WO2018195865A1 - 制甲苯、对二甲苯、低碳烯烃中至少一种的催化剂的原位制备方法及反应工艺 - Google Patents

制甲苯、对二甲苯、低碳烯烃中至少一种的催化剂的原位制备方法及反应工艺 Download PDF

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WO2018195865A1
WO2018195865A1 PCT/CN2017/082222 CN2017082222W WO2018195865A1 WO 2018195865 A1 WO2018195865 A1 WO 2018195865A1 CN 2017082222 W CN2017082222 W CN 2017082222W WO 2018195865 A1 WO2018195865 A1 WO 2018195865A1
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reaction
catalyst
xylene
toluene
methanol
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PCT/CN2017/082222
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English (en)
French (fr)
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刘中民
于政锡
朱书魁
杨越
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中国科学院大连化学物理研究所
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Priority to SG11201909968S priority Critical patent/SG11201909968SA/en
Priority to DE112017007489.4T priority patent/DE112017007489T5/de
Priority to RU2019134156A priority patent/RU2747308C1/ru
Priority to US16/608,818 priority patent/US11179714B2/en
Priority to JP2019555921A priority patent/JP6894530B2/ja
Priority to PCT/CN2017/082222 priority patent/WO2018195865A1/zh
Priority to KR1020197034515A priority patent/KR102326358B1/ko
Publication of WO2018195865A1 publication Critical patent/WO2018195865A1/zh

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Definitions

  • the invention relates to an in-situ preparation method for preparing at least one catalyst of toluene, p-xylene and low-carbon olefin, and at least one reaction process for preparing toluene, p-xylene and low-carbon olefin, belonging to the field of chemical engineering.
  • Ethylene and propylene are the cornerstones of the vast petrochemical industry, and most organic chemicals are derived from ethylene and propylene.
  • Para-xylene (PX) is a raw material for producing polyesters such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate) and PTT (polytrimethylene terephthalate).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT polytrimethylene terephthalate
  • the source of PX is mainly prepared by disproportionation, isomerization and separation by adsorption or cryogenic separation using toluene, C9 aromatic hydrocarbon and mixed xylene obtained by naphtha reforming.
  • the equipment investment is large and the operation cost is high.
  • p-xylene since the content of p-xylene in the product is thermodynamically controlled, p-xylene only accounts for about 20% of the xylene isomer, and the boiling points of the three xylene isomers are small, which cannot be obtained by ordinary distillation techniques. Purity p-xylene must use an expensive adsorption separation process.
  • the method uses cheap and easily available toluene and methanol as raw materials; the selectivity of PX in one reaction product is high, and its production process High-purity p-xylene can be obtained by simple crystallization separation by using expensive adsorption separation technology; the benzene content in the product is low.
  • Metallic or/and non-metal modified HZSM-5 molecular sieve catalysts are mainly used.
  • USP 4,250,345 uses a phosphorus and magnesium two-element modified ZSM-5 molecular sieve catalyst with an optimum selectivity to para-xylene of -98% at 450 °C.
  • Chinese patent CN101485994A reports a ZSM-5 catalyst modified by Pt, Si, Mg, P and mixed rare earth elements.
  • the toluene conversion rate is >20% when the toluene/methanol molar ratio is 2/1 and the reaction temperature is 460 °C.
  • PX selectivity > 98%.
  • Chinese patent CN102716763A discloses a HZSM-5 molecular sieve catalyst modified by P, Ni element and SiO 2 deposition. The catalyst is used for alkylation of toluene methanol in a fixed bed reactor, and the conversion of toluene is ⁇ 31%. PX selectivity is ⁇ 91%.
  • Chinese patent CN101417236A discloses a fluidized bed catalyst for the alkylation of toluene with methanol to produce p-xylene and a low-carbon olefin.
  • the HZSM-5 molecular sieve catalyst modified with alkaline earth metal, non-metal, rare earth metal and siloxane-based compound,
  • the selectivity of PX in the xylene product reaches 99%, the selectivity of ethylene and propylene in C 1 -C 5 non-condensable gas is more than 90%, but the conversion of toluene is only -20%, and the methanol conversion rate is not mentioned;
  • the preparation process of the catalyst is complicated, and multiple modification and baking processes are required.
  • a process for the in situ preparation of a catalyst which is simple in process and easy to handle, which is prepared from p-xylene, toluene and/or light olefins from a feedstock containing methanol and/or dimethyl ether.
  • catalyst By directly preparing the catalyst in the reaction system, the entire chemical production process is simplified, the catalyst preparation and transfer steps are saved, and the operation is easy. The existing chemical industry is broken, and the finished catalyst is prepared in the catalyst production unit, and then transported to the catalyst.
  • the chemical production unit the traditional production mode of filling the catalyst and then driving the vehicle, overcomes the technical bias in the large-scale industrial production in the multiphase catalytic field.
  • the in-situ preparation method of the catalyst, the modifier is contacted with the molecular sieve in the reactor, and a catalyst for preparing p-xylene, toluene and/or low-carbon olefin from a raw material containing methanol and/or dimethyl ether is prepared in situ;
  • the reactor is a reactor for reacting p-xylene, toluene and/or lower olefins from a feedstock containing methanol and/or dimethyl ether.
  • the modifier comprises at least one of the following:
  • Modifier I a phosphorus reagent and a silylation reagent
  • Modifier II silylation reagent
  • Modifier III silylating agent and water vapor
  • Modifier IV phosphorus reagent, silylation reagent and water vapor;
  • the catalyst is a catalyst for at least one of the following reactions:
  • Reaction I co-production of para-xylene with methanol and/or dimethyl ether and toluene low-carbon olefin;
  • Reaction II at least one of methanol and/or dimethyl ether and benzene toluene, p-xylene, and light olefin.
  • the reactor is a reactor in which at least one of Reaction I or Reaction II occurs.
  • reaction I is methanol and/or dimethyl ether and toluene to para-xylene.
  • reaction I is methanol and toluene to para-xylene.
  • the reaction II is the co-production of p-xylene and a light olefin with methanol and/or dimethyl ether and benzene toluene.
  • reaction II is the co-production of p-xylene with methanol and/or dimethyl ether and benzene toluene.
  • reaction II is a co-production of a lower olefin with methanol and/or dimethyl ether and benzene para-xylene.
  • reaction II is methanol and/or dimethyl ether and benzene para-xylene.
  • reaction II is methanol and benzene para-xylene.
  • the phosphorus reagent is selected from at least one of the organophosphine compounds.
  • the phosphorus reagent is selected from at least one of the compounds having the formula of formula I:
  • R 1 , R 2 and R 3 are independently selected from a C 1 - C 10 alkyl group or a C 1 - C 10 alkoxy group.
  • R 1 , R 2 and R 3 are independently selected from a C 1 - C 5 alkyl group or a C 1 - C 5 alkoxy group.
  • At least one of R 1 , R 2 and R 3 in the formula I is selected from a C 1 to C 10 alkoxy group. Further preferably, at least one of R 1 , R 2 and R 3 in the formula I is selected from a C 1 -C 5 alkoxy group. Still more preferably, in the formula I, R 1 , R 2 and R 3 are the same alkoxy group.
  • the phosphorus reagent is at least one selected from the group consisting of trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine, and methyldiethoxyphosphine.
  • the silylating agent is selected from at least one of organosilicon compounds.
  • the silylating agent is selected from at least one of the compounds having the formula of formula II:
  • R 4 , R 5 , R 6 and R 7 are independently selected from a C 1 - C 10 alkyl group or a C 1 - C 10 alkoxy group.
  • R 4 , R 5 , R 6 , and R 7 in the formula II are independently selected from a C 1 -C 5 alkyl group or a C 1 -C 5 alkoxy group.
  • At least one of R 4 , R 5 , R 6 and R 7 in the formula II is selected from a C 1 -C 10 alkoxy group. Further preferably, at least one of R 4 , R 5 , R 6 and R 7 in the formula II is selected from a C 1 -C 5 alkoxy group. Still more preferably, in the formula II, R 4 , R 5 , R 6 and R 7 are the same alkoxy group.
  • the silylating agent is at least one selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, and tetrabutyl silicate.
  • the reactor is selected from at least one of a fixed bed, a fluidized bed, and a moving bed reactor.
  • the molecular sieve is a shaped molecular sieve formed according to a reactor type
  • the shaped molecular sieve is composed of molecular sieves
  • the shaped molecular sieve contains a molecular sieve and a binder.
  • the shaped molecular sieve is prepared by a method in which a molecular sieve tablet is crushed and formed, a molecular sieve and a binder are mixed and extruded, and then the strand is formed, and the molecular sieve and the binder are mixed and spray-dried.
  • the molecule is selected from at least one of a molecular sieve having an MFI skeleton structure and a molecular sieve having a MEL skeleton structure.
  • the molecular sieve is a HZSM-5 molecular sieve and/or an HZSM-11 molecular sieve.
  • the in-situ preparation method of the catalyst comprises at least the following steps:
  • the material A in the step (2) contains at least one of the raw materials and a modifier.
  • the material A in the step (2) contains toluene and/or benzene.
  • the step (2) is to pass the material A containing the modifier I into the reactor; the modifier I contains a phosphorus reagent and a silylation reagent.
  • the material A in the step (2) contains the modifier I and toluene.
  • the material A containing the phosphorus reagent and the silylating agent is introduced into the reactor at a temperature of from 130 ° C to 500 ° C.
  • material A contains a phosphorus reagent, a silylating agent and toluene.
  • the mass ratio of the phosphorus reagent to the silylating reagent in the material A in the step (2) is:
  • the phosphorus reagent in the material A in the step (2) accounts for 1 wt% to 10 wt% of the total weight of the material A; the silylation reagent accounts for 1 wt% to 40 wt% of the total weight of the material A, and the toluene accounts for 50 wt% of the total weight of the material A. ⁇ 98wt%.
  • the phosphorus reagent in the material A in the step (2) accounts for 2wt% to 10wt% of the total weight of the material A; the silylation reagent accounts for 8wt% to 40wt% of the total weight of the material A, and the toluene accounts for 50wt of the total weight of the material A. % ⁇ 90wt%.
  • the total weight space velocity of the material A introduced into the reactor in the step (2) is from 0.5 h -1 to 2 h -1 .
  • the time for introducing the material A into the reactor in the step (2) is from 30 min to 225 min.
  • the material A is stopped from flowing into the reactor, and after being purged by the inert gas, the temperature is further calcined.
  • the inert gas is at least one selected from the group consisting of nitrogen, helium, and argon.
  • the calcination temperature in the step (3) is from 500 ° C to 700 ° C, and the calcination time is from 1 to 6 hours.
  • step (2) is to introduce a material B containing modifier II into the reactor; the modifier II contains a silylating agent.
  • the material B in the step (2) contains at least one of methanol, toluene, dimethyl ether and the modifier II.
  • step (2) is to pass a material containing modifier III to the reactor; said modifier III contains a silylating agent and water vapor.
  • the in-situ preparation method of the catalyst comprises at least the following steps:
  • the temperature of the reactor is raised to 550 ° C or higher, and the material E containing water vapor is passed to the water vapor. After that, the catalyst is obtained.
  • the material D in the step (2) contains a silylating agent and benzene.
  • the step (2) is D material WHSV 0.1h -1 ⁇ 1h -1, D is passed through the material for 0.1 to 5 hours.
  • the weight space velocity of the material D in the step (2) is 0.2 h -1 to 0.4 h -1
  • the time for introducing the material D is 0.5 to 2 hours.
  • the material E in the step (4) contains water vapor and benzene.
  • the in-situ preparation method of the catalyst comprises at least the following steps:
  • the temperature of the reactor is raised to 550 ° C or higher, and the material G containing steam is subjected to steam treatment to obtain the catalyst.
  • the material F in the step (2) contains a phosphorus reagent, a silylating agent and benzene.
  • the mass ratio of the silylating agent to the phosphorus reagent in the material F in the step (2) is:
  • the calcination temperature in the step (3) is from 500 ° C to 700 ° C, and the calcination time is from 1 to 6 hours.
  • the inert gas in the step (4) is at least one selected from the group consisting of nitrogen, helium, and argon.
  • the temperature of the steam treatment in the step (4) is from 550 ° C to 800 ° C, and the treatment time is from 1 to 10 hours.
  • the material G in the step (4) contains water vapor and benzene.
  • the weight space velocity of the water vapor in the material G in the step (4) is 0.5 h -1 to 5 h -1 . Further preferably, the weight space velocity of the water vapor in the material G in the step (4) is from 1 h -1 to 3 h -1 .
  • the material G containing water vapor may be 100% water vapor, or may be an inert gas and/or other agent which can improve (adjust) the steam reforming efficiency without affecting the catalyst reaction performance.
  • the temperature of the steam treatment in the step (4) is 550 ° C to 800 ° C, and the treatment time is 1 to 10 hours.
  • the phosphorus reagent in the material A in the step (2) accounts for 1 wt% to 10 wt% of the total weight of the material A; the silylation reagent accounts for 1 wt% to 40 wt% of the total weight of the material A, and the toluene accounts for 50 wt% of the total weight of the material A. ⁇ 98wt%.
  • the phosphorus reagent in the material F in the step (2) accounts for 1 wt% to 10 wt% of the total weight of the material F; the silylation reagent accounts for 1 wt% to 40 wt% of the total weight of the material F, and the benzene accounts for 50 wt% of the total weight of the material F. ⁇ 98wt%.
  • the calcination temperature in the step (3) is from 500 ° C to 700 ° C, and the calcination time is from 1 to 6 hours.
  • the material containing the modifier is introduced into the reactor at a temperature of from 130 ° C to 500 ° C.
  • the material containing the modifier is introduced into the reactor at a temperature of from 200 ° C to 400 ° C.
  • a process for co-production of p-xylene (Reaction I) of methanol and/or dimethyl ether with toluene to produce a low carbon olefin characterized in that it will contain methanol and/or dimethyl ether.
  • the feedstock of toluene is contacted with a catalyst for the co-production of a low carbon olefin co-produced in a reactor in accordance with any of the methods described above to produce a lower olefin to produce para-xylene.
  • the reaction of the low-carbon olefin co-production of p-xylene is started directly from the calcination temperature to the reaction temperature.
  • the catalyst separation process after catalyst modification, the catalyst cooling process to room temperature after calcination, the catalyst transportation step, the catalyst charging step, and the high temperature preactivation after the catalyst is charged into the reactor are saved.
  • the steps, etc. greatly improve the production efficiency, avoid the safety problems that may occur in the above saved steps; more importantly, the reactor can start the reaction from the calcination temperature to the reaction temperature, and the heat energy is fully utilized, and the saving is greatly saved. The energy consumption in production.
  • Reaction I co-production of p-xylene with methanol and/or dimethyl ether and toluene olefins.
  • reaction I is methanol and/or dimethyl ether and toluene to para-xylene.
  • reaction I is methanol and toluene to para-xylene.
  • the phosphorus reagent and the silylating reagent are contacted with the molecular sieve in the reactor, and the catalyst of the reaction I is prepared in situ;
  • the reactor is a reactor in which reaction I occurs.
  • the starting material is contacted with the catalyst at a reaction temperature of from 350 ° C to 650 ° C.
