 1-10 alkyl and C 1-10 alkoxy means that the total number of carbon atoms in the alkyl or alkoxy is 1-10.
  • the method provided by this application utilizes naphtha and CO coupling to prepare p-xylene, methanol is added to the raw material, and the components containing benzene and toluene in the by-products are returned to the reaction system, realizing the recycling of raw materials , has extremely high economic benefits.
  • the method for preparing p-xylene provided by the application has simple technique and strong implementability, can greatly improve the selectivity and yield of p-xylene, has important application value, and provides a great opportunity for large-scale utilization of CO A new path.
  • Fig. 1 is a schematic diagram of the process flow for preparing p-xylene.
  • the raw materials and catalysts in the examples of the present application were purchased through commercial channels and used directly without treatment, and the instruments and equipment used used the scheme and parameters recommended by the manufacturer.
  • the inner diameter of the fixed bed reactor is 1.5 cm.
  • FIG. 1 The process flow diagram of the method for preparing p-xylene provided by the present application is shown in FIG. 1 .
  • Fig. 1 first feed the raw material containing naphtha, CO2 and methanol into the reaction system, and make the raw material containing naphtha, CO2 and methanol contact with the catalyst in the reaction system to react to obtain mixture A.
  • Mixture A enters the first separation system, where other components and C5 + components are separated.
  • the C 5+ components enter the second separation system, and the products containing benzene and toluene components, p-xylene and other C 5+ components are separated.
  • the components containing benzene and toluene are pumped back to the reaction system to generate p-xylene, which is finally separated.
  • the type of naphtha is coal direct liquefaction naphtha, and its specific composition is as shown in the following table:
  • Embodiment 1 The preparation of HZSM-5 molding molecular sieve sample for fixed bed
  • Molecular sieve particles denoted as FX ⁇ HZSM ⁇ 5.
  • Immerse at 90°C for 4 hours drain and dry at 120°C for 4 hours in an air atmosphere, and then bake the [La]HZSM-5 molecular sieve sample in an air atmosphere at 550°C for 4 hours. Crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 meshes, which are denoted as FX-[La]HZSM-5.
  • mass ratio i.e. solid-to-liquid ratio
  • the 100g [Zn]HZSM-5 molecular sieve sample prepared in Example 2 is mixed with an amorphous binder containing aluminum or silicon and spray-dried to form, and the specific steps are:
  • [Zn]HZSM-5 molecular sieve sample, pseudo-boehmite, silica sol, xanthan gum (biological glue) and water were mixed evenly, and the slurry was obtained through beating, rubber milling, and defoaming; the components in the slurry The parts by weight are:
  • the resulting slurry was spray-dried to obtain a microsphere particle sample with a particle size distribution of 20-100 ⁇ m; after the microsphere particle sample was roasted in a muffle furnace at 550 °C for 3 hours, a [Zn]HZSM-5 particle with a wear index of 1.2 was obtained.
  • Shaped molecular sieves are denoted as FL ⁇ [Zn]HZSM ⁇ 5.
  • the reaction conditions are as follows: 5 grams of the FX-[Zn]HZSM-5 catalyst prepared in Example 2 were loaded into a fixed-bed reactor, and first treated with 50ml/min nitrogen at 550°C for 1 hour.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Example 10 The operation was the same as in Example 10, and a fixed-bed catalyst for the coupled conversion of naphtha and CO 2 to produce benzene, toluene and p-xylene was obtained, which was named FXNCC-1.
  • Benzene and toluene in the reaction product are formulated as raw materials, and feed with a micro-feed pump (equal to methanol, naphtha and CO).
  • the reaction product is separated from benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 4.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX-[Ga]HZSM-5 catalysts prepared in Example 3 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then under nitrogen The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Example 12 The operation was the same as that in Example 12, and a fixed-bed catalyst for producing benzene, toluene, and p-xylene by coupled conversion of naphtha and CO 2 was obtained, which was named FXNCC-2.
  • Benzene and toluene composition in the reaction product are formulated as raw materials, and are fed with a micro-feed pump (equal to methanol, naphtha and CO).
  • the reaction product is separated from benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 6.
  • Catalyst for on-line preparation of naphtha and coupled conversion of CO2 to p-xylene in a micro-fixed-bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX-[La]HZSM-5 catalysts prepared in Example 4 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Example 14 The operation was the same as that in Example 14, and a fixed-bed catalyst for producing p-xylene by coupled conversion of naphtha and CO2 was obtained, which was named FXNCC-3.
  • Benzene, toluene composition in the reaction product is formulated as raw material, and feeds with micro-feed pump (equal to methanol, naphtha and CO).
  • micro-feed pump equal to methanol, naphtha and CO
  • the reaction product is separated out benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 8.
  • Catalyst for on-line preparation of naphtha and coupled conversion of CO2 to p-xylene in a micro-fixed-bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX-[Fe]HZSM-5 catalysts prepared in Example 5 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Example 16 The operation was the same as that in Example 16, and a fixed-bed catalyst for producing p-xylene through coupled conversion of naphtha and CO2 was obtained, which was named FXNCC-4.