  • the starting material is contacted with the catalyst at a reaction temperature of from 400 ° C to 500 ° C.
  • methanol and/or dimethyl ether and toluene are as follows:
  • the reaction raw material contains methanol and toluene. Since methanol may be converted to dimethyl ether on the catalyst, that is, the interaction between methanol and dimethyl ether in the raw material is the same, so the actual reaction is introduced.
  • the feedstock contains methanol and toluene, often with methanol, dimethyl ether and toluene present on the catalyst of the reactor.
  • the following raw materials are exemplified by methanol and toluene, but the case where dimethyl ether is contained in the raw material is not excluded. In the calculation, the number of moles of carbon atoms of dimethyl ether corresponds to the number of moles of methanol.
  • the ratio between the low-carbon olefin and the para-xylene in the product can be adjusted by adjusting the ratio of methanol to toluene in the raw material according to specific production requirements.
  • the methanol/toluene ratio in the feed is increased, the olefin content of the product is increased; when the methanol/toluene ratio in the feed is reduced, the p-xylene content of the product is increased.
  • the total weight space velocity of the feedstock containing methanol and toluene is from 1 h -1 to 3 h -1 .
  • reaction system stream I in contact with the catalyst, to give II stream, separating the C 4 olefins, or C 5+ hydrocarbon chain of the return stream from the reaction system II, is separated from the light olefins stream II and dimethyl Toluene as a product;
  • the stream I contains methanol and/or dimethyl ether, toluene.
  • the reaction system comprises a first reaction zone and second reaction zone, stream I to give II-A stream in a first reaction zone with a catalyst, separating the C 4 or C 5 olefin stream from the II-A + chain hydrocarbons are introduced into the second reaction zone to contact the catalyst to obtain a stream II-B;
  • the lower olefins and p-xylene separated in the streams II-A and II-B are used as products.
  • the reaction system comprises a first reaction zone and a second reaction zone, the stream I contacting the catalyst in the first reaction zone to obtain a stream II-A, the stream II-A being passed to the separation system and separated Producing C 4 olefins, light olefins and p-xylene;
  • the lower olefins and p-xylene separated in the separation system are used as products.
  • the reaction system comprises a first reaction zone and a second reaction zone, the stream I is contacted with a catalyst in a first reaction zone to obtain a stream II-A, and the stream II-A is passed to a separation system.
  • the separation system outputs C 5+ chain hydrocarbons, lower olefins and para-xylene;
  • the lower olefins and p-xylene output from the separation system are used as products.
  • the reaction system comprises a first reaction zone and a second reaction zone, the first reaction zone and the second reaction zone both contain a catalyst A;
  • the catalyst A is a phosphorus reagent and a silylation reagent modified HZSM-5 molecular sieve catalyst, and the specific preparation steps are as follows:
  • the temperature is raised to 500 ° C or higher, and calcined in an air atmosphere for 1-6 hours to obtain the catalyst A.
  • the reaction system comprises a first reaction zone containing a catalyst A and a second reaction zone containing a catalyst B.
  • the catalyst A is a phosphorus reagent and a silylation reagent modified HZSM-5 molecular sieve catalyst, and the specific preparation steps are as follows:
  • the temperature is raised to 500 ° C or higher, and calcined in an air atmosphere for 1-6 hours to obtain the catalyst A.
  • the catalyst B is a silylation reagent-modified HZSM-5 molecular sieve catalyst, and the specific preparation steps are as follows:
  • the reaction system comprises one reactor or a plurality of reactors connected by series and/or parallel.
  • the reactor is at least one of a fixed bed, a fluidized bed or a moving bed.
  • the reaction system includes a first reaction zone and a second reaction zone, the first reaction zone and the second reaction zone being in the same reactor.
  • the reaction system comprises a first reaction zone and a second reaction zone, the first reaction zone comprising a reactor or a plurality of reactors connected by series and / or parallel, the second reaction zone comprising One reactor or a plurality of reactors connected by series and/or parallel.
  • first reaction zone and the second reaction zone are connected by series or parallel connection.
  • the first reaction zone undergoes a methanol conversion reaction and a toluene methanol alkylation reaction
  • the second reaction zone undergoes a shape selective aromatization reaction
  • the total feed space velocity of the feedstock 0.1h -1 ⁇ 10h -1.
  • the total feed space velocity of the feedstock 0.8h -1 ⁇ 3h -1.
  • the molar content of toluene in the raw material is from 5 mol% to 50 mol%.
  • the molar content of toluene in the raw material is from 20 mol% to 40 mol%.
  • the phosphorus reagent and the silylating agent are contacted with the molecular sieve in the reactor, and the catalyst for producing the low-carbon olefin co-produced para-xylene is prepared in situ;
  • the reactor is a reactor for the production of low carbon olefins co-produced para-xylene.
  • a method of reacting at least one of methanol, and/or dimethyl ether with benzene toluene, p-xylene, and a lower olefin (Reaction II), characterized in that it will contain methanol and/or Or a feedstock of dimethyl ether and benzene is contacted in a reactor with a catalyst of reaction II prepared in situ according to any of the methods described above to produce toluene, p-xylene and/or lower olefins.
  • the catalyst separation process after catalyst modification, the catalyst cooling process to room temperature after calcination, the catalyst transportation step, the catalyst charging step, and the high temperature preactivation after the catalyst is charged into the reactor are saved.
  • the steps, etc. greatly improve the production efficiency, avoid the safety problems that may occur in the above saved steps; more importantly, the reactor can start the reaction from the calcination temperature to the reaction temperature, and the heat energy is fully utilized, and the saving is greatly saved. The energy consumption in production.
  • Reaction II at least one of methanol and/or dimethyl ether and benzene toluene, p-xylene, and light olefin.
  • the silylating agent and water vapor are contacted with the molecular sieve in the reactor to prepare the catalyst of the reaction II in situ;
  • the reactor is the reactor of Reaction II.
  • the reaction temperature is lowered from the steam reforming temperature to the reaction temperature, and the reaction of methanol and/or dimethyl ether with benzene alkylation to toluene to produce p-xylene is started.
  • the catalyst separation process after catalyst modification, the catalyst cooling process to room temperature after calcination, the catalyst transportation step, the catalyst charging step, and the high temperature preactivation after the catalyst is charged into the reactor are saved.
  • the steps, etc. greatly improve the production efficiency, avoid the safety problems that may occur in the above saved steps; more importantly, the reactor can start the reaction from the calcination temperature to the reaction temperature, and the heat energy is fully utilized, and the saving is greatly saved. The energy consumption in production.
  • the starting materials of the present application are benzene and methanol, wherein the methanol comprises the form of a methanol and/or dimethyl ether feed. Since methanol may be converted to dimethyl ether on the catalyst, that is, the interaction between methanol and dimethyl ether in the raw materials is common, the actual reaction raw materials are introduced into methanol and toluene, which are often present on the catalyst of the reactor. Methanol, dimethyl ether and toluene. The following raw materials are exemplified by methanol and toluene, but the case where dimethyl ether is contained in the raw material is not excluded. In the calculation, the number of moles of carbon atoms of dimethyl ether corresponds to the number of moles of methanol.
  • toluene of benzene and methanol is co-produced with p-xylene and a low-carbon olefin, wherein the raw material contains benzene and methanol, and the case where methanol includes methanol and/or dimethyl ether.
  • the methanol in the present application may be replaced by all or part of dimethyl ether, and the amount of methanol may be calculated by converting dimethyl ether into methanol having the same number of carbon atoms.
  • the reactor is selected from at least one of a fixed bed, a fluidized bed, and a moving bed reactor.
  • the reaction temperature of the reaction II is from 350 ° C to 600 ° C.
  • the reaction temperature of the reaction II is from 400 ° C to 500 ° C.
  • the ratio of low-carbon olefins to toluene and p-xylene in the product can be adjusted by adjusting the ratio of methanol to benzene in the raw materials according to specific production requirements.
  • the methanol/benzene ratio in the feedstock is increased, the olefin content of the product is increased; when the methanol/benzene ratio in the feedstock is reduced, the toluene and para-xylene content of the product is increased.
  • the total weight space velocity of the feedstock containing methanol and benzene is from 1 h -1 to 4 h -1 .
  • the in-situ preparation method of the catalyst of the reaction II comprises at least the following steps:
  • the temperature of the reactor is raised to 550 ° C or higher, and the material E containing water vapor is subjected to steam treatment to obtain the catalyst of the reaction II.
  • the in-situ preparation method of the catalyst of the reaction II comprises at least the following steps:
  • the temperature of the reactor is raised to 550 ° C or higher, and the material G containing steam is subjected to steam treatment to obtain the catalyst of the reaction II.
  • the reaction raw material contains methanol in the case where the raw material methanol includes methanol and/or dimethyl ether.
  • the methanol in the present application may be replaced by all or part of dimethyl ether, and the amount of methanol may be calculated by converting dimethyl ether into methanol having the same number of carbon atoms.
  • the C 1 to C 10 , C 1 to C 5 and the like mean the number of carbon atoms contained in the group.
  • alkyl is a group formed by the loss of any one of the hydrogen atoms in the molecule of the alkane compound.
  • the alkane compound includes a linear alkane, a branched alkane, a cycloalkane, a branched cycloalkane.
  • the "alkoxy group” is a group formed by the loss of a hydrogen atom on a hydroxyl group from an alkyl alcohol compound.
  • the "low carbon olefin” means ethylene and propylene.
  • the "methanol and / or dimethyl ether and toluene” includes three cases: methanol and toluene; or dimethyl ether and toluene; or methanol, dimethyl ether and toluene.
  • the "methanol and / or dimethyl ether and benzene” includes three cases: methanol and benzene; or dimethyl ether and benzene; or methanol, dimethyl ether and benzene.
  • the methanol in the present application may be replaced by all or part of dimethyl ether, and the amount of methanol may be calculated by converting dimethyl ether into methanol having the same number of carbon atoms.
  • the in-situ preparation method of at least one catalyst for producing toluene, p-xylene and low-carbon olefin breaks the existing chemical industry, first prepares a finished catalyst in a catalyst production unit, and then transports it to The chemical production unit, the traditional production mode of filling the catalyst and then driving the vehicle, overcomes the technical bias in the large-scale industrial production in the multiphase catalytic field.
  • the method for producing at least one of toluene, p-xylene, and low-carbon olefin saves the washing and separating process after the catalyst modification and decreases after calcination, compared with the production method inherent in the chemical industry.
  • the room temperature catalyst cooling process, the catalyst transportation step, the catalyst charging step, the high temperature preactivation step after the catalyst is charged into the reactor, etc. greatly improve the production efficiency, and avoid the safety problems that may occur in the above saved steps; It is important that the reactor is cooled from the calcination temperature to the reaction temperature to start the reaction, and the heat energy is fully utilized, which greatly saves energy consumption in production.
  • 1 is a process flow diagram of an embodiment of the application of the present application.
  • FIG. 2 is a process flow diagram of an embodiment to which the present application is applied.
  • FIG. 3 is a process flow diagram of an embodiment of the application of the present application.
  • FIG. 4 is a process flow diagram of an embodiment to which the present application is applied.
  • Figure 5 is a process flow diagram of an embodiment of the application of the present application.
  • FIG. 6 is a process flow diagram of an embodiment to which the present application is applied.
  • the catalyst wear index was measured on an MS-C type wear indexer of Shenyang Hexing Machinery & Electronics Co., Ltd.
  • the fixed bed reactor has an inner diameter of 1.5 cm; the fixed fluidized bed reactor has an inner diameter of 3 cm; and the circulating fluidized bed reactor has an inner diameter of 12 cm.
  • Molecular sieve particles denoted as FXHZSM-5-A.
  • Molecular sieve particles denoted as FXHZSM-5-B.
  • Molecular sieve particles denoted as FXHZSM-5-C.
  • Molecular sieve particles denoted as FXHZSM-11-A.
  • the specific steps are as follows:
  • HZSM-5 zeolite molecular sieve raw powder, pseudo-boehmite, silica sol, xanthan gum (bio-gel) and water are uniformly mixed, and the slurry is obtained by beating, grinding and defoaming; the weight of each component in the slurry The number of copies is:
  • the obtained slurry was spray-dried to obtain a sample of microsphere particles having a particle size distribution of 20 to 100 ⁇ m; and the sample of the microsphere particles was calcined at 550 ° C for 3 hours in a muffle furnace to obtain a HZSM-5 shaped molecular sieve having a wear index of 1.2. Recorded as FLHZSM-5-A.
  • the specific preparation conditions and steps are the same as those in the third embodiment, except that the raw material HZSM-5 zeolite molecular sieve raw powder is used in an amount of 10 kg, and the obtained microsphere particle sample has a particle size distribution of 20 to 120 ⁇ m and a wear index of 1.2, which is recorded as FLHZSM. -5-B.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 1.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 2.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 3.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 4.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 5.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 6.
  • reaction performance was evaluated by preparing methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst in a micro fixed bed reactor.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 7.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 60 min. The reaction results are shown in Table 8.
  • a micro-fixed bed reactor was used to produce low-carbon olefins to produce para-xylene using methanol toluene as a raw material.
  • the in-situ preparation of the catalyst was as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-A was charged into a micro fixed bed reactor, first treated with 50 mL/min of nitrogen at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered. Up to 300 ° C.
  • the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined in an air atmosphere for 4 hours to obtain a methanol-toluene low-carbon olefin co-produced p-xylene fixed bed catalyst, which was named FXCAT-8.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 9.
  • stream I comprises methanol and toluene, and methanol toluene is used as a raw material to produce a low carbon olefin to produce para-xylene.
  • the reaction system was charged with 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A prepared in Example 1, first treated with 50 mL/min of nitrogen at 550 ° C for 1 hour, and then cooled to 300 ° C under a nitrogen atmosphere.
  • the stream I is passed to the reaction system and contacted with the catalyst FXCAT-9 and reacted.
  • II containing product stream leaving the reaction system and enter the separation system to separate the light olefins (ethylene and propylene), C 4 olefins, xylene, and other components.
  • C 4 olefins are returned to the reaction system, and low carbon olefins (ethylene and propylene) and p-xylene are used as products.
  • Other components are used as by-products.
  • the product was analyzed by online Agilent 7890 gas chromatography as shown in Table 10.
  • stream I comprises dimethyl ether and toluene, and dimethyl ether toluene is used as a raw material to produce a lower olefin to co-produce para-xylene.
  • Example 14 The difference from Example 14 was that the separation system was the same as in Example 14, and a fixed bed catalyst was obtained, which was named FXCAT-10.
  • the separation system of this example separates C 1 to 3 chain hydrocarbons, C 4 olefins, C 4 alkane, C 5+ chain hydrocarbons, and aromatic hydrocarbons. Among them, the C 4 olefin is returned to the reaction system. Ethylene and propylene are separated from the C 1 to 3 chain hydrocarbons as a low carbon olefin product. Para-xylene is separated from the aromatic hydrocarbon as a product. Other components are used as by-products. The reaction results were in agreement with Example 14 (the deviation was not more than ⁇ 1%).
  • stream I comprises methanol and toluene, and methanol toluene is used as a raw material to produce low carbon olefins to produce para-xylene.
  • the first reaction zone is 10 fixed beds in parallel, and the second reaction zone is a fluidized bed.
  • trimethoxyphosphorus the total WHSV of tetraethylorthosilicate and toluene 1h -1 atmospheric pressure.
  • the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined in an air atmosphere for 4 hours to obtain a methanol-toluene low-carbon olefin co-produced p-xylene fixed bed catalyst, which was named FXCAT-11.
  • Stream I is passed to a fixed bed in the first reaction zone in contact with catalyst FXCAT-11 to provide stream II-A, stream II-A exiting the first reaction zone and entering the separation system. Ethylene, propylene, C 4 olefins and p-xylene were separated from the separation system.
  • the C 4 olefin separated in the separation system is introduced into the fluidized bed of the second reaction zone to be contacted with the catalyst FXCAT-12, and the second reaction zone is subjected to a fluidized bed amorphous aromatization reaction at a reaction temperature of 450 °C.
  • the second reaction zone receives stream II-B, which leaves the second reaction zone and enters the separation system.
  • Ethylene and propylene separated from the separation system are used as low carbon olefin products and p-xylene as a product. Other components are used as by-products.
  • the hydrocarbon product of the second reaction zone was analyzed by on-line Agilent 7890 gas chromatography as shown in Table 11; the product distribution after deducting the C 4 olefin component is shown in Table 12.
  • the first reaction zone and the second reaction zone mixed hydrocarbon product were analyzed by on-line Agilent 7890 gas chromatography, and the product distribution after deducting the C 4 olefin component is shown in Table 13.
  • stream I comprises dimethyl ether, methanol and toluene, and dimethyl ether, methanol and toluene are used as raw materials to produce low carbon olefins to co-produce p-xylene.
  • Example 16 The difference from Example 16 was that the first reaction zone was a fixed bed filled with 50 g of molecular sieve sample FXHZSM-5-A. Also, in the separation system, the separation system of the present embodiment separates C 1 to 3 chain hydrocarbons, C 4 olefins, C 4 alkane, C 5+ chain hydrocarbons, and aromatic hydrocarbons. Wherein the C 4 olefin is returned to the second reaction zone. Ethylene and propylene are separated from the C 1 to 3 chain hydrocarbons as a low carbon olefin product. Para-xylene is separated from the aromatic hydrocarbon as a product. Other components are used as by-products. The rest was the same as in Example 23, and the fixed bed catalyst was designated as FXCAT-13, and the fluidized bed catalyst was designated as FLCAT-14. The reaction results were in agreement with Example 16 (the deviation did not exceed ⁇ 1%).
  • a low carbon olefin is co-produced with p-xylene using methanol and toluene as raw materials according to the process flow chart shown in FIG. Stream I includes methanol and toluene.
  • the reaction system is two fixed beds.
  • the reaction system parts shown in Figure 5 are arranged in series above and below.
  • the stage I feeds the feed I from the upper fixed bed, and the recirculated C 5+ chain hydrocarbons enter the lower part. bed.
  • the feed was stopped after 90 minutes of feeding, nitrogen purged, temperature raised to 550 ° C, and calcined for 4 hours in an air atmosphere.
  • In-situ methanol toluene was prepared to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst, which was recorded as FXCAT-15.
  • Stream I enters the fixed bed reactor in the upper part of the reaction system, contacts the catalyst FXCAT-15, and performs methanol conversion reaction and selective alkylation reaction of toluene methanol.
  • the separation system separating the hydrocarbon chain C 1 ⁇ 4, C 5+ chain hydrocarbons and aromatic hydrocarbons.
  • the C 5+ chain hydrocarbon is returned to the fixed bed in the lower part of the reaction system, and is contacted with the catalyst FXCAT-15 to carry out a reaction such as cracking and shape-selective aromatization, and the reaction temperature of the fixed bed in the lower part of the reaction system is 630 °C.
  • Ethylene and propylene are separated from the C 1-4 hydrocarbons as a low olefin product.
  • Para-xylene is separated from the aromatic hydrocarbon as a product.
  • Other components are used as by-products.
  • the product was analyzed by online Agilent 7890 gas chromatography as shown in Table 14.
  • a low carbon olefin is co-produced with p-xylene according to the process flow diagram shown in FIG. 6 using methanol toluene as a raw material.
  • Stream I includes methanol and toluene.
  • the first reaction zone is a fixed bed and the second reaction zone is a fixed bed.
  • the feed was stopped after 90 minutes of feeding, nitrogen purged, temperature raised to 550 ° C, and calcined for 4 hours in an air atmosphere.
  • methanol toluene to produce a low-carbon olefin co-produced p-xylene fixed bed catalyst was prepared in the first fixed bed reaction zone and the second fixed bed reaction zone, respectively, and recorded as FXCAT-16.
  • Stream I enters the fixed bed of the first reaction zone and contacts the catalyst FXCAT-16 and undergoes a methanol conversion reaction and a selective alkylation reaction of toluene methanol.
  • the product containing stream II-A exits the fixed bed of the first reaction zone and enters the separation system.
  • the separation system separates C 1-4 hydrocarbons, C 5+ chain hydrocarbons, and aromatic hydrocarbons.
  • the C 5+ chain hydrocarbon separated from the separation system enters the fixed bed of the second reaction zone, contacts with the catalyst FXCAT-16, and undergoes a reaction such as cracking, amorphous aromatization, etc., and the fixed bed reaction temperature of the second reaction zone is 630 ° C.
  • the product containing stream II-B exits the fixed bed of the second reaction zone and enters the separation system.
  • Ethylene and propylene are separated from the C 1 to 4 chain hydrocarbons separated from the separation system as a low carbon olefin product.
  • Para-xylene is separated from the aromatic hydrocarbon as a product.
  • Other components are used as by-products.
  • the hydrocarbon product of the second reaction zone was analyzed by on-line Agilent 7890 gas chromatography as shown in Table 15; the product distribution after deducting the C 5+ chain hydrocarbon component is shown in Table 16.
  • the first reaction zone and the second reaction zone mixed hydrocarbon product were analyzed by on-line Agilent 7890 gas chromatography, and the product distribution after deducting the C 5+ chain hydrocarbon component is shown in Table 17.
  • the flowchart is the same as that of Embodiment 19, as shown in FIG. The difference is in the raw materials and reactors.
  • the stream I comprises dimethyl ether, methanol and toluene, and the dimethyl ether, methanol and toluene are used as raw materials to produce low-carbon olefins to co-produce p-xylene.
  • the first reaction zone was a fluidized bed, and 1 kg of the molecular sieve sample FLHZSM-5-C of Example 4 was charged.
  • the second reaction zone was a fluidized bed packed with 1 kg of the same molecular sieve sample FLHZSM-5-C of Example 4.
  • Catalyst preparation process The catalyst in each fluidized bed reactor was treated with 10 L/min of nitrogen at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 300 ° C. The same as in Example 19, a fixed bed catalyst was obtained named FLCAT-17. The reaction results were in agreement with Example 19 (deviation does not exceed ⁇ 1%).
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by co-production of toluene, and was named FXCAT-18. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The results of the reaction are shown in Table 18.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight space of tetraethyl silicate was 0.1 h -1 , atmospheric pressure. After 2 hours of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by the co-production of toluene, and was named FXCAT-19. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 19.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.4 h -1 , atmospheric pressure. The feed was stopped after 0.5 hours of feeding, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by co-production of toluene, and was named FXCAT-20. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 20.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 300. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by the co-production of toluene, and was named FXCAT-21. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 21.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 450. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by the co-production of toluene, and was named FXCAT-22. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 22.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 300. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 800 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 2 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by co-production of toluene, and was named FXCAT-23. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 23.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 300. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere.
  • the temperature was raised to 600 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump at a water weight of 2 h -1 . At normal pressure, the feed was stopped after 8 hours of feeding, and methanol and/or dimethyl ether and phenylalkyl were obtained.
  • a toluene fixed bed catalyst was produced by the co-production of toluene, and was named FXCAT-24. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 24.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-11-B was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • the toluene was combined to produce a p-xylene fixed bed catalyst, which was named FXCAT-25. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 25.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 150 ° C. °C.
  • the tetramethyl silicate was fed with a micro feed pump, and the weight of the tetramethyl silicate was 0.2 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • a toluene fixed bed catalyst was produced by the co-production of toluene, and was named FXCAT-26. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 26.
  • the benzene and methanol are alkylated in a fixed fluidized bed reactor to prepare a paraxylene co-produced fluidized bed catalyst.
  • the catalyst conditions were prepared on-line as follows: 10 g of the shaped molecular sieve sample FLHZSM-5-C was charged into a fixed fluidized bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200 ° C. Tetraethyl silicate was fed with a micro feed pump, and the weight space of tetraethyl silicate was 0.2 h -1 at atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 4 hours of feeding to obtain methanol and/or dimethyl ether and phenylalkyl.
  • the toluene co-produced p-xylene fluidized bed catalyst was named FLCAT-27. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and methanol and/or dimethyl ether is reacted with benzene to form toluene to produce p-xylene.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 27.
  • the in-line preparation of methanol and/or dimethyl ether in a micro fixed bed reactor was carried out to produce a p-xylene fixed bed catalyst by alkylation of benzene to toluene, and the reaction performance was evaluated.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-C was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.2 h -1 , atmospheric pressure.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 28.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst, named FXCAT-29 Low carbon olefin fixed bed catalyst, named FXCAT-29.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 29.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1.5 hours of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours. Under a nitrogen atmosphere was heated to 700 deg.] C, with a trace of water feed pump feed water WHSV 2h -1, atmospheric pressure, 4 hours after the feed stop feed, prepared as benzene, toluene and methanol co-production of low xylene A carbon olefin fixed bed catalyst, designated FXCAT-30. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 30.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1.5 hours of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours. The temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump. The water weight was 2 h -1 , and the pressure was normal. After 4 hours of feeding, the feed was stopped, and benzene and methanol were mixed to produce paraxylene. Low carbon olefin fixed bed catalyst, named FXCAT-31. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • FXCAT-31 Low carbon olefin fixed bed catalyst
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 31.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 32.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst, named FXCAT-33 Low carbon olefin fixed bed catalyst, named FXCAT-33.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 33.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 800 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , at normal pressure, and the feed was stopped after 2 hours of feeding, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst named FXCAT-34.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 34.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 600 ° C under a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst, named FXCAT-35 Low carbon olefin fixed bed catalyst, named FXCAT-35.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The results of the reaction are shown in Table 35.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-11-A catalyst was tableted and crushed into 40-60 mesh, and 5 g (40-60 mesh) catalyst was charged into a fixed bed reaction. The apparatus was first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200 ° C.
  • trimethoxy phosphine (mass ratio) 2, total of trimethoxy phosphine and tetraethyl silicate
  • the airspeed is 0.1h -1 and the pressure is normal.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours. The temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst named FXCAT-36.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The results of the reaction are shown in Table 36.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours.
  • the temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal.
  • the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst, named FXCAT-37 Low carbon olefin fixed bed catalyst, named FXCAT-37.
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 37.
  • the benzene and methanol toluene are co-produced in a fixed fluidized bed reactor to produce a p-xylene and a low-carbon olefin fluidized bed catalyst.
  • the feed was stopped after 1 hour of feeding, and the temperature was raised to 550 ° C in an air atmosphere and calcined for 4 hours. The temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump. The water weight was 2 h -1 , and the pressure was normal. After 4 hours of feeding, the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • reaction conditions are as follows: the raw material is fed by a micro feed pump.
  • Raw material benzene: methanol (molar ratio) 1:1, total weight of benzene and methanol airspeed 2h -1 , atmospheric pressure.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The results of the reaction are shown in Table 38.
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the feed was stopped, nitrogen was purged, the temperature was raised to 550 ° C, and calcination was carried out for 4 hours in an air atmosphere to obtain a fixed-bed catalyst of p-xylene and low-carbon olefins, which was named FXCAT-39. .
  • the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction conditions are as follows: the raw material is fed by a micro feed pump, and the raw material is benzene: methanol (molar ratio).
  • reaction performance was evaluated by preparing benzene and methanol toluene in a micro fixed bed reactor to produce p-xylene and a low-carbon olefin fixed bed catalyst.
  • the catalyst conditions were prepared on-line as follows: 5 g (40-60 mesh) shaped molecular sieve sample FXHZSM-5-A was charged into a fixed bed reactor, first treated with 50 mL/min of air at 550 ° C for 1 hour, and then the nitrogen atmosphere was lowered to 200. °C. Tetraethyl silicate was fed with a micro feed pump, and the weight of tetraethyl silicate was 0.067 h -1 , atmospheric pressure. After 1 hour of feeding, the feed was stopped, nitrogen purged, and the temperature was raised to 550 ° C, and calcined for 4 hours in an air atmosphere. The temperature was raised to 700 ° C in a nitrogen atmosphere, and the water was fed with a micro feed pump.
  • the water weight was 2 h -1 , and the pressure was normal. After 4 hours of feeding, the feed was stopped, and benzene and methanol were mixed to produce paraxylene.
  • Low carbon olefin fixed bed catalyst named FXCAT-40. Then, the nitrogen atmosphere is cooled to a reaction temperature of 450 ° C, and the reaction of benzene and methanol toluene to produce p-xylene and a low-carbon olefin is tested.
  • the reaction product was analyzed by on-line Agilent 7890 gas chromatography, and the reaction was sampled at 120 min. The reaction results are shown in Table 40.
  • the apparatus, operation and conditions are the same as those in the embodiment 5 except that the trimethoxyphosphorus is replaced with methyldiethoxyphosphorus during the preparation of the catalyst, and the others are unchanged, and the methanol toluene is prepared to produce a low-carbon olefin co-produced paraxylene fixed bed catalyst.
  • the reaction evaluation conditions were the same as in Example 5, and the reaction results were in agreement with Example 5 (the deviation was not more than ⁇ 1%).
  • reaction temperature 450 ° C reaction temperature 450 ° C
  • weight space of toluene and methanol mixture was 2 h -1 , atmospheric pressure.
  • the reaction product was analyzed by online Agilent 7890 gas chromatography. The reaction results are shown in Table 1.