  • Benzene and toluene in the reaction product are formulated as raw materials, and are fed with a micro-feed pump (equal to methanol, naphtha and CO).
  • the reaction product is separated from benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 10.
  • Catalyst for on-line preparation of naphtha and coupled conversion of CO2 to p-xylene in a micro-fixed-bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX-[Cr]HZSM-5 catalyst prepared in Example 6 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Example 18 The operation was the same as that in Example 18, and a fixed-bed catalyst for preparing p-xylene through coupled conversion of naphtha and CO2 was obtained, which was named FXNCC-5.
  • Benzene, toluene composition in the reaction product is formulated as raw material, and feeds with micro-feed pump (equal to methanol, naphtha and CO).
  • micro-feed pump equal to methanol, naphtha and CO
  • the reaction product is separated out benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 12.
  • Catalysts for on-line preparation of naphtha and coupled conversion of CO2 to p-xylene in a miniature fixed fluidized bed reactor The conditions for preparing the catalyst online are as follows: 10 grams of the FL-[Zn]HZSM-5 catalyst prepared in Example 7 are packed into a fixed fluidized bed reactor, and first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The temperature was lowered to 300° C. under a nitrogen atmosphere. Under nitrogen atmosphere (mass flow meter control, 200ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • the feed was stopped after 75 minutes of feeding, purged with nitrogen, the temperature was raised to 550 ° C, and roasted for 4 hours in an air atmosphere to prepare a fixed-bed catalyst for the coupled conversion of naphtha and CO 2 to p-xylene, named FLNCC-1.
  • Example 20 The operation was the same as that in Example 20, and a fixed-bed catalyst for producing p-xylene through coupled conversion of naphtha and CO2 was obtained, named FLNCC-1.
  • the benzene in the reaction product, toluene composition is formulated as raw material, and feeds with micro-feeding pump (equal to methanol, naphtha and CO).
  • micro-feeding pump equal to methanol, naphtha and CO
  • the reaction product is separated out benzene and toluene, and pumped back into the fixed-bed reactor with a micro-feed pump).
  • the reaction products were analyzed by online Agilent7890 gas chromatography, and samples were taken for analysis after 30 minutes of reaction. The reaction results are shown in Table 14.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 400°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.4h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for preparing the catalyst online are as follows: 5 grams of FX ⁇ [Zn]HZSM ⁇ 5 catalysts prepared in Example 2 are packed into a fixed bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.05h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for online preparation of catalyst are as follows: 5 grams of FX-[Zn]HZSM-5 catalyst prepared in Example 2 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.
  • Catalysts for on-line preparation of naphtha and CO2 coupled conversion to benzene, toluene and p-xylene in a micro-fixed bed reactor The conditions for online preparation of catalyst are as follows: 5 grams of FX-[Zn]HZSM-5 catalyst prepared in Example 2 are packed into a fixed-bed reactor, first treated with 50ml/min nitrogen at 550°C for 1 hour, and then The atmosphere was cooled down to 300°C. Under nitrogen atmosphere (mass flow meter control, 100ml/min), tetraethyl silicate is pumped into the reactor, the weight space velocity of tetraethyl silicate is 0.2h -1 , normal pressure.

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Abstract

本申请公开了一种制备对二甲苯的方法，将含有甲醇、石脑油和CO 2的原料通过装有催化剂的反应器，反应，生成对二甲苯。通过加入甲醇，调节了产品分布，显著的提高了对二甲苯的选择性。另外，将芳烃产品中含有苯和甲苯的组分返回反应系统，并与所述原料共进料反应生成对二甲苯，实现了原料的循环利用，具有极高的经济效益。该方法工艺简单，可实施性强，可大幅提高对二甲苯的选择性和收率，具有重要的应用价值，为CO 2的大规模利用提供了一条新的途径。

Description

一种制备对二甲苯的方法 技术领域
本申请涉及一种制备对二甲苯的方法，尤其是涉及一种在沸石分子筛基催化剂上甲醇、石脑油和CO 2耦合转化制对二甲苯的方法，属于石油化工领域。
背景技术
随着现代工业的发展，二氧化碳(CO 2)作为主要的温室气体，其在大气中的浓度与日俱增，从而导致温室效应的日益凸显。2020年，全球CO 2排放量已达340亿吨，我国CO 2排放量超过100亿吨。2020年，在第75届联合国大会期间，中方提出CO 2排放力争于2030年前达到峰值，努力争取2060年前实现碳中和。因此，CO 2的回收、固定和资源化利用，已成为世界各国密切关注的问题。从资源角度，CO 2是世界上最为廉价的碳一资源。
以三苯(苯、甲苯、对二甲苯)为代表的芳烃是基础化工原料，其中，对二甲苯是芳烃中最受关注的产品，市场规模庞大，且大量依赖进口。2019年，对二甲苯产量1346万吨，进口量达1594万吨，对外依存度52％。工业上，对二甲苯主要由石脑油通过催化重整、芳烃联合装置来生产，步骤繁多，过程复杂，投资巨大，且因此巨大部分芳烃都来自石脑油制芳烃技术。其中，石脑油催化重整生产的芳烃占石油基芳烃量的80％。因此，大力发展CO 2利用技术，特别将CO 2转化为芳烃，具有重要的经济和社会意义，一方面能够解决我国化学品不足的局面，另一方面由于芳烃产品市场规模大，能够较大规模的实现CO 2减排。
CN108160104A公开了一种二氧化碳加氢制芳烃的催化剂及其制备方法和应用，采用机械混合、研磨混合或球磨混合的纳米金属氧化物&ZSM-5分子筛催化剂，二氧化碳加氢产物中C 5+含量达80％，芳烃选择性达70％以上。CN107840778A公开了一种在复合催化剂作用下二氧化碳加氢制取芳烃的方法，所述的复合催化剂由铁基二氧化碳加氢制低碳烯烃催化剂作为第一组分，与主要起到烯烃芳构化作用的金属改性或不改性分子筛混合而成，该复合催化剂作用下CO 2转化率为33％，C 5+烃选择性可以达到65％，其中芳烃占C 5+烃的63％。研究表明，CO 2首先在金属氧化物作用下被活化，然后与氢气反应生成的中间组分在分子筛作用下经历碳链增长、转移、成环等过程生成芳烃。上述研究都是通过CO 2加氢制液态烃或芳烃，除了技术指标，氢气的来源也是制约其工业应用的关键问题。
发明内容
本申请提供一种新的利用CO 2制芳烃的技术路线，即利用石脑油作为原料，与CO 2耦合制芳烃，为芳烃生产和CO 2大规模利用提供了新的途径。
根据本申请的第一方面，提供一种制备对二甲苯的方法。该方法不仅可以制备得到二甲苯，同时还可以得到苯、甲苯，苯和甲苯可以作为反应原料进行循环利用。
一种制备对二甲苯的方法，将含有甲醇、石脑油和CO 2的原料通过装有催化剂的反应器，反应，生成对二甲苯。
可选地，所述反应的条件：反应温度450～650℃，反应压力0.1～3.5MPa，石脑油重量空速0.1～5h -1，CO 2重量空速0.1～3h -1，甲醇重量空速0.1～5h -1。
可选地，所述反应的条件：反应温度500～600℃，反应压力0.1～3MPa，石脑油重量空速0.5～2h -1，CO 2重量空速0.5～2h -1，甲醇重量空速0.5～2h -1。
可选地，反应温度500～600℃，反应压力0.1～1MPa，石脑油重量空速0.5～2h -1，CO 2重量空速0.5～2h -1，甲醇重量空速0.5～2h -1。
可选地，反应温度独立地选自450℃、480℃、500℃、520℃、550℃、570℃、600℃、620℃、650℃中的任意值或任意两者之间的范围值。
可选地，反应压力独立地选自0.1MPa、0.15MPa、0.2MPa、0.5MPa、1.0MPa、1.5MPa、2.0MPa、2.5MPa、3MPa中的任意值或任意两者之间的范围值。