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Abstract

一种反应Ⅰ：甲醇和/或二甲醚与甲苯制低碳烯烃联产对二甲苯，和/或反应Ⅱ：甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种催化剂的原位制备方法，将磷试剂、硅烷化试剂、水蒸气中的至少一种与反应器中的分子筛接触，原位制备反应Ⅰ和/或反应Ⅱ的催化剂；反应器为反应Ⅰ和/或反应Ⅱ的反应器。通过直接在反应系统中进行催化剂制备，简化了整个化工生产的流程，节省了催化剂制备和转移步骤，易于操作。经过原位制备的催化剂可以直接进行原位反应。

Description

制甲苯、对二甲苯、低碳烯烃中至少一种的催化剂的原位制备方法及反应工艺 技术领域
本申请涉及一种制甲苯、对二甲苯、低碳烯烃中至少一种催化剂的原位制备方法及制甲苯、对二甲苯、低碳烯烃中至少一种反应工艺，属于化学工程领域。
背景技术
乙烯和丙烯是庞大的石油化工产业的基石，绝大多数有机化工产品都是由乙烯和丙烯衍生而来。对二甲苯(PX)是生产PET(聚对苯二甲酸乙二醇酯),PBT(聚对苯二甲酸丁二醇酯)和PTT(聚对苯二甲酸丙二醇酯)等聚酯的原料。近年来聚酯在纺织服装、饮料包装等领域的大量应用带动了PTA(精对苯二甲酸)以及上游产品PX产量和消费量的快速增长。目前，PX来源是主要采用石脑油重整得到的甲苯、C9芳烃及混合二甲苯为原料通过歧化、异构化并通过吸附分离或深冷分离而制取，设备投资大，操作费用高。由于产物中对二甲苯的含量受热力学控制，对二甲苯在二甲苯异构体中只占20％左右，而三个二甲苯异构体的沸点相差很小，采用普通的蒸馏技术不能得到高纯度对二甲苯，必须采用昂贵的吸附分离工艺。
USP 3,911,041，USP 4,049,573，USP 4,100,219等专利公开了在磷、镁、硅等改性的HZSM-5催化剂上甲醇转化制取烯烃的反应；USP 5,367,100和USP 5,573,990中公开了中科院大连化学物理研究所使用磷、镧改性的HZSM-5分子筛催化剂由甲醇或二甲醚制取低碳烯烃的反应。自20世纪70年代以来，国内外相继开展了甲苯甲醇烷基化制对二甲苯技术的研究，该方法以廉价易得的甲苯、甲醇为原料；一次反应产物中PX选择性高，其生产过程中可避免使用昂贵的吸附分离技术，通过简单的结晶分离即可获得高纯度的对二甲苯；产物中苯含量低。主要采用金属或/和非金属改性的HZSM-5分子筛催化剂。USP 4,250,345使用磷和镁双元素改性的ZSM-5分子筛催化剂，在450℃条件下对二甲苯的最佳选择性～98％。中国专利CN101485994A报道了一种Pt、Si、Mg、P和混合稀土元素共同修饰的ZSM-5催化剂，在甲苯/甲醇摩尔比为2/1，反应温度为460℃时，甲苯转化率>20％，PX选择性>98％。中国专利CN102716763A公开了一种P、Ni元素改性和SiO2沉积改性的HZSM-5分子筛催化剂，采用该催化剂在固定床反应器中进行甲苯甲醇烷基化反应，甲苯转化率～31％，PX选择性～91％。
上述报道表明，在HZSM-5分子筛催化剂上，既可实现甲醇转化制取低碳烯烃反应，也可实现甲醇甲苯烷基化制对二甲苯反应。然而，由于两个反应过程不同，其催化剂物化性质也存在较大差异。因此，采用适宜的改性方法制备一种催化剂可同时满足甲醇转化制低碳烯烃和甲醇甲苯烷基化制对二甲苯两个反应的要求，就可实现采用同一个催化剂同时生产低碳烯烃(乙烯、丙烯)和对二甲苯。中国专利CN101417236A中公开了一种甲苯甲醇烷基化制对二甲苯和低碳烯烃的流化床催化剂，采用碱土金属、非金属、稀土金属以及硅氧烷基化合物修饰的HZSM-5分子筛催化剂，二甲苯产物中PX选择性达到99％，乙烯和丙烯在C1-C5不凝气中的选择性大于90％，但甲苯转化率仅～20％，且未提及甲醇转化率；另外，该催化剂制备过程复杂，需要进行多次改性、焙烧过程。
因此，发展一种过程简单、易于操作的制对二甲苯或制低碳烯烃联产对二甲苯催化剂的在线制备方法具有非常重要的意义和显著的实际应用性。
发明内容
根据本申请的一个方面，提供一种过程简单、易于操作的催化剂的原位制备方法，所述催化剂为由含有甲醇和/或二甲醚的原料制对二甲苯、甲苯和/或低碳烯烃催化剂。通过直接在反应系统中进行催化剂制备，简化了整个化工生产的流程，节省了催化剂制备和转移步骤，易于操作，打破了现有化工领域中，先在催化剂生产单位制备好成品催化剂，再运输至化工生产单位，装填好催化剂再开车生产的传统生产模式，克服了多相催化领域大规模工业化生产中的技术偏见。
该催化剂的原位制备方法，将改性剂与反应器中的分子筛接触，原位制备由含有甲醇和/或二甲醚的原料制对二甲苯、甲苯和/或低碳烯烃的催化剂；
所述反应器为由含有甲醇和/或二甲醚的原料制备对二甲苯、甲苯和/或低碳烯烃反应的反应器。
优选地，所述改性剂包括以下至少一种：
改性剂I：磷试剂和硅烷化试剂；
改性剂II：硅烷化试剂；
改性剂III：硅烷化试剂和水蒸气；
改性剂IV：磷试剂、硅烷化试剂和水蒸气；
优选地，所述催化剂为以下至少一种反应的催化剂：
反应I：甲醇和/或二甲醚与甲苯制低碳烯烃联产对二甲苯；
反应II：甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种。
优选地，所述反应器为发生反应I或反应II中至少一个反应的反应器。
作为一个优选的实施方式，所述反应I为甲醇和/或二甲醚与甲苯制对二甲苯。
作为一个进一步优选的实施方式，所述反应I为甲醇与甲苯制对二甲苯。
作为一种实施方式，所述反应II为甲醇和/或二甲醚与苯制甲苯联产对二甲苯和低碳烯烃。
作为一个优选的实施方式，所述反应II为甲醇和/或二甲醚与苯制甲苯联产对二甲苯。
作为一个优选的实施方式，所述反应II为甲醇和/或二甲醚与苯制对二甲苯联产低碳烯烃。
作为一个进一步优选的实施方式，所述反应II为甲醇和/或二甲醚与苯制对二甲苯。
作为一个更进一步优选的实施方式，所述反应II为甲醇与苯制对二甲苯。
作为一种实施方式，所述磷试剂选自有机膦化合物中的至少一种。优选地，所述磷试剂选自具有式I所示化学式的化合物中的至少一种：
Figure PCTCN2017082222-appb-000001
R1，R2，R3独立地选自C1～C10的烷基或C1～C10的烷氧基。
进一步优选地，所述式I中R1，R2，R3独立地选自C1～C5的烷基或C1～C5的烷氧基。
优选地，所述式I中R1、R2、R3中至少有一个选自C1～C10的烷氧基。进一步优选地，所述式I中R1，R2，R3中至少有一个选自C1～C5的烷氧基。更进一步优选地，所述式I中R1，R2，R3为相同的烷氧基。
作为一种实施方式，所述磷试剂选自三甲氧基膦、三乙氧基膦、三丙氧基膦、三丁氧基膦、甲基二乙氧基膦中的至少一种。
作为一种实施方式，所述硅烷化试剂选自有机硅化合物中的至少一种。优选地，所述硅烷化试剂选自具有式II所示化学式的化合物中的至少一种：
Figure PCTCN2017082222-appb-000002
R4，R5，R6，R7独立地选自C1～C10的烷基或C1～C10的烷氧基。
进一步优选地，所述式II中R4，R5，R6，R7独立地选自C1～C5的烷基或C1～C5的烷氧基。
优选地，所述式II中R4，R5，R6，R7中至少有一个选自C1～C10的烷氧基。进一步优选地，所述式II 中R4，R5，R6，R7中至少有一个选自C1～C5的烷氧基。更进一步优选地，所述式II中R4，R5，R6，R7为相同的烷氧基。
作为一种实施方式，所述硅烷化试剂选自硅酸四甲酯、硅酸四乙酯、硅酸四丙酯、硅酸四丁酯中的至少一种。
优选地，所述反应器选自固定床、流化床、移动床反应器中的至少一种。
优选地，所述分子筛为根据反应器类型成型后的成型分子筛；
所述成型分子筛由分子筛组成；或者
所述成型分子筛中含有分子筛和粘结剂。
作为可选择的实施方式，所述成型分子筛由分子筛压片破碎成型、将分子筛与粘结剂混合挤条后断条成型、将分子筛与粘结剂混合喷雾干燥成型中的一种方法制备得到。
优选地，所述分子筛选自具有MFI骨架结构的分子筛、具有MEL骨架结构的分子筛中的至少一种。
进一步优选地，所述分子筛为HZSM-5分子筛和/或HZSM-11分子筛。
优选地，所述分子筛中的硅铝比(原子比)Si/Al＝5～35。
优选地，所述催化剂的原位制备方法至少包括如下步骤：
(1)将成型分子筛置于反应器中；
(2)向反应器中通入含有改性剂的物料；
(3)停止向反应器中通入所述含有改性剂的物料，将反应器温度升至400℃以上并通入空气焙烧后，即得所述催化剂。
优选地，步骤(2)中的物料A含有原料中的至少一种和改性剂。
优选地，步骤(2)中的物料A含有甲苯和/或苯。
优选地，步骤(2)为向反应器中通入含有改性剂I的物料A；所述改性剂I含有磷试剂和硅烷化试剂。
进一步优选地，步骤(2)中的物料A含有改性剂I和甲苯。
优选地，步骤(2)为130℃～500℃条件下，向反应器中通入含有磷试剂和硅烷化试剂的物料A。
优选地，物料A含有磷试剂、硅烷化试剂和甲苯。
进一步优选地，步骤(2)所述物料A中磷试剂与硅烷化试剂的质量比为：
硅烷化试剂:磷试剂＝1:2至5:1。
物料A中，除磷试剂、硅烷化试剂和甲苯外，不排除含有其他可以提高磷试剂和硅烷化试剂对分子筛改性效率且不影响催化剂反应性能的试剂。优选地，步骤(2)所述物料A中磷试剂占物料A总重量的1wt％～10wt％；硅烷化试剂占物料A总重量的1wt％～40wt％，甲苯占物料A总重量的50wt％～98wt％。进一步优选地，步骤(2)所述物料A中磷试剂占物料A总重量的2wt％～10wt％；硅烷化试剂占物料A总重量的8wt％～40wt％，甲苯占物料A总重量的50wt％～90wt％。
本领域技术人员可根据实际生产中的具体要求，调整步骤(2)中向反应器中通入物料A的空速和时间。
优选地，步骤(2)中向反应器中通入物料A的总重量空速为0.5h-1～2h-1。
优选地，步骤(2)中向反应器中通入物料A的时间为30min～225min。
优选地，步骤(3)停止向反应器中通入物料A后，经非活性气体吹扫后，再进行升温焙烧。进一步优选地，所述非活性气体选自氮气、氦气、氩气中的至少一种。
优选地，步骤(3)中焙烧温度为500℃～700℃，焙烧时间为1～6小时。
优选地，步骤(2)为向反应器中通入含有改性剂II的物料B；所述改性剂II含有硅烷化试剂。
进一步优选地，步骤(2)中的物料B含有甲醇、甲苯、二甲醚中的至少一种和改性剂II。
优选地，步骤(2)为向反应器中通入含有改性剂III的物料；所述改性剂III含有硅烷化试剂和水蒸气。
优选地，所述催化剂的原位制备方法至少包括如下步骤：
(1)将成型分子筛置于反应器中；
(2)向反应器中通入含有硅烷化试剂的物料D；
(3)停止向反应器中通入物料D，将反应器温度升至500℃以上并通入空气焙烧；
(4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料E进行水蒸气处 理后，即得到所述催化剂。
进一步优选地，步骤(2)中的物料D含有硅烷化试剂和苯。
进一步优选地，步骤(2)物料D的重量空速为0.1h-1～1h-1，通入物料D的时间为0.1～5小时。
进一步优选地，步骤(2)物料D的重量空速为0.2h-1～0.4h-1，通入物料D的时间为0.5～2小时。
进一步优选地，步骤(4)中的物料E含有水蒸气和苯。
优选地，所述催化剂的原位制备方法至少包括如下步骤：
(1)将成型分子筛置于反应器中；
(2)向反应器中通入含有磷试剂和硅烷化试剂的物料F；
(3)停止向反应器中通入物料F，将反应器温度升至500℃以上并通入空气焙烧；
(4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料G进行水蒸气处理后，即得所述催化剂。
进一步优选地，步骤(2)中的物料F含有磷试剂、硅烷化试剂和苯。
进一步优选地，步骤(2)所述物料F中硅烷化试剂与磷试剂的质量比为：
硅烷化试剂：磷试剂＝1:2至5:1。
进一步优选地，步骤(3)中焙烧温度为500℃～700℃，焙烧时间为1～6小时。
进一步优选地，步骤(4)中所述非活性气体选自氮气、氦气、氩气中的至少一种。
进一步优选地，步骤(4)中水蒸气处理的温度为550℃～800℃，处理时间为1～10小时。
进一步优选地，步骤(4)中的物料G含有水蒸气和苯。
优选地，步骤(4)物料G中水蒸气的重量空速为0.5h-1～5h-1。进一步优选地，步骤(4)物料G中水蒸气的重量空速为1h-1～3h-1。
含有水蒸气的物料G可以为100％的水蒸气，也可以非活性气体和/或其他可以提高(调节)水蒸气改性效率且不影响催化剂反应性能的试剂。
优选地，步骤(4)中水蒸气处理的温度为550℃～800℃，处理时间为1～10小时。
优选地，步骤(2)所述物料A中磷试剂占物料A总重量的1wt％～10wt％；硅烷化试剂占物料A总重量的1wt％～40wt％，甲苯占物料A总重量的50wt％～98wt％。
优选地，步骤(2)所述物料F中磷试剂占物料F总重量的1wt％～10wt％；硅烷化试剂占物料F总重量的1wt％～40wt％，苯占物料F总重量的50wt％～98wt％。
优选地，步骤(3)中焙烧温度为500℃～700℃，焙烧时间为1～6小时。
优选地，步骤(2)为130℃～500℃条件下，向反应器中通入含有改性剂的的物料。
优选地，步骤(2)为200℃～400℃条件下，向反应器中通入含有改性剂的物料。
根据本申请的又一方面，提供一种甲醇和/或二甲醚与甲苯制低碳烯烃联产对二甲苯(反应I)的方法，其特征在于，将含有甲醇和/或二甲醚与甲苯的原料在反应器中与根据上述任意所述方法原位制备得到的制低碳烯烃联产对二甲苯的催化剂接触，制备低碳烯烃联产对二甲苯。即，在改性后催化剂焙烧完成后，直接从焙烧温度降至反应温度，开始进行制低碳烯烃联产对二甲苯的反应。与化工领域固有的生产方式相比，节省了催化剂改性后的洗涤分离过程、焙烧后降至室温的催化剂冷却过程、催化剂运输步骤、催化剂装填步骤、催化剂装入反应器中后需要高温预活化的步骤等，大幅提高了生产效率，避免了在上述已节省步骤中可能出现的安全问题；更重要的是，反应器从焙烧温度降温至反应温度即可开始反应，热能得到充分利用，大幅节省了生产中的能耗。
该实现反应I的方法，将含有甲醇和/或二甲醚与甲苯的原料在反应器中与上述一个方面所述方法中原位和在线制备得到的反应I的催化剂接触，制低碳烯烃联产对二甲苯；
反应I：甲醇和/或二甲醚与甲苯制低碳烯烃联产对二甲苯。
作为一个优选的实施方式，所述反应I为甲醇和/或二甲醚与甲苯制对二甲苯。
作为一个优选的实施方式，所述反应I为甲醇与甲苯制对二甲苯。
作为一个优选的实施方式，将磷试剂和硅烷化试剂与反应器中的分子筛接触，原位制备所述反应I的催化剂；
所述反应器为发生反应I的反应器。
优选地，所述原料与所述催化剂接触，反应温度为350℃～650℃。
优选地，所述原料与所述催化剂接触，反应温度为400℃～500℃。
优选地，所述含有甲醇和/或二甲醚、甲苯的原料中，甲醇和/或二甲醚与甲苯的比如下：
甲醇和二甲醚的碳原子数：甲苯的摩尔数＝0.5～10。
作为可选择的实施方式，所述反应原料含有甲醇和甲苯，由于甲醇在催化剂上可能转化为二甲醚，即甲醇和二甲醚在原料中的作用是相通的，所以实际的通入的反应原料含有甲醇和甲苯，往往在反应器的催化剂上是同时存在甲醇、二甲醚和甲苯。以下原料虽以甲醇和甲苯为例，但不排除原料中含有二甲醚的情况。在计算中二甲醚的碳原子摩尔数即相当于甲醇的摩尔数。
所述含有甲醇和甲苯的原料中，甲醇与甲苯的摩尔比为甲醇：甲苯＝0.5～20：1。优选地，所述含有甲醇和甲苯的原料中，甲醇与甲苯的摩尔比为甲醇：甲苯＝1～15:1。进一步优选地，所述含有甲醇和甲苯的原料中，甲醇与甲苯的摩尔比为甲醇：甲苯＝5～15:1。实际生产中，可根据具体生产要求，通过调节原料中甲醇和甲苯的比例，来调节产物中低碳烯烃和对二甲苯之间的比例。大体上，当提高原料中甲醇/甲苯比例时，产物中烯烃含量升高；当减低原料中甲醇/甲苯比例时，产物中对二甲苯含量升高。
优选地，含有甲醇和甲苯的原料的总重量空速为1h-1～3h-1。
优选地，物流I在反应系统中与催化剂接触，得到物流II，从物流II中分离出C4烯烃或C5+链烃返回所述反应系统，从物流II中分离出低碳烯烃和对二甲苯作为产品；
所述物流I含有甲醇和/或二甲醚、甲苯。
进一步优选地，所述反应系统包括第一反应区和第二反应区，物流I在第一反应区内与催化剂接触得到物流II-A，从物流II-A中分离出C4烯烃或C5+链烃通入第二反应区内与催化剂接触得到物流II-B；
从物流II-B中分离出C4烯烃或C5+链烃返回第二反应区；
物流II-A和物流II-B中分离出的低碳烯烃和对二甲苯作为产品。
进一步优选地，所述反应系统包括第一反应区和第二反应区，所述物流I在第一反应区内与催化剂接触得到物流II-A，所述物流II-A通入分离系统并分离出C4烯烃、低碳烯烃和对二甲苯；
将所述分离系统中分离出的C4烯烃通入第二反应区内与催化剂接触得到物流II-B，将所述物流II-B通入所述分离系统；
所述分离系统中分离出的低碳烯烃和对二甲苯作为产品。
进一步优选地，所述反应系统包括第一反应区和第二反应区，所述物流I在第一反应区内与催化剂接触得到物流II-A，所述物流II-A通入分离系统，所述分离系统输出C5+链烃、低碳烯烃和对二甲苯；
将所述分离系统中分离出的C5+链烃通入第二反应区内与催化剂接触得到物流II-B，将所述物流II-B通入所述分离系统；
所述分离系统中输出的低碳烯烃和对二甲苯作为产品。
优选地，所述反应系统包括第一反应区和第二反应区，所述第一反应区和第二反应区均含有催化剂A；
所述催化剂A为磷试剂和硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
(A1)在130℃～500℃下，将磷试剂和硅烷化试剂引入装有HZSM-5分子筛的第一反应区中；
(A2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂A。
优选地，所述反应系统包括第一反应区和第二反应区，所述第一反应区含有催化剂A，所述第二反应区含有催化剂B。
进一步优选地，所述催化剂A为磷试剂和硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
(A1)在130℃～500℃下，将磷改性试剂、硅烷化试剂和甲苯的混合物引入装有HZSM-5分子筛的第一反应区中；
(A2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂A。
进一步优选地，所述催化剂B为硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
(B1)在120℃～250℃下，将硅烷化试剂和甲醇的混合物引入装有HZSM-5分子筛的第二反应区中；
(B2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂B。
优选地，所述反应系统包括一个反应器，或多个通过串联和/或并联方式连接的反应器。
进一步优选地，所述反应器为固定床、流化床或移动床中的至少一种。
优选地，所述反应系统包括第一反应区和第二反应区，所述第一反应区和所述第二反应区在同一个反应器内。
优选地，所述反应系统包括第一反应区和第二反应区，所述第一反应区包含一个反应器或多个通过串联和/或并联方式连接的反应器，所述第二反应区包含一个反应器或多个通过串联和/或并联方式连接的反应器。
进一步优选地，所述第一反应区和所述第二反应区之间通过串联或并联方式连接。
本申请的一种实施方式中，第一反应区进行甲醇转化反应和甲苯甲醇烷基化反应，第二反应区进行择形芳构化反应。
优选地，所述原料的总进料空速为0.1h-1～10h-1。
优选地，所述原料的总进料空速为0.8h-1～3h-1。
优选地，所述原料中甲苯的摩尔含量为5mol％～50mol％。
优选地，所述原料中甲苯的摩尔含量为20mol％～40mol％。
优选地，将磷试剂和硅烷化试剂与反应器中的分子筛接触，原位制备所述制低碳烯烃联产对二甲苯的催化剂；
所述反应器为制低碳烯烃联产对二甲苯的反应器。
根据本申请的又一方面，提供一种甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种(反应II)的方法，其特征在于，将含有甲醇和/或二甲醚与苯的原料在反应器中与根据上述任意所述方法原位制备得到的反应II的催化剂接触，制备甲苯、对二甲苯和/或低碳烯烃。即，在完成改性剂I至改性剂IV的改性后，直接从改性温度降至反应温度，开始进行甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种的反应。与化工领域固有的生产方式相比，节省了催化剂改性后的洗涤分离过程、焙烧后降至室温的催化剂冷却过程、催化剂运输步骤、催化剂装填步骤、催化剂装入反应器中后需要高温预活化的步骤等，大幅提高了生产效率，避免了在上述已节省步骤中可能出现的安全问题；更重要的是，反应器从焙烧温度降温至反应温度即可开始反应，热能得到充分利用，大幅节省了生产中的能耗。
该实现反应II的方法，将含有甲醇和/或二甲醚与苯的原料在反应器中与根据权利要求1至40任一项所述方法原位和在线制备得到的反应II的催化剂接触，制甲苯联产对二甲苯；
反应II：甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种。
优选地，将硅烷化试剂和水蒸气与反应器中的分子筛接触，原位制备所述反应II的催化剂；
所述反应器为所述反应II的反应器。
在完成水蒸气改性后，直接从水蒸气改性温度降至反应温度，开始进行甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯的反应。与化工领域固有的生产方式相比，节省了催化剂改性后的洗涤分离过程、焙烧后降至室温的催化剂冷却过程、催化剂运输步骤、催化剂装填步骤、催化剂装入反应器中后需要高温预活化的步骤等，大幅提高了生产效率，避免了在上述已节省步骤中可能出现的安全问题；更重要的是，反应器从焙烧温度降温至反应温度即可开始反应，热能得到充分利用，大幅节省了生产中的能耗。
本申请的原料苯和甲醇，其中甲醇包括甲醇和/或二甲醚进料的形式。由于甲醇在催化剂上可能转化为二甲醚，即甲醇和二甲醚在原料中的作用是相通的，所以实际的反应原料通入的是甲醇和甲苯，往往在反应器的催化剂上是同时存在甲醇、二甲醚和甲苯的。以下原料虽以甲醇和甲苯为例，但不排除原料中含有二甲醚的情况。在计算中二甲醚的碳原子摩尔数即相当于甲醇的摩尔数。
本申请中，苯、甲醇制甲苯联产对二甲苯和低碳烯烃，其中原料含有苯和甲醇，其中甲醇包括甲醇和/或二甲醚的情况。如无特别说明，本申请中的甲醇均可以全部或部分的被二甲醚代替，涉及甲醇的量，也可以将二甲醚换算为相同碳原子数的甲醇进行计算。
进一步优选地，所述反应器选自固定床、流化床、移动床反应器中的至少一种。
优选地，所述反应II的反应温度为350℃～600℃。
优选地，所述反应II的反应温度为400℃～500℃。
所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：苯＝0.5～10：1。优选地，所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：苯＝1～5:1。进一步优选地，所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：甲苯＝1～2:1。实际生产中，可根据具体生产要求，通过调节原料中甲醇和苯的比例，来调节产物中低碳烯烃和甲苯、对二甲苯之间的比例。大体上，当提高原料中甲醇/苯比例时，产物中烯烃含量升高；当减低原料中甲醇/苯比例时，产物中甲苯和对二甲苯含量升高。
优选地，所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：苯＝(0.5～2):1。进一步优选地，所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：苯＝(1～1.5):1。
优选地，含有甲醇和苯的原料的总重量空速为1h-1～4h-1。
优选地，所述反应II的催化剂的原位制备方法至少包括如下步骤：
(1)将成型分子筛置于反应器中；
(2)向反应器中通入含有硅烷化试剂和苯的物料D；
(3)停止向反应器中通入物料D，将反应器温度升至500℃以上并通入空气焙烧；
(4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料E进行水蒸气处理后，即得到所述反应II的催化剂。
优选地，所述反应II的催化剂的原位制备方法至少包括如下步骤：
(1)将成型分子筛置于反应器中；
(2)向反应器中通入含有磷试剂、硅烷化试剂和苯的物料F；
(3)停止向反应器中通入物料F，将反应器温度升至500℃以上并通入空气焙烧；
(4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料G进行水蒸气处理后，即得所述反应II的催化剂。
本申请中，反应原料含有甲醇，其中原料甲醇包括甲醇和/或二甲醚的情况。如无特别说明，本申请中的甲醇均可以全部或部分的被二甲醚代替，涉及甲醇的量，也可以将二甲醚换算为相同碳原子数的甲醇进行计算。
本申请中，所述C1～C10、C1～C5等均指基团所包含的碳原子数。
本申请中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。所述烷烃化合物包括直链烷烃、支链烷烃、环烷烃、带有支链的环烷烃。
本申请中，所述“烷氧基”是由烷基醇类化合物分子上失去羟基上的氢原子所形成的基团。
本申请中，所述“低碳烯烃”是指乙烯和丙烯。
本申请中，所述“甲醇和/或二甲醚与甲苯”，包括三种情况：甲醇和甲苯；或者二甲醚和甲苯；或者甲醇、二甲醚和甲苯。
本申请中，所述“甲醇和/或二甲醚与苯”，包括三种情况：甲醇和苯；或者二甲醚和苯；或者甲醇、二甲醚和苯。
如无特别说明，本申请中的甲醇均可以全部或部分的被二甲醚代替，涉及甲醇的量，也可以将二甲醚换算为相同碳原子数的甲醇进行计算。
本申请的有益效果包括但不限于：
(1)本申请所提供的制甲苯、对二甲苯、低碳烯烃中至少一种催化剂的原位制备方法，打破了现有化工领域中，先在催化剂生产单位制备好成品催化剂，再运输至化工生产单位，装填好催化剂再开车生产的传统生产模式，克服了多相催化领域大规模工业化生产中的技术偏见。
(2)本申请所提供的制甲苯、对二甲苯、低碳烯烃中至少一种催化剂的原位制备方法，简化了整个化工生产的流程，节省了催化剂制备和转移步骤，易于操作。
(3)本申请所提供的制甲苯、对二甲苯、低碳烯烃中至少一种的方法，与化工领域固有的生产方式相比，节省了催化剂改性后的洗涤分离过程、焙烧后降至室温的催化剂冷却过程、催化剂运输步骤、催化剂装填步骤、催化剂装入反应器中后需要高温预活化的步骤等，大幅提高了生产效率，避免了在上述已节省步骤中可能出现的安全问题；更重要的是，反应器从焙烧温度降温至反应温度即可开始反应，热能得到充分利用，大幅节省了生产中的能耗。
(4)本申请所提供的制甲苯、对二甲苯、低碳烯烃中至少一种的方法，从催化剂制备到反应进行，在一个系统中原位完成，在大规模化工生产中，有利于催化剂制备过程中废弃物的回收和循环利用，环境友好。
(5)本申请所提供的甲醇和/或二甲醚与甲苯制甲苯、对二甲苯、低碳烯烃中至少一种的方法，甲醇转化率100％，对二甲苯在二甲苯中的选择性高达99.6wt％以上。
(6)本申请所提供的甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种的方法，甲醇转化率100％，芳烃产物中(甲苯+对二甲苯)选择性>85wt％，二甲苯产物中对二甲苯选择性>99.6wt％，C8芳烃中对二甲苯选择性>90wt％。
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图4是应用本申请一种实施方式的工艺流程图。
图5是应用本申请一种实施方式的工艺流程图。
图6是应用本申请一种实施方式的工艺流程图。
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。
如无特殊说明，本申请所用原料和试剂均来自商业购买，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，催化剂磨损指数在沈阳合兴机械电子有限公司的MS-C型磨损指数测定仪上测定。
实施例中，固定床反应器内径为1.5cm；固定流化床反应器内径为3cm；循环流化床反应器内径为12cm。
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＝30)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FXHZSM-5-A。
将100g HZSM-5沸石分子筛原粉(南开大学催化剂厂，Si/Al＝5)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FXHZSM-5-B。
将100g HZSM-5沸石分子筛原粉(南开大学催化剂厂，Si/Al＝10)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FXHZSM-5-C。
实施例2固定床用HZSM-11成型分子筛样品的制备
将100g HZSM-11沸石分子筛原粉(南开大学催化剂厂，Si/Al＝35)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FXHZSM-11-A。
将100g HZSM-11沸石分子筛原粉(南开大学催化剂厂，Si/Al＝12)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FXHZSM-11-B。
实施例3流化床用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＝30)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HZSM-5沸石分子筛原粉、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 PCTCN2017082222-appb-000003
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HZSM-5成型分子筛，记为FLHZSM-5-A。
实施例4流化床用HZSM-5成型分子筛样品的制备
具体的制备条件和步骤同实施例3，不同之处在于，原料HZSM-5沸石分子筛原粉的用量为10kg，得到的微球颗粒样品粒径分布20～120μm，磨损指数为1.2，记为FLHZSM-5-B。
具体的制备条件和步骤同实施例3，不同之处在于，原料HZSM-5沸石分子筛原粉的硅铝比Si/Al＝10，得到的微球颗粒样品粒径分布20～100μm，磨损指数为1.2，记为FLHZSM-5-C。
实施例5固定床催化剂FXCAT-1的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40～60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，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200℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫后，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-1。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表1所示。
表1
催化剂 FXCAT-1
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 36.09
对二甲苯在二甲苯异构体中选择性(wt％) 99.64
产物分布(wt％)  
链烃 77.74
苯 0.06
乙苯 0.25
对二甲苯 19.26
间二甲苯 0.04
邻二甲苯 0.03
C9+芳烃 2.61
链烃产物分布(wt％)  
CH4 1.26
C2H4 39.84
C2H6 0.1
C3H6 35.32
C3H8 0.89
C4 11.99
C5 5.06
C6+ 5.53
C2H4+C3H6 75.16
实施例6固定床催化剂FXCAT-2的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝10:40:50，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料45min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-2。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表2所示。
表2
催化剂 FXCAT-2
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 36.68
对二甲苯在二甲苯异构体中选择性(wt％) 99.64
产物分布(wt％)  
链烃 77.59
苯 0.08
乙苯 0.29
对二甲苯 19.18
间二甲苯 0.04
邻二甲苯 0.03
C9+芳烃 2.79
链烃产物分布(wt％)  
CH4 1.23
C2H4 39.76
C2H6 0.13
C3H6 35.25
C3H8 0.96
C4 12.06
C5 5.11
C6+ 5.5
C2H4+C3H6 75.01
实施例7固定床催化剂FXCAT-3的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝2:8:90，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料225min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-3。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原 料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表3所示。
表3
催化剂 FXCAT-3
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 35.59
对二甲苯在二甲苯异构体中选择性(wt％) 99.69
产物分布(wt％)  
链烃 77.9
苯 0.06
乙苯 0.21
对二甲苯 19.19
间二甲苯 0.03
邻二甲苯 0.03
C9+芳烃 2.58
链烃产物分布(wt％)  
CH4 1.31
C2H4 39.91
C2H6 0.09
C3H6 35.46
C3H8 0.83
C4 11.91
C5 5.01
C6+ 5.48
C2H4+C3H6 75.37
实施例8固定床催化剂FXCAT-4的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-4。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表4所示。
表4
催化剂 FXCAT-4
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 35.20
对二甲苯在二甲苯异构体中选择性(wt％) 99.90
产物分布(wt％)  
链烃 77.58
苯 0.09
乙苯 0.35
对二甲苯 20.33
间二甲苯 0.01
邻二甲苯 0.01
C9+芳烃 1.63
链烃产物分布(wt％)  
CH4 1.11
C2H4 41.57
C2H6 0.1
C3H6 36.98
C3H8 1.18
C4 12.21
C5 3.43
C6+ 3.42
C2H4+C3H6 78.55
实施例9固定床催化剂FXCAT-5的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至450℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-5。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表5所示。
表5
催化剂 FXCAT-5
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 35.80
对二甲苯在二甲苯异构体中选择性(wt％) 99.63
产物分布(wt％)  
链烃 75.29
苯 0.07
乙苯 0.35
对二甲苯 21.32
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 2.89
链烃产物分布(wt％)  
CH4 1.08
C2H4 40.96
C2H6 0.11
C3H6 36.49
C3H8 1.41
C4 12.65
C5 3.76
C6+ 3.54
C2H4+C3H6 77.45
实施例10固定床催化剂FXCAT-6的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至150℃。三甲氧基磷、硅酸四甲酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四甲酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四甲酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-6。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表6所示。
表6
催化剂 FXCAT-6
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 34.79
对二甲苯在二甲苯异构体中选择性(wt％) 99.95
产物分布(wt％)  
链烃 78.37
苯 0.08
乙苯 0.21
对二甲苯 19.98
间二甲苯 0
邻二甲苯 0.01
C9+芳烃 1.35
链烃产物分布(wt％)  
CH4 0.96
C2H4 41.03
C2H6 0.11
C3H6 37.96
C3H8 1.03
C4 11.01
C5 4.08
C6+ 3.82
C2H4+C3H6 78.99