可选地，石脑油重量空速独立地选自0.1h -1、0.2h -1、0.5h -1、0.7h -1、1h -1、1.2h -1、1.5h -1、2h -1、2.5h -1、3h -1、3.5h -1、4h -1、4.5h -1、5h -1中的任意值或任意两者之间的范围值。
可选地，CO 2重量空速独立地选自0.1h -1、0.2h -1、0.5h -1、0.7h -1、1h -1、1.2h -1、1.5h -1、2h -1、2.5h -1、3h -1中的任意值或任意两者之间的范围值。
可选地，甲醇重量空速独立地选自0.1h -1、0.2h -1、0.5h -1、0.7h -1、1h -1、1.2h -1、1.5h -1、2h -1、2.5h -1、3h -1、3.5h -1、4h -1、4.5h -1、5h -1中的任意值或任意两者之间的范围值。
可选地，CO 2、石脑油和甲醇的用量比为0.3～2：1：0.3～2。
可选地，CO 2、石脑油和甲醇的用量比为0.3～1.5：1：0.3～1.5。
可选地，CO 2、石脑油和甲醇的用量比为0.5～1.0：1：0.5～1.0。
可选地，CO 2、石脑油和甲醇的用量比为1：3：2。
可选地，CO 2、石脑油和甲醇的用量比为0.8：1：0.6。
可选地，CO 2、石脑油和甲醇的用量比为0.8：1：1.2。
可选地，CO 2、石脑油和甲醇的用量比为1.5：1：1.5。
可选地，将反应得到的混合物中含有苯和甲苯的组分从所得混合物中分离出来，并返回反应系统，并与所述原料在所述催化剂上共进料反应生成对二甲苯。
本申请中，通过将反应得到的混合物中含有苯和甲苯的组分从所得混合物中分离出来，即把副产品中的含有苯和甲苯的组分返回反应系统，实现了原料的循环利用。
可选地，所述催化剂为酸性分子筛。
可选地，所述酸性分子筛为HZSM-5沸石分子筛。
可选地，所述HZSM-5沸石分子筛的硅铝比Si/Al＝10～50。
可选地，所述HZSM-5沸石分子筛的硅铝比Si/Al＝15。
本申请中，HZSM-5沸石分子筛的硅铝比不是影响催化活性的主要因素，选用通常用的硅铝比Si/Al即可。
可选地，所述HZSM-5沸石分子筛为金属改性的HZSM-5沸石分子筛。
可选地，所述金属改性用的金属选自La、Zn、Ga、Fe、Mo、Cr中的至少一种。
可选地，所述HZSM-5沸石分子筛为金属改性和硅烷化试剂改性的HZSM-5沸石分子筛。
本申请中，金属改性和硅烷化试剂改性的HZSM-5沸石分子筛是指对HZSM-5沸石分子筛进行金属改性后继续进行硅烷化试剂改性。
可选地，所述硅烷化试剂改性用的硅烷化试剂选自具有以下化学式的化合物中的至少一种：
Figure PCTCN2021137211-appb-000001
其中R 1、R 2、R 3和R 4各自独立地选自C 1-10的烷基、C 1-10的烷氧基中的至少一种。
可选地，所述R 1、R 2、R 3和R 4中的至少一个选自C 1-10的烷氧基。
可选地，所述硅烷化试剂选自硅酸四乙酯和\或硅酸四甲酯。
可选地，在反应前，还包括催化剂的制备步骤：
将HZSM-5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM-5沸石分子筛。
可选地，所述金属改性的方法包括：将HZSM-5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM-5沸石分子筛。
可选地，所述浸渍的条件：浸渍温度60～100℃，浸渍时间2～10小时。
可选地，所述浸渍的条件：浸渍温度70～90℃，浸渍时间4～8小时。
可选地，浸渍温度独立地选自60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃中的任意值或任意两者之间的范围值。
可选地，浸渍时间独立地选自2h、3h、4h、5h、6h、7h、8h、9h、10h中的任意值或任意两者之间的范围值。
可选地，所述HZSM-5沸石分子筛和金属盐溶液的固液比为1：20～1：1。
其中，固液比指的是质量比。
可选地，所述HZSM-5沸石分子筛和金属盐溶液的固液比为1：10～1：1。
可选地，所述HZSM-5沸石分子筛和金属盐溶液的固液比独立地选自1：10、1：9、1：8、1：7、1：6、1：5、1：4、1：3、1：2、1：1中的任意值或任意两者之间的范围值。
可选地，所述金属盐为金属改性用的金属对应的可溶性金属盐。
本申请中，可溶性金属盐可为金属改性用的金属对应的硝酸盐、硫酸盐等。如硝酸锌、硝酸镓、硝酸镧、硝酸铬等。
可选地，所述金属改性的方法中，干燥的条件为：在空气气氛、100～150℃条件下干燥。
可选地，所述金属改性的方法中，焙烧的条件为：在空气气氛、500～700℃下焙烧。
可选地，，在反应前，催化剂的制备还包括以下步骤：将含有硅烷化试剂的物料和金属改性后的HZSM-5沸石分子筛接触处理，非活性气体吹扫，焙烧，得到所述金属改性和硅烷化试剂改性的HZSM-5沸石分子筛。
可选地，所述硅烷化试剂改性的方法包括：将含有硅烷化试剂的物料和金属改性后的HZSM-5沸石分子筛接触处理，非活性气体吹扫，焙烧，得到所述金属改性和硅烷化试剂改性的HZSM-5沸石分子筛。
可选地，所述接触处理的温度为250～450℃。
可选地，所述接触处理的温度为300～400℃。
可选地，所述硅烷化试剂的重量空速为0.02～0.5h -1。
可选地，所述硅烷化试剂的重量空速为0.05～0.4h -1。
可选地，所述接触处理的温度为300℃。
可选地，所述硅烷化试剂的重量空速为0.2h -1。
可选地，所述非活性气体选自氮气、氦气、氩气中的至少一种。
可选地，接触处理的温度独立地选自250℃、270℃、300℃、320℃、350℃、370℃、400℃、420℃、450℃中的任意值或任意两者之间的范围值。
可选地，所述硅烷化试剂的重量空速独立地选自0.02h -1、0.05h -1、0.1h -1、0.15h -1、0.2h -1、0.25h -1、0.3h -1、0.35h -1、0.4h -1、0.45h -1、0.5h -1中的任意值或任意两者之间的范围值。
可选地，所述硅烷化试剂改性的方法中，焙烧的条件为：400℃～650℃温度下通入空气焙烧。
可选地，所述反应器为固定床反应器、流化床反应器或移动床反应器。
可选地，所述石脑油选自加氢裂化石脑油、催化裂化石脑油、抽余油、拔头油、煤直接液化石脑油中的至少一种。
可选地，所述石脑油的烃类的碳数分布范围为C 4-C 12。
作为本申请的另一方面，还提供了一种制备对二甲苯的工艺流程，包括：将含有石脑油、CO 2和甲醇的原料进料至反应系统，和催化剂接触反应，得到混合物A，混合物A进入第一分离系统，分离得到C 5+组分，C 5+组分进入第二分离系统，分离得到对二甲苯。
可选地，C 5+组分进入第二分离系统，分离得到含有苯和甲苯的组分，将含有苯和甲苯的组分与含有石脑油、CO 2和甲醇的原料共进料至反应系统。
一种用于甲醇、石脑油和CO 2的原料制备对二甲苯的催化剂的制备方法，包括：
将HZSM-5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM-5沸石分子筛。
一种用于甲醇、石脑油和CO 2的原料制备对二甲苯的催化剂的制备方法，包括：
(1)将HZSM‐5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM‐5沸石分子筛；
(2)将含有硅烷化试剂的物料和金属改性后的HZSM‐5沸石分子筛接触处理，非活性气体吹扫，焙烧，得到所述金属改性和硅烷化试剂改性的HZSM‐5沸石分子筛。
一种制备对二甲苯的方法，包括如下步骤：
(S1)制备催化剂的步骤；
将HZSM‐5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM‐5沸石分子筛；
(S2)将含有甲醇、石脑油和CO 2的原料通过装有(S1)步骤制备得到的催化剂的反应器，反应，生成对二甲苯。
可选地，步骤(s1)制备催化剂的步骤还包括：
将含有硅烷化试剂的物料和金属改性后的HZSM‐5沸石分子筛接触处理，非活性气体吹扫，焙烧，得到所述金属改性和硅烷化试剂改性的HZSM‐5沸石分子筛。
具体的制备条件如上所述。
本申请中，如无特别说明，所给出的数据范围选自范围中的任意值，且包含范围的端点值。
本申请中，C 1-10的烷基、C 1-10的烷氧基中的C 1-10，是指烷基、烷氧基中的总碳原子数目为1-10。
本申请能产生的有益效果包括：
1)本申请所提供的利用石脑油和CO 2耦合来制备对二甲苯的方法，通过加入甲醇，调节了产品分布，显著的提高了对二甲苯的选择性。
2)本申请所提供的利用石脑油和CO 2耦合来制备对二甲苯的方法，原料中加入甲醇，并将副产品中的含有苯和甲苯的组分返回反应系统，实现了原料的循环利用，具有极高的经济效益。
3)本申请所提供的制备对二甲苯的方法，工艺简单，可实施性强，可大幅提高对二甲苯的选择性和收率，具有重要的应用价值，为CO 2的大规模利用提供了一条新的途径。
附图说明
图1为制备对二甲苯的工艺流程示意图。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买，未经处理直接使用，所用仪器设备采用厂家推荐的方案和参数。
实施例中，固定床反应器内径为1.5cm。
本申请提供的制备对二甲苯的方法，工艺流程示意图如图1所示。
参见图1，首先将含有石脑油、CO 2和甲醇的原料进料至反应系统，使含有石脑油、CO 2和甲醇的原料在反应系统中与催化剂接触发生反应，得到混合物A。混合物A进入第一分离系统，分离得到其它组分和C 5+组分。C 5+组分进入第二分离系统，分离得到含有苯和甲苯的组分、对二甲苯和其它C 5+组分的产物。将含有苯和甲苯的组分泵送回反应系统以生成对二甲苯，最后分离对二甲苯。
在本申请的实施例中，石脑油的类型为煤直接液化石脑油，其具体组成为如下表所示：
煤直接液化石脑油的组成
碳数 正构烷烃 异构烷烃 环烷烃 芳烃
6 0.03 0.00 0.00 0.00
7 3.76 0.71 31.85 1.60
8 9.36 2.62 27.53 1.94
9 2.03 2.44 13.88 0.40
10 0.15 0.75 0.74 0.07
11 0.01 0.03 0.10 0.00
总计 15.34 6.55 74.10 4.01
实施例1固定床用HZSM‐5成型分子筛样品的制备
将100g HZSM‐5沸石分子筛原粉(南开大学催化剂厂，Si/Al＝15)在空气气氛、550℃下焙烧4小时后，压片成型并破碎、筛分得到40～60目粒径的成型分子筛颗粒，记为FX‐HZSM‐5。
实施例2固定床用锌改性HZSM‐5分子筛成型样品的制备
将100g HZSM‐5沸石分子筛(南开大学催化剂厂，Si/Al＝15)置于10wt％的硝酸锌水溶液中，HZSM‐5沸石分子筛与硝酸锌水溶液的质量比(即固液比)为1/10，在80℃条件浸渍6小时，沥干后在空气气氛、120℃条件下干燥4小时，然后在空气气氛、550℃下焙烧4小时后制得[Zn]HZSM‐5分子筛样品，压片成型并破碎、筛分得到40～60目粒径的成型分子筛颗粒，记为FX‐[Zn]HZSM‐5。
实施例3固定床用镓改性HZSM‐5分子筛成型样品的制备
将100g HZSM‐5沸石分子筛(南开大学催化剂厂，Si/Al＝15)置于10wt％的硝酸镓水溶液中，HZSM‐5沸石分子筛与硝酸镓水溶液的质量比(即固液比)为1/10，在80℃条件浸渍6小时，沥干后在空气气氛、120℃条件下干燥4小时，然后在空气气氛、550℃下焙烧4小时后[Ga]HZSM‐5分子筛样品，压片成型并破碎、筛分得到40～60目粒径的成型分子筛颗粒，记为FX‐[Ga]HZSM‐5。
实施例4固定床用镧改性HZSM‐5分子筛成型样品的制备
将100g HZSM‐5沸石分子筛(南开大学催化剂厂，Si/Al＝15)置于10wt％的硝酸镧水溶液中，HZSM‐5沸石分子筛与硝酸镧水溶液的质量比(即固液比)为1/10，在90℃条件浸渍4小时，沥干后在空气气氛、120℃条件下干燥4小时，然后在空气气氛、550℃下焙烧4小时后[La]HZSM‐5分子筛样品，压片成型并破碎、筛分得到40～60目粒径 的成型分子筛颗粒，记为FX‐[La]HZSM‐5。
实施例5固定床用铁改性HZSM‐5分子筛成型样品的制备
将100g HZSM‐5沸石分子筛(南开大学催化剂厂，Si/Al＝15)置于10wt％的硝酸铁水溶液中，HZSM‐5沸石分子筛与硝酸铁水溶液的质量比(即固液比)为1/10，在70℃条件浸渍8小时，沥干后在空气气氛、120℃条件下干燥4小时，然后在空气气氛、550℃下焙烧4小时后[Fe]HZSM‐5分子筛样品，压片成型并破碎、筛分得到40～60目粒径的成型分子筛颗粒，记为FX‐[Fe]HZSM‐5。
实施例6固定床用铬改性HZSM‐5分子筛成型样品的制备
将100g HZSM‐5沸石分子筛(南开大学催化剂厂，Si/Al＝15)置于10wt％的硝酸铬水溶液中，HZSM‐5沸石分子筛与硝酸铬水溶液的质量比(即固液比)为1/10，在70℃条件浸渍8小时，沥干后在空气气氛、120℃条件下干燥4小时，然后在空气气氛、550℃下焙烧4小时后[Cr]HZSM‐5分子筛样品，压片成型并破碎、筛分得到40～60目粒径的成型分子筛颗粒，记为FX‐[Cr]HZSM‐5。