实施例11固定床催化剂FXCAT-7的制备及反应评价
在微型固定床反应装置内在线制备甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-11-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-7。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表7所示。
表7
催化剂 FXCAT-7
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 33.58
对二甲苯在二甲苯异构体中选择性(wt％) 99.90
产物分布(wt％)  
链烃 77.79
苯 0.07
乙苯 0.28
对二甲苯 19.88
间二甲苯 0.01
邻二甲苯 0.01
C9+芳烃 1.96
链烃产物分布(wt％)  
CH4 0.85
C2H4 40.51
C2H6 0.11
C3H6 37.79
C3H8 0.83
C4 10.57
C5 4.53
C6+ 4.81
C2H4+C3H6 78.30
实施例12流化床催化剂FLCAT-1的制备及反应评价
在固定流化床反应装置内在线制备甲醇甲苯制对二甲苯联产低碳烯烃流化床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将10g实施例3中制备的成型分子筛样品FLHZSM-5-A装入固定流化床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯流化床催化剂，命名为FLCAT-1。然后，氮气气氛下降温至反应温度450℃，测试甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应60min时取样分析。反应结果如表8所示。
表8
催化剂 FLCAT-1
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 31.33
对二甲苯在二甲苯异构体中选择性(wt％) 99.61
产物分布(wt％)  
链烃 76.56
苯 0.09
乙苯 0.31
对二甲苯 20.25
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 2.71
链烃产物分布(wt％)  
CH4 1.37
C2H4 40.78
C2H6 0.12
C3H6 35.72
C3H8 1.5
C4 11.94
C5 4.52
C6+ 4.05
C2H4+C3H6 76.50
实施例13固定床催化剂FXCAT-8的制备及反应
采用微型固定床反应装置，以甲醇甲苯为原料制低碳烯烃联产对二甲苯。
原位制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入微型固定床反应器，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90min后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-8。然后，氮气气氛下降温至反应温度450℃，进行甲醇甲苯制低碳烯烃联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表9所示。
表9
催化剂 FXCAT-8
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 35.20
链烃产物中(C2H4+C3H6)选择性(wt％) 73.55
对二甲苯在二甲苯异构体中选择性(wt％) 99.71
烃类产物分布(wt％)  
CH4 0.84
C2H4 30.09
C2H6 0.08
C3H6 25.84
C3H8 0.90
C4烯烃 9.25
C4烷烃 1.55
C5+链烃 7.49
苯 0.09
乙苯 0.35
对二甲苯 20.33
间二甲苯 0.04
邻二甲苯 0.02
C9+芳烃 3.14
实施例14固定床催化剂FXCAT-9的制备及反应
根据本申请的一种实施方式，如图1所示，物流I包括甲醇和甲苯，以甲醇甲苯为原料制低碳烯烃联产对二甲苯。
反应系统中装有5g(40-60目)实施例1中制备的成型分子筛样品FXHZSM-5-A，先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90分钟后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇 甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-9。
物流I通入反应系统与催化剂FXCAT-9接触并反应。含有产物的物流II离开反应系统并进入分离系统，分离出低碳烯烃(乙烯和丙烯)、C4烯烃、对二甲苯和其他组分。其中，C4烯烃返回反应系统，低碳烯烃(乙烯和丙烯)和对二甲苯作为产品。其他组分作为副产物。
反应条件如下：原料用微量进料泵进料，物流I的原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，反应温度450℃，常压。产物通过在线Agilent7890气相色谱进行分析，如表10所示。
表10
催化剂 FXCAT-9
反应温度(℃) 450
甲醇转化率(％) 100
甲苯转化率(％) 37.01
链烃产物中(C2H4+C3H6)选择性(wt％) 82.19
对二甲苯在二甲苯异构体中选择性(wt％) 99.62
烃类产物分布(wt％)  
CH4 0.99
C2H4 31.87
C2H6 0.19
C3H6 27.54
C3H8 1.87
C4烷烃 1.62
C5+链烃 8.2
苯 0.58
乙苯 0.46
对二甲苯 23.1
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 3.5
实施例15固定床催化剂FXCAT-10的制备及反应
根据本申请的一种实施方式，如图2所示，物流I包括二甲醚和甲苯，以二甲醚甲苯为原料制低碳烯烃联产对二甲苯。
与实施例14的区别在于分离系统，其余与实施例14相同，制得固定床催化剂，命名为FXCAT-10。本实施例的分离系统分离出C1～3链烃、C4烯烃、C4烷烃、C5+链烃、芳烃。其中，C4烯烃返回反应系统。从C1～3链烃中分离出乙烯和丙烯，作为低碳烯烃产品。从芳烃中分离出对二甲苯，作为产品。其他组分作为副产物。反应结果与实施例14一致(偏差不超过±1％)。
实施例16固定床催化剂FXCAT-11和流化床FLCAT-12的制备及反应
根据本申请的一种实施方式，按照图3中所示的工艺流程图，物流I包括甲醇和甲苯，以甲醇甲苯为原料制低碳烯烃联产对二甲苯。
第一反应区为10个固定床并联，第二反应区为一个流化床。
将50g(40-60目)实施例1中制备的成型分子筛样品FXHZSM-5-A装入第一反应区的10个固定床内，每个固定床中装填5g，每个固定床先经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90分钟后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-11。
将50g(40-60目)实施例4中制备的微球分子筛样品FLHZSM-5-B装入第二反应区的流化床内，先经500mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯和甲醇的混合液用微 量进料泵进料，汽化后进入第二反应区的流化床内，硅酸四乙酯:甲醇(重量比)＝40:60，硅酸四乙酯和甲醇的总重量空速2h-1，常压。进料3小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FLCAT-12。
第一反应区进行甲醇转化反应和甲苯甲醇烷基化反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，反应温度450℃，常压。物流I通入第一反应区的固定床与催化剂FXCAT-11接触，得到物流II-A，物流II-A离开第一反应区并进入分离系统。从分离系统中分离出乙烯、丙烯、C4烯烃和对二甲苯。将分离系统中分离出的C4烯烃通入第二反应区的流化床内与催化剂FXCAT-12接触，第二个反应区进行流化床择形芳构化反应，反应温度450℃。第二个反应区得到物流II-B，物流II-B离开第二反应区并进入分离系统。从分离系统中分离出的乙烯和丙烯作为低碳烯烃产品，对二甲苯作为产品。其他组分作为副产物。
第二反应区的烃类产物通过在线Agilent7890气相色谱进行分析，如表11所示；扣除C4烯烃组分后产品分布如表12所示。第一个反应区和第二个反应区混合烃类产物通过在线Agilent7890气相色谱进行分析，扣除C4烯烃组分后产品分布如表13所示。
表11
C4烯烃转化率(％) 83.25
对二甲苯在二甲苯异构体中选择性(wt％) 99.56
烃类产物分布(wt％)  
CH4 0.74
C2H4 0.60
C2H6 1.02
C3H6 0.26
C3H8 9.55
C4烯烃 16.76
C4烷烃 0.04
C5+ 0.23
苯 4.94
甲苯 35.74
乙苯 0.90
对二甲苯 27.07
间二甲苯 0.07
邻二甲苯 0.05
C9+芳烃 2.03
表12
C4烯烃转化率(％) 83.25
对二甲苯在二甲苯异构体中选择性(wt％) 99.56
烃类产物分布(wt％)  
CH4 0.89
C2H4 0.72
C2H6 1.22
C3H6 0.31
C3H8 11.47
C4烷烃 0.05
C5+链烃 0.28
苯 5.93
甲苯 42.94
乙苯 1.08
对二甲苯 32.52
间二甲苯 0.08
邻二甲苯 0.06
C9+芳烃 2.44
表13
甲醇转化率(％) 100
甲苯转化率(％) 38.08
链烃产物中(C2H4+C3H6)选择性(wt％) 82.44
对二甲苯在二甲苯异构体中选择性(wt％) 99.69
烃类产物分布(wt％)  
CH4 0.94
C2H4 31.68
C2H6 0.19
C3H6 27.18
C3H8 1.85
C4烷烃 1.64
C5+链烃 7.90
苯 0.58
乙苯 0.46
对二甲苯 24.00
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 3.50
实施例17催化剂FXCAT-13和FLCAT-14的制备及反应
根据本申请的一种实施方式，如图4所示，物流I包括二甲醚、甲醇和甲苯，以二甲醚、甲醇和甲苯为原料制低碳烯烃联产对二甲苯。
与实施例16的区别在于第一反应区为1个固定床，装填50g分子筛样品FXHZSM-5-A。还有分离系统不同，本实施例的分离系统分离出C1～3链烃、C4烯烃、C4烷烃、C5+链烃、芳烃。其中，C4烯烃返回第二反应区。从C1～3链烃中分离出乙烯和丙烯，作为低碳烯烃产品。从芳烃中分离出对二甲苯，作为产品。其他组分作为副产物。其余与实施例23相同，制得固定床催化剂命名为FXCAT-13，制得流化床催化剂命名为FLCAT-14。反应结果与实施例16一致(偏差不超过±1％)。
实施例18固定床催化剂FXCAT-15的制备及反应
根据本申请的一种实施方式，按照图5中所示的工艺流程图，以甲醇和甲苯为原料制低碳烯烃联产对二甲苯。物流I包括甲醇和甲苯。
反应系统为两个固定床如图5所示的反应系统部位上下串联布置，采用分段进料的方式，物流I从上部的固定床进料，回炼的C5+链烃进入下部的固定床。
将10g(40-60目)实施例1中制备的成型分子筛样品FXHZSM-5-A分别装入两个固定床中，两个固定床装填量相同，均为5g。催化剂制备过程：每个固定床经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90分钟后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。原位制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，记为FXCAT-15。
物流I进入反应系统上部的固定床反应器，与催化剂FXCAT-15接触并进行甲醇转化反应和甲苯甲醇择形烷基化反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，反应温度450℃，常压。
含有产物的物流II离开反应系统并进入分离系统，分离出C1～4链烃、C5+链烃和芳烃。其中，C5+链烃返 回反应系统下部的固定床，与催化剂FXCAT-15接触并进行裂解、择形芳构化等反应，反应系统下部的固定床反应温度630℃。从C1～4链烃中分离出乙烯和丙烯，作为低碳烯烃产品。从芳烃中分离出对二甲苯，作为产品。其他组分作为副产物。
产物通过在线Agilent7890气相色谱进行分析，如表14所示。
表14
甲醇转化率(％) 100
甲苯转化率(％) 36.55
链烃中(C2H4+C3H6)选择性 80.83
对二甲苯在二甲苯异构体中选择性(wt％) 99.70
烃类产物分布(wt％)  
CH4 1.11
C2H4 33.02
C2H6 0.31
C3H6 27.25
C3H8 1.17
C4 11.7
苯 0.65
乙苯 0.39
对二甲苯 21.05
间二甲苯 0.04
邻二甲苯 0.02
C9+芳烃 3.29
实施例19固定床催化剂FXCAT-16的制备及反应
根据本申请的一种实施方式，按照图6中所示的工艺流程图，以甲醇甲苯为原料制低碳烯烃联产对二甲苯。物流I包括甲醇和甲苯。
第一反应区为一个固定床，第二反应区为一个固定床。
分别将5g(40-60目)实施例1中制备的成型分子筛样品FXHZSM-5-A装入第一反应区的固定床和第二反应区的固定床，催化剂制备过程相同：每个固定床反应器中的催化剂经50mL/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基磷、硅酸四乙酯和甲苯的混合液用微量进料泵进料，三甲氧基磷:硅酸四乙酯:甲苯(重量比)＝5:20:75，三甲氧基磷、硅酸四乙酯和甲苯的总重量空速1h-1，常压。进料90分钟后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。按照上述过程分别在第一个固定床反应区和第二个固定床反应区在线制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，记为FXCAT-16。
物流I进入第一反应区的固定床与催化剂FXCAT-16接触并进行甲醇转化反应和甲苯甲醇择形烷基化反应，反应条件如下：原料用微量进料泵进料，原料甲醇:甲苯(摩尔比)＝10:1，甲醇和甲苯总重量空速2h-1，反应温度450℃，常压。含有产物的物流II-A离开第一反应区的固定床并进入分离系统。分离系统分离出C1～4链烃、C5+链烃和芳烃。
从分离系统分离出的C5+链烃进入第二反应区的固定床，与催化剂FXCAT-16接触并进行裂解、择形芳构化等反应，第二反应区的固定床反应温度630℃，含有产物的物流II-B离开第二反应区的固定床并进入分离系统。
从分离系统分离出的C1～4链烃中分离出乙烯和丙烯，作为低碳烯烃产品。从芳烃中分离出对二甲苯，作为产品。其他组分作为副产物。
第二反应区的烃类产物通过在线Agilent7890气相色谱进行分析，如表15所示；扣除C5+链烃组分后产品分布如表16所示。第一个反应区和第二个反应区混合烃类产物通过在线Agilent7890气相色谱进行分析， 扣除C5+链烃组分后产品分布如表17所示。
表15
C5+链烃转化率(％) 93.92
对二甲苯在二甲苯异构体中选择性(wt％) 99.70
烃类产物分布(wt％)  
CH4 4.32
C2H4 20.83
C2H6 3.02
C3H6 23.37
C3H8 3.45
C4 8.51
C5+ 6.08
苯 7.46
甲苯 11.07
乙苯 0.52
对二甲苯 9.96
间二甲苯 0.03
邻二甲苯 0.02
C9+芳烃 1.36
表16
C5+链烃转化率(％) 93.92
对二甲苯在二甲苯异构体中选择性(wt％) 99.70
烃类产物分布(wt％)  
CH4 4.60
C2H4 22.18
C2H6 3.22
C3H6 24.88
C3H8 3.67
C4 9.06
苯 7.94
甲苯 11.79
乙苯 0.55
对二甲苯 10.60
间二甲苯 0.03
邻二甲苯 0.02
C9+芳烃 1.45
表17
甲醇转化率(％) 100
甲苯转化率(％) 37.11
链烃中(C2H4+C3H6)选择性 80.81
对二甲苯在二甲苯异构体中选择性(wt％) 99.70
烃类产物分布(wt％)  
CH4 1.18
C2H4 32.06
C2H6 0.31
C3H6 27.95
C3H8 1.17
C4 11.59
苯 0.65
乙苯 0.39
对二甲苯 21.35
间二甲苯 0.04
邻二甲苯 0.02
C9+芳烃 3.29
实施例20流化床催化剂FXCAT-17的制备及反应
根据本申请的一种实施方式，流程图与实施例19相同，如图6所示。区别在于原料、反应器不同。
本实施例中物流I包括二甲醚、甲醇和甲苯，以二甲醚、甲醇和甲苯为原料制低碳烯烃联产对二甲苯。
本实施例中第一反应区为一个流化床，装填1kg实施例4中的分子筛样品FLHZSM-5-C。第二反应区为一个流化床，装填1kg相同的实施例4中的分子筛样品FLHZSM-5-C。催化剂制备过程：每个流化床反应器中的催化剂经10L/min氮气在550℃下处理1小时，然后氮气气氛下降温至300℃。余与实施例19相同，制得固定床催化剂命名为FLCAT-17。反应结果与实施例19一致(偏差不超过±1％)。
实施例21固定床催化剂FXCAT-18的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-18。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表18所示。
表18
催化剂 FXCAT-18
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.93
二甲苯产物中对二甲苯选择性(wt％) 99.63
C8芳烃产物中对二甲苯选择性(wt％) 91.06
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.16
产物分布(wt％)  
C1-C6+链烃 14.72
甲苯 53.09
乙苯 2.57
对二甲苯 27.21
间二甲苯 0.06
邻二甲苯 0.04
C9+芳烃 2.31
实施例22固定床催化剂FXCAT-19的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.1h-1，常压。进料2小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-19。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表19所示。
表19
催化剂 FXCAT-19
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.43
二甲苯产物中对二甲苯选择性(wt％) 99.78
C8芳烃产物中对二甲苯选择性(wt％) 91.33
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.37
产物分布(wt％)  
C1-C6+链烃 14.81
甲苯 53.32
乙苯 2.51
对二甲苯 27.07
间二甲苯 0.04
邻二甲苯 0.02
C9+芳烃 2.23
实施例23固定床催化剂FXCAT-20的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.4h-1，常压。进料0.5小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-20。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表20所示。
表20
催化剂 FXCAT-20
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 36.37
二甲苯产物中对二甲苯选择性(wt％) 99.67
C8芳烃产物中对二甲苯选择性(wt％) 90.95
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 93.99
产物分布(wt％)  
C1-C6+链烃 14.61
甲苯 52.92
乙苯 2.63
对二甲苯 27.34
间二甲苯 0.05
邻二甲苯 0.04
C9+芳烃 2.41
实施例24固定床催化剂FXCAT-21的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至300℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-21。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表21所示。
表21
催化剂 FXCAT-21
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.37
二甲苯产物中对二甲苯选择性(wt％) 99.70
C8芳烃产物中对二甲苯选择性(wt％) 90.48
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 93.09
产物分布(wt％)  
C1-C6+链烃 13.62
甲苯 53.41
乙苯 2.76
对二甲苯 26.99
间二甲苯 0.04
邻二甲苯 0.04
C9+芳烃 3.13
实施例25固定床催化剂FXCAT-22的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至450℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-22。然后，氮气气氛下 降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表22所示。
表22
催化剂 FXCAT-22
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 36.71
二甲苯产物中对二甲苯选择性(wt％) 99.63
C8芳烃产物中对二甲苯选择性(wt％) 90.28
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 92.88
产物分布(wt％)  
C1-C6+链烃 13.33
甲苯 53.65
乙苯 2.79
对二甲苯 26.85
间二甲苯 0.06
邻二甲苯 0.04
C9+芳烃 3.28
实施例26固定床催化剂FXCAT-23的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至300℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至800℃，水用微量进料泵进料，水重量空速2h-1，常压，进料2小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-23。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表23所示。
表23
催化剂 FXCAT-23
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 33.26
二甲苯产物中对二甲苯选择性(wt％) 99.65
C8芳烃产物中对二甲苯选择性(wt％) 91.19
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 93.68
产物分布(wt％)  
C1-C6+链烃 14.57
甲苯 54.35
乙苯 2.39
对二甲苯 25.68
间二甲苯 0.05
邻二甲苯 0.04
C9+芳烃 2.92
实施例27固定床催化剂FXCAT-24的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至300℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至600℃，水用微量进料泵进料，水重量空速2h-1，常压，进料8小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-24。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表24所示。
表24
催化剂 FXCAT-24
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 36.97
二甲苯产物中对二甲苯选择性(wt％) 99.70
C8芳烃产物中对二甲苯选择性(wt％) 91.48
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 93.42
产物分布(wt％)  
C1-C6+链烃 14.07
甲苯 53.96
乙苯 2.37
对二甲苯 26.31
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 3.20
实施例28固定床催化剂FXCAT-25的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-11-B装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-25。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表25所示。
表25
催化剂 FXCAT-25
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.56
二甲苯产物中对二甲苯选择性(wt％) 99.82
C8芳烃产物中对二甲苯选择性(wt％) 91.40
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.39
产物分布(wt％)  
C1-C6+链烃 15.31
甲苯 52.72
乙苯 2.51
对二甲苯 27.22
间二甲苯 0.03
邻二甲苯 0.02
C9+芳烃 2.19
实施例29固定床催化剂FXCAT-26的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至150℃。硅酸四甲酯用微量进料泵进料，硅酸四甲酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-26。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表26所示。
表26
催化剂 FXCAT-26
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.87
二甲苯产物中对二甲苯选择性(wt％) 99.89
C8芳烃产物中对二甲苯选择性(wt％) 91.38
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.44
产物分布(wt％)  
C1-C6+链烃 15.11
甲苯 52.91
乙苯 2.54
对二甲苯 27.26
间二甲苯 0.02
邻二甲苯 0.01
C9+芳烃 2.15
实施例30流化床催化剂FLCAT-27的制备及反应评价
在固定流化床反应装置内在线制备苯、甲醇烷基化制对甲苯联产对二甲苯流化床催化剂。
在线制备催化剂条件如下：将10g成型分子筛样品FLHZSM-5-C装入固定流化床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸 四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯流化床催化剂，命名为FLCAT-27。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表27所示。
表27
催化剂 FLCAT-27
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 32.71
二甲苯产物中对二甲苯选择性(wt％) 99.66
C8芳烃产物中对二甲苯选择性(wt％) 90.79
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.03
产物分布(wt％)  
C1-C6+链烃 17.41
甲苯 51.05
乙苯 2.61
对二甲苯 26.61
间二甲苯 0.05
邻二甲苯 0.04
C9+芳烃 2.23
实施例31固定床催化剂FXCAT-28的制备及反应评价
在微型固定床反应装置内在线制备甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-C装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.2h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得甲醇和/或二甲醚与苯烷基化制甲苯联产对二甲苯固定床催化剂，命名为FXCAT-28。然后，氮气气氛下降温至反应温度450℃，测试苯甲醇烷基化制甲苯联产对二甲苯反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析，反应结果如表28所示。
表28
催化剂 FXCAT-28
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 38.01
二甲苯产物中对二甲苯选择性(wt％) 93.60
C8芳烃产物中对二甲苯选择性(wt％) 80.64
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 82.91
产物分布(wt％)  
C1-C6+链烃 14.06
甲苯 44.92
乙苯 4.52
对二甲苯 26.33
间二甲苯 0.99
邻二甲苯 0.81
C9+芳烃 8.37
实施例32固定床催化剂FXCAT-29的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-29。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表29所示。
表29
催化剂 FXCAT-29
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.51
二甲苯产物中对二甲苯选择性(wt％) 99.74
C8芳烃产物中对二甲苯选择性(wt％) 94.31
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.20
产物分布(wt％)  
C1-C6+链烃 16.81
甲苯 52.17
乙苯 1.56
对二甲苯 27.03
间二甲苯 0.04
邻二甲苯 0.03
C9+芳烃 2.36
链烃产物分布(wt％)  
CH4 1.03
C2H4 39.66
C2H6 0.12
C3H6 31.63
C3H8 1.92
C4 13.43
C5 7.07
C6+ 5.13
C2H4+C3H6 71.29
实施例33固定床催化剂FXCAT-30的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝4，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1.5小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯低碳烯烃固定床催化剂，命名为FXCAT-30。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表30所示。
表30
催化剂 FXCAT-30
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 36.01
二甲苯产物中对二甲苯选择性(wt％) 99.66
C8芳烃产物中对二甲苯选择性(wt％) 93.24
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.58
产物分布(wt％)  
C1-C6+链烃 16.57
甲苯 52.31
乙苯 1.84
对二甲苯 26.60
间二甲苯 0.05
邻二甲苯 0.04
C9+芳烃 2.59
链烃产物分布(wt％)  
CH4 1.12
C2H4 37.13
C2H6 0.16
C3H6 33.02
C3H8 2.17
C4 14.52
C5 7.14
C6+ 4.74
C2H4+C3H6 70.15
实施例34固定床催化剂FXCAT-31的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝1，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1.5小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-31。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表31所示。
表31
催化剂 FXCAT-31
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 33.68
二甲苯产物中对二甲苯选择性(wt％) 99.71
C8芳烃产物中对二甲苯选择性(wt％) 94.72
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.35
产物分布(wt％)  
C1-C6+链烃 17.64
甲苯 51.46
乙苯 1.43
对二甲苯 27.07
间二甲苯 0.04
邻二甲苯 0.04
C9+芳烃 2.32
链烃产物分布(wt％)  
CH4 0.91
C2H4 38.18
C2H6 0.11
C3H6 34
C3H8 1.75
C4 12.97
C5 6.82
C6+ 5.26
C2H4+C3H6 72.18
实施例35固定床催化剂FXCAT-32的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至250℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-32。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表32所示。
表32
催化剂 FXCAT-32
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.32
二甲苯产物中对二甲苯选择性(wt％) 99.82
C8芳烃产物中对二甲苯选择性(wt％) 94.60
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.39
产物分布(wt％)  
C1-C6+链烃 17.15
甲苯 52.05
乙苯 1.49
对二甲苯 26.98
间二甲苯 0.03
邻二甲苯 0.02
C9+芳烃 2.28
链烃产物分布(wt％)  
CH4 0.97
C2H4 37.92
C2H6 0.1
C3H6 33.95
C3H8 1.83
C4 13.07
C5 6.93
C6+ 5.23
C2H4+C3H6 71.87
实施例36固定床催化剂FXCAT-33的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至300℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-33。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表33所述。
表33
催化剂 FXCAT-33
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.95
二甲苯产物中对二甲苯选择性(wt％) 99.63
C8芳烃产物中对二甲苯选择性(wt％) 93.09
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.18
产物分布(wt％)  
C1-C6+链烃 16.39
甲苯 51.94
乙苯 1.89
对二甲苯 26.80
间二甲苯 0.06
邻二甲苯 0.04
C9+芳烃 2.88
链烃产物分布(wt％)  
CH4 0.95
C2H4 36.92
C2H6 0.18
C3H6 33.39
C3H8 2.22
C4 13.57
C5 6.95
C6+ 5.82
C2H4+C3H6 70.31
实施例37固定床催化剂FXCAT-34的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至800℃，水用微量进料泵进料，水重量空速2h-1，常压，进料2小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-34。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表34所述。
表34
催化剂 FXCAT-34
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 32.17
二甲苯产物中对二甲苯选择性(wt％) 99.88
C8芳烃产物中对二甲苯选择性(wt％) 94.69
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.50
产物分布(wt％)  
C1-C6+链烃 18.23
甲苯 52.05
乙苯 1.43
对二甲苯 26.04
间二甲苯 0.02
邻二甲苯 0.01
C9+芳烃 2.22
链烃产物分布(wt％)  