实施例7流化床用锌改性HZSM‐5成型分子筛样品的制备
将实施例2制备的100g[Zn]HZSM‐5分子筛样品与含铝或硅的无定形粘结剂混合喷雾干燥成型，具体步骤为：
将[Zn]HZSM‐5分子筛样品、拟薄水铝石、硅溶胶、黄原胶(生物胶)和水混合均匀，经过打浆、胶磨、去泡得到浆料；浆料中各组分的重量份数为：
Figure PCTCN2021137211-appb-000002
所得浆料经喷雾干燥成型，得到粒径分布20～100μm的微球颗粒样品；将微球颗粒样品在马弗炉中550℃焙烧3小时后，得到磨损指数为1.2的[Zn]HZSM‐5成型分子筛，记为FL‐[Zn]HZSM‐5。
实施例8甲醇、石脑油和CO 2耦合转化制芳烃反应评价
在微型固定床反应装置上评价甲醇、石脑油和CO 2耦合转化制芳烃反应。反应条件如下：将5克实施例1中制备的FX‐HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时。然后，甲醇、石脑油和CO 2共进料；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝1:3:2，石脑油重量空速1.0h ‐1，CO 2重量空速0.33h ‐1，甲醇重量空速0.67h ‐1，反应压力1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表1所示。
表1实施例8催化剂反应评价结果
Figure PCTCN2021137211-appb-000003
Figure PCTCN2021137211-appb-000004
实施例9甲醇、石脑油和CO 2耦合转化制芳烃反应评价
在微型固定床反应装置上评价甲醇、石脑油和CO 2耦合转化制芳烃反应。反应条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时。然后，甲醇、石脑油和CO 2共进料；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表2所示。
表2实施例9催化剂反应评价结果
Figure PCTCN2021137211-appb-000005
实施例10甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表3所示。
表3实施例10催化剂反应评价结果
Figure PCTCN2021137211-appb-000006
Figure PCTCN2021137211-appb-000007
实施例11甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例10，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例10中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表4所示。
表4实施例11催化剂的反应评价结果
Figure PCTCN2021137211-appb-000008
实施例12甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例3中制备的FX‐[Ga]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐2。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表5所示。
表5实施例12催化剂反应评价结果
Figure PCTCN2021137211-appb-000009
实施例13甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例12，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐2。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例12中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表6所示。
表6实施例13催化剂的反应评价结果
Figure PCTCN2021137211-appb-000010
Figure PCTCN2021137211-appb-000011
实施例14甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例4中制备的FX‐[La]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐3。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表7所示。
表7实施例14催化剂反应评价结果
Figure PCTCN2021137211-appb-000012
Figure PCTCN2021137211-appb-000013
实施例15甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例14，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐3。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例14中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表8所示。
表8实施例15催化剂的反应评价结果
Figure PCTCN2021137211-appb-000014
实施例16甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例5中制备的FX‐[Fe]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐4。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表9所示。
表9实施例16催化剂反应评价结果
Figure PCTCN2021137211-appb-000015
Figure PCTCN2021137211-appb-000016