CH4 1.09
C2H4 39.52
C2H6 0.11
C3H6 32.09
C3H8 1.83
C4 13.19
C5 6.95
C6+ 5.22
C2H4+C3H6 71.61
实施例38固定床催化剂FXCAT-35的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至600℃，水用微量进料泵进料，水重量空速2h-1，常压，进料8小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-35。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表35所述。
表35
催化剂 FXCAT-35
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.59
二甲苯产物中对二甲苯选择性(wt％) 99.74
C8芳烃产物中对二甲苯选择性(wt％) 94.23
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.07
产物分布(wt％)  
C1-C6+链烃 16.15
甲苯 52.94
乙苯 1.57
对二甲苯 26.78
间二甲苯 0.04
邻二甲苯 0.03
C9+芳烃 2.49
链烃产物分布(wt％)  
CH4 1.01
C2H4 39.25
C2H6 0.13
C3H6 31.55
C3H8 1.93
C4 13.51
C5 7.27
C6+ 5.35
C2H4+C3H6 70.80
实施例39固定床催化剂FXCAT-36的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-11-A催化剂压片成型并破碎筛分为40-60目，将5g(40-60目)催化剂装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-36。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表36所述。
表36
催化剂 FXCAT-36
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 34.17
二甲苯产物中对二甲苯选择性(wt％) 99.85
C8芳烃产物中对二甲苯选择性(wt％) 94.49
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.46
产物分布(wt％)  
C1-C6+链烃 18.13
甲苯 51.89
乙苯 1.49
对二甲苯 26.26
间二甲苯 0.03
邻二甲苯 0.01
C9+芳烃 2.19
链烃产物分布(wt％)  
CH4 0.91
C2H4 38.61
C2H6 0.09
C3H6 34.07
C3H8 1.6
C4 12.23
C5 6.85
C6+ 5.64
C2H4+C3H6 72.68
实施例40固定床催化剂FXCAT-37的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四甲酯的混合液用微量进料泵进料，硅酸四甲酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四甲酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-37。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表37所述。
表37
催化剂 FXCAT-37
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 33.86
二甲苯产物中对二甲苯选择性(wt％) 99.85
C8芳烃产物中对二甲苯选择性(wt％) 94.59
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 95.51
产物分布(wt％)  
C1-C6+链烃 18.67
甲苯 51.46
乙苯 1.46
对二甲苯 26.22
间二甲苯 0.02
邻二甲苯 0.02
C9+芳烃 2.15
链烃产物分布(wt％)  
CH4 1.05
C2H4 37.59
C2H6 0.1
C3H6 34.03
C3H8 1.69
C4 13.02
C5 6.77
C6+ 5.75
C2H4+C3H6 71.62
实施例41流化床催化剂FLCAT-38的制备及反应评价
在固定流化床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃流化床催化剂。
在线制备催化剂条件如下：将10g成型分子筛样品FLHZSM-5-A装入固定流化床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，空气气氛下升温至550℃，焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃流化床催化剂，命名为FLCAT-38。然后，氮气气氛下降温至反应温度450℃，测试甲醇和/或二甲醚与 苯烷基化制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表38所述。
表38
催化剂 FLCAT-38
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 30.18
二甲苯产物中对二甲苯选择性(wt％) 99.70
C8芳烃产物中对二甲苯选择性(wt％) 93.30
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.56
产物分布(wt％)  
C1-C6+链烃 17.43
甲苯 51.48
乙苯 1.83
对二甲苯 26.60
间二甲苯 0.05
邻二甲苯 0.03
C9+芳烃 2.58
链烃产物分布(wt％)  
CH4 1.01
C2H4 36.73
C2H6 0.11
C3H6 34.09
C3H8 1.93
C4 13.55
C5 7.20
C6+ 5.38
C2H4+C3H6 70.82
实施例42固定床催化剂FXCAT-39的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。三甲氧基膦和硅酸四乙酯的混合液用微量进料泵进料，硅酸四乙酯：三甲氧基膦(质量比)＝2，三甲氧基膦和硅酸四乙酯的总重量空速0.1h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-39。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯：甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表39所述。
表39
催化剂 FXCAT-39
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 37.97
二甲苯产物中对二甲苯选择性(wt％) 95.28
C8芳烃产物中对二甲苯选择性(wt％) 83.25
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 88.45
产物分布(wt％)  
C1-C6+链烃 15.91
甲苯 48.53
乙苯 3.92
对二甲苯 25.85
间二甲苯 0.71
邻二甲苯 0.57
C9+芳烃 4.51
链烃产物分布(wt％)  
CH4 0.98
C2H4 33.21
C2H6 0.23
C3H6 31.15
C3H8 2.62
C4 16.99
C5 8.94
C6+ 5.88
C2H4+C3H6 64.36
实施例43固定床催化剂FXCAT-40的制备及反应评价
在微型固定床反应装置内在线制备苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂后，进行反应性能评价。
在线制备催化剂条件如下：将5g(40-60目)成型分子筛样品FXHZSM-5-A装入固定床反应器，先经50mL/min空气在550℃下处理1小时，然后氮气气氛下降温至200℃。硅酸四乙酯用微量进料泵进料，硅酸四乙酯的重量空速0.067h-1，常压。进料1小时后停止进料，氮气吹扫，升温至550℃，空气气氛下焙烧4小时。氮气气氛下升温至700℃，水用微量进料泵进料，水重量空速2h-1，常压，进料4小时后停止进料，制得苯、甲醇制甲苯联产对二甲苯和低碳烯烃固定床催化剂，命名为FXCAT-40。然后，氮气气氛下降温至反应温度450℃，测试苯、甲醇制甲苯联产对二甲苯和低碳烯烃反应，反应条件如下：原料用微量进料泵进料，原料苯:甲醇(摩尔比)＝1:1，苯和甲醇总重量空速2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析，反应120min时取样分析。反应结果如表40所述。
表40
催化剂 FXCAT-40
反应温度(℃) 450
甲醇转化率(％) 100
苯转化率(％) 35.93
二甲苯产物中对二甲苯选择性(wt％) 99.49
C8芳烃产物中对二甲苯选择性(wt％) 90.93
芳烃产物中(甲苯+对二甲苯)选择性(wt％) 94.11
产物分布(wt％)  
C1-C6+链烃 14.72
甲苯 53.09
乙苯 2.57
对二甲苯 27.17
间二甲苯 0.09
邻二甲苯 0.05
C9+芳烃 2.31
链烃产物分布(wt％)  
CH4 1.31
C2H4 11.73
C2H6 0.98
C3H6 20.65
C3H8 11.31
C4 29.13
C5 14.86
C6+ 10.03
C2H4+C3H6 32.38
实施例44固定床催化剂FXCAT-41的制备及反应评价
装置、操作和条件同实施例5，只是制备催化剂过程中将三甲氧基磷替换为甲基二乙氧基磷，其他不变，制得甲醇甲苯制低碳烯烃联产对二甲苯固定床催化剂，命名为FXCAT-41。反应评价条件与实施例5一样，反应结果与实施例5一致(偏差不超过±1％)。
实施例45流化床催化剂FLCAT-42的制备及反应评价
在固定流化床反应器上在线制备甲苯甲醇烷基化制对二甲苯流化床催化剂后，进行反应性能评价。
在线制备催化剂的条件如下：将1kg成型分子筛样品FLHZSM-5-B装入固定流化床反应器，反应器温度300℃，硅酸四乙酯在硅酸四乙酯和甲苯、甲醇的混合物中的含量为10wt％，并且甲苯:甲醇(摩尔比)＝2:1，硅酸四乙酯和甲苯、甲醇的混合物的重量空速2h-1。进料10小时后停止进料，制得甲苯甲醇烷基化制对二甲苯催化剂，命名为FLCAT-42。
在线制备FLCAT-42后，切换为甲苯甲醇烷基化反应，反应条件为：反应温度450℃，原料甲苯:甲醇(摩尔比)＝2:1，甲苯和甲醇混合物的重量空速为2h-1，常压。反应产物通过在线Agilent7890气相色谱进行分析。反应结果如表1所示。
表41
催化剂 FLCAT-42
反应温度(℃) 450
进料时间(min) 120
甲醇转化率(％) 100
甲苯转化率(％) 27.15
对二甲苯在二甲苯异构体中选择性(wt％) 95.08
产物分布(wt％)  
C1-C6+链烃 17.22
苯 0.51
乙苯 0.18
对二甲苯 73.85
间二甲苯 2.03
邻二甲苯 1.79
C9+芳烃 4.42
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 (75)

  1. 一种催化剂的原位制备方法，其特征在于，将改性剂与反应器中的分子筛接触，原位制备由含有甲醇和/或二甲醚的原料制对二甲苯、甲苯和/或低碳烯烃的催化剂；
    所述反应器为由含有甲醇和/或二甲醚的原料制备对二甲苯、甲苯和/或低碳烯烃反应的反应器。
  2. 根据权利要求1所述的方法，其特征在于，所述改性剂包括以下至少一种：
    改性剂I：磷试剂和硅烷化试剂；
    改性剂II：硅烷化试剂；
    改性剂III：硅烷化试剂和水蒸气；
    改性剂IV：磷试剂、硅烷化试剂和水蒸气；
  3. 根据权利要求1所述的方法，其特征在于，所述催化剂为以下至少一种反应的催化剂：
    反应I：甲醇和/或二甲醚、甲苯制低碳烯烃联产对二甲苯；
    反应II：甲醇和/或二甲醚与苯制甲苯、对二甲苯、低碳烯烃中至少一种；
    所述反应器为发生反应I或反应II中至少一个反应的反应器。
  4. 根据权利要求2所述的方法，其特征在于，所述磷试剂选自具有式I所示化学式的化合物中的至少一种：
    Figure PCTCN2017082222-appb-100001
    R1，R2，R3独立地选自C1～C10的烷基或C1～C10的烷氧基。
  5. 根据权利要求4所述的方法，其特征在于，所述式I中R1、R2、R3中至少有一个选自C1～C10的烷氧基。
  6. 根据权利要求2所述的方法，其特征在于，所述磷试剂选自三甲氧基膦、三乙氧基膦、三丙氧基膦、三丁氧基膦、甲基二乙氧基膦中的至少一种。
  7. 根据权利要求2所述的方法，其特征在于，所述硅烷化试剂选自具有式II所示化学式的化合物中的至少一种：
    Figure PCTCN2017082222-appb-100002
    R4，R5，R6，R7独立地选自C1～C10的烷基或C1～C10的烷氧基。
  8. 根据权利要求7所述的方法，其特征在于，所述式II中R4，R5，R6，R7中至少有一个选自C1～C10的烷氧基。
  9. 根据权利要求2所述的方法，其特征在于，所述硅烷化试剂选自硅酸四甲酯、硅酸四乙酯、硅酸四丙酯、硅酸四丁酯中的至少一种。
  10. 根据权利要求1所述的方法，其特征在于，所述反应器选自固定床、流化床、移动床反应器中的至少一种。
  11. 根据权利要求1或10所述的方法，其特征在于，所述分子筛为根据反应器类型成型后的成型分子 筛；
    所述成型分子筛由分子筛组成；或者
    所述成型分子筛中含有分子筛和粘结剂。
  12. 根据权利要求11所述的方法，其特征在于，所述成型分子筛由分子筛压片破碎成型、将分子筛与粘结剂混合挤条后断条成型、将分子筛与粘结剂混合喷雾干燥成型中的一种方法制备得到。
  13. 根据权利要求1所述的方法，其特征在于，所述分子筛选自具有MFI骨架结构的分子筛、具有MEL骨架结构的分子筛中的至少一种。
  14. 根据权利要求1所述的方法，其特征在于，所述分子筛为HZSM-5分子筛和/或HZSM-11分子筛。
  15. 根据权利要求11所述的方法，其特征在于，所述催化剂的原位制备方法至少包括如下步骤：
    (1)将成型分子筛置于反应器中；
    (2)向反应器中通入含有改性剂的物料；
    (3)停止向反应器中通入所述含有改性剂的物料，将反应器温度升至400℃以上并通入空气焙烧后，即得所述催化剂。
  16. 根据权利要求15所述的方法，其特征在于，步骤(2)中的物料A含有原料中的至少一种和改性剂。
  17. 根据权利要求15所述的方法，其特征在于，步骤(2)中的物料A含有甲苯和/或苯。
  18. 根据权利要求15所述的方法，其特征在于，步骤(2)为向反应器中通入含有改性剂I的物料A；所述改性剂I含有磷试剂和硅烷化试剂。
  19. 根据权利要求18所述的方法，其特征在于，步骤(2)中的物料A含有改性剂I和甲苯。
  20. 根据权利要求18所述的方法，其特征在于，步骤(2)所述物料A中磷试剂与硅烷化试剂的质量比为：
    硅烷化试剂:磷试剂＝1:2至5:1。
  21. 根据权利要求15所述的方法，其特征在于，步骤(2)为向反应器中通入含有改性剂II的物料B；所述改性剂II含有硅烷化试剂。
  22. 根据权利要求21所述的方法，其特征在于，步骤(2)中的物料B含有甲醇、甲苯、二甲醚中的至少一种和改性剂II。
  23. 根据权利要求15所述的方法，其特征在于，步骤(2)为向反应器中通入含有改性剂III的物料；所述改性剂III含有硅烷化试剂和水蒸气。
  24. 根据权利要求15所述的方法，其特征在于，所述催化剂的原位制备方法至少包括如下步骤：
    (1)将成型分子筛置于反应器中；
    (2)向反应器中通入含有硅烷化试剂的物料D；
    (3)停止向反应器中通入物料D，将反应器温度升至500℃以上并通入空气焙烧；
    (4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料E进行水蒸气处理后，即得到所述催化剂。
  25. 根据权利要求24所述的方法，其特征在于，步骤(2)中的物料D含有硅烷化试剂和苯。
  26. 根据权利要求24所述的方法，其特征在于，步骤(2)物料D的重量空速为0.1h-1～1h-1，通入物料D的时间为0.1～5小时。
  27. 根据权利要求24所述的方法，其特征在于，步骤(2)物料D的重量空速为0.2h-1～0.4h-1，通入物料D的时间为0.5～2小时。
  28. 根据权利要求24所述的方法，其特征在于，步骤(4)中的物料E含有水蒸气和苯。
  29. 根据权利要求15所述的方法，其特征在于，所述催化剂的原位制备方法至少包括如下步骤：
    (1)将成型分子筛置于反应器中；
    (2)向反应器中通入含有磷试剂和硅烷化试剂的物料F；
    (3)停止向反应器中通入物料F，将反应器温度升至500℃以上并通入空气焙烧；
    (4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料G进行水蒸气处 理后，即得所述催化剂。
  30. 根据权利要求29所述的方法，其特征在于，步骤(2)中的物料F含有磷试剂、硅烷化试剂和苯。
  31. 根据权利要求29所述的方法，其特征在于，步骤(2)所述物料F中硅烷化试剂与磷试剂的质量比为：
    硅烷化试剂：磷试剂＝1:2至5:1。
  32. 根据权利要求24或29所述的方法，其特征在于，步骤(3)中焙烧温度为500℃～700℃，焙烧时间为1～6小时。
  33. 根据权利要求24或29所述的方法，其特征在于，步骤(4)中所述非活性气体选自氮气、氦气、氩气中的至少一种。
  34. 根据权利要求24或29所述的方法，其特征在于，步骤(4)中水蒸气处理的温度为550℃～800℃，处理时间为1～10小时。
  35. 根据权利要求29所述的方法，其特征在于，步骤(4)中的物料G含有水蒸气和苯。
  36. 根据权利要求15所述的方法，其特征在于，步骤(2)为130℃～500℃条件下，向反应器中通入含有改性剂的物料。
  37. 根据权利要求15所述的方法，其特征在于，步骤(2)为200℃～400℃条件下，向反应器中通入含有改性剂的物料。
  38. 根据权利要求19所述的方法，其特征在于，步骤(2)所述物料A中磷试剂占物料A总重量的1wt％～10wt％；硅烷化试剂占物料A总重量的1wt％～40wt％，甲苯占物料A总重量的50wt％～98wt％。
  39. 根据权利要求30所述的方法，其特征在于，步骤(2)所述物料F中磷试剂占物料F总重量的1wt％～10wt％；硅烷化试剂占物料F总重量的1wt％～40wt％，苯占物料F总重量的50wt％～98wt％。
  40. 根据权利要求15所述的方法，其特征在于，步骤(3)中焙烧