实施例17甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例16，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐4。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例16中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表10所示。
表10实施例17催化剂的反应评价结果
Figure PCTCN2021137211-appb-000017
实施例18甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例6中制备的FX‐[Cr]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐5。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表11所示。
表11实施例18催化剂反应评价结果
Figure PCTCN2021137211-appb-000018
实施例19甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例18，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FXNCC‐5。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例18中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表12所示。
表12实施例19催化剂的反应评价结果
Figure PCTCN2021137211-appb-000019
Figure PCTCN2021137211-appb-000020
实施例20甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
在微型固定流化床反应装置内在线制备石脑油和CO 2耦合转化制对二甲苯催化剂。在线制备催化剂的条件如下：将10克实施例7中制备的FL‐[Zn]HZSM‐5催化剂装入固定流化床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，200ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料75min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FLNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表13所示。
表13实施例20催化剂反应评价结果
Figure PCTCN2021137211-appb-000021
Figure PCTCN2021137211-appb-000022
实施例21甲醇、石脑油和CO 2耦合转化制对二甲苯催化剂的制备和反应评价
操作同实施例20，制得石脑油和CO 2耦合转化制对二甲苯固定床催化剂，命名为FLNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。根据实施例20中甲醇、石脑油和CO 2反应产物中的苯、甲苯组成配制成原料，并用微量进料泵进料(等同于将甲醇、石脑油和CO 2反应产物中分离出苯和甲苯，并用微量进料泵泵送回固定床反应器中)。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表14所示。
表14实施例21催化剂的反应评价结果
Figure PCTCN2021137211-appb-000023
对比例1石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油(质量比)＝0.8:1，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表15所示。
表15对比例1催化剂的反应性能评价
Figure PCTCN2021137211-appb-000024
Figure PCTCN2021137211-appb-000025
可以看出，当原料中没有甲醇时候，烃类产物组成中，对二甲苯含量为12.31％，和实施例10相比，因为甲醇的加入，对二甲苯含量提高到32.53％。因此，甲醇的加入大大提高了对二甲苯的选择性。
实施例22甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:1.2，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速1.2h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表16所示。
表16实施例22催化剂反应评价结果
Figure PCTCN2021137211-appb-000026
Figure PCTCN2021137211-appb-000027
可以看出，和实施例10相比，当甲醇的添加量增加的时候，烃类产物组成中，对二甲苯含量由32.53％提高到44.36％。进一步说明，甲醇的加入提高了对二甲苯的选择性。
实施例23甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至400℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐6。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表17所示。
表17实施例23催化剂反应评价结果
Figure PCTCN2021137211-appb-000028
实施例24甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.4h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下 焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐7。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表18所示。
表18实施例24催化剂反应评价结果
Figure PCTCN2021137211-appb-000029
实施例25甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.05h ‐1，常压。进料240min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐8。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表19所示。
表19实施例25催化剂反应评价结果
Figure PCTCN2021137211-appb-000030
Figure PCTCN2021137211-appb-000031
实施例26甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝0.8:1:0.6，石脑油重量空速1.0h ‐1，CO 2重量空速0.8h ‐1，甲醇重量空速0.6h ‐1，反应压力3MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表20所示。
表20实施例26催化剂反应评价结果
Figure PCTCN2021137211-appb-000032
Figure PCTCN2021137211-appb-000033
实施例27甲醇、石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂的制备和反应评价
在微型固定床反应装置内在线制备石脑油和CO 2耦合转化制苯、甲苯和对二甲苯催化剂。在线制备催化剂的条件如下：将5克实施例2中制备的FX‐[Zn]HZSM‐5催化剂装入固定床反应器中，先经50ml/min氮气在550℃下处理1小时，然后在氮气气氛下降温至300℃。在氮气气氛下(质量流量计控制，100ml/min)，将硅酸四乙酯泵入反应器，硅酸四乙酯的重量空速为0.2h ‐1，常压。进料60min后停止进料，用氮气吹扫，升温至550℃，在空气气氛下焙烧4小时，制得石脑油和CO 2耦合转化制苯、甲苯和对二甲苯固定床催化剂，命名为FXNCC‐1。
然后，在氮气气氛下调节温度至反应温度550℃；甲醇、石脑油原料用微量进料泵进料，CO 2流量用质量流量计控制，原料CO 2:石脑油:甲醇(质量比)＝1.5:1:1.5，石脑油重量空速1.0h ‐1，CO 2重量空速1.5h ‐1，甲醇重量空速1.5h ‐1，反应压力0.1MPa。反应产物通过在线Agilent7890气相色谱进行分析，反应30min时取样分析。反应结果如表21所示。
表21实施例27催化剂反应评价结果
Figure PCTCN2021137211-appb-000034
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (23)

  1. 一种制备对二甲苯的方法，其特征在于，将含有甲醇、石脑油和CO 2的原料通过装有催化剂的反应器，反应，生成对二甲苯。
  2. 根据权利要求1所述的方法，其特征在于，所述反应的条件：反应温度450～650℃，反应压力0.1～3.5MPa，石脑油重量空速0.1～5h ‐1，CO 2重量空速0.1～3h ‐1，甲醇重量空速0.1～5h ‐1。
  3. 根据权利要求1所述的方法，其特征在于，所述反应的条件：反应温度500～600℃，反应压力0.1～3MPa，石脑油重量空速0.5～2h ‐1，CO 2重量空速0.5～2h ‐1，甲醇重量空速0.5～2h ‐1。
  4. 根据权利要求1所述的方法，其特征在于，CO 2、石脑油和甲醇的用量比为0.3～2：1：0.3～2。
  5. 根据权利要求1所述的方法，其特征在于，CO 2、石脑油和甲醇的用量比为0.3～1.5：1：0.3～1.5。
  6. 根据权利要求1所述的方法，其特征在于，将反应得到的混合物中含有苯和甲苯的组分从所得混合物中分离出来，并返回反应系统，并与所述原料在所述催化剂上共进料反应生成对二甲苯。
  7. 根据权利要求1所述的方法，其特征在于，所述催化剂为酸性分子筛。
  8. 根据权利要求1所述的方法，其特征在于，所述酸性分子筛为HZSM‐5沸石分子筛。
  9. 根据权利要求1所述的方法，其特征在于，所述HZSM‐5沸石分子筛的硅铝比Si/Al＝10～50。
  10. 根据权利要求8所述的方法，其特征在于，所述HZSM‐5沸石分子筛为金属改性的HZSM‐5沸石分子筛。
  11. 根据权利要求10所述的方法，其特征在于，所述金属改性用的金属选自La、Zn、Ga、Fe、Mo、Cr中的至少一种。
  12. 根据权利要求8所述的方法，其特征在于，所述HZSM‐5沸石分子筛为金属改性和硅烷化试剂改性的HZSM‐5沸石分子筛。
  13. 根据权利要求12所述的方法，其特征在于，所述硅烷化试剂改性用的硅烷化试剂选自具有以下化学式的化合物中的至少一种：
    Figure PCTCN2021137211-appb-100001
    其中R 1、R 2、R 3和R 4各自独立地选自C 1‐10的烷基、C 1‐10的烷氧基中的至少一种。
  14. 根据权利要求13所述的方法，其特征在于，所述R 1、R 2、R 3和R 4中的至少一个选自C 1‐10的烷氧基。
  15. 根据权利要求13所述的方法，其特征在于，所述硅烷化试剂选自硅酸四乙酯和\或硅酸四甲酯。
  16. 根据权利要求1所述的方法，其特征在于，在反应前，还包括催化剂的制备步骤：
    将HZSM‐5沸石分子筛置于金属盐溶液中，浸渍，干燥，焙烧，得到所述金属改性的HZSM‐5沸石分子筛。
  17. 根据权利要求16所述的方法，其特征在于，所述浸渍的条件：浸渍温度60～100℃，浸渍时间2～10小时。
  18. 根据权利要求16所述的方法，其特征在于，所述HZSM‐5沸石分子筛和金属盐溶液的固液比为1：20～1：1。
  19. 根据权利要求16所述的方法，其特征在于，所述金属盐为金属改性用的金属对应的可溶性金属盐。
  20. 根据权利要求16所述的方法，其特征在于，在反应前，催化剂的制备还包括以下步骤：将含有硅烷化试剂的物料和金属改性后的HZSM‐5沸石分子筛接触处理，非活性气体吹扫，焙烧，得到所述金属改性和硅烷化试剂改性的HZSM‐5沸石分子筛。
  21. 根据权利要求20所述的方法，其特征在于，所述接触处理的温度为250～450℃。
  22. 根据权利要求20所述的方法，其特征在于，所述硅烷化试剂的重量空速为0.02～0.5h ‐1。
  23. 根据权利要求1所述的方法，其特征在于，所述反应器为固定床反应器、流化床反应器或移动床反应器。
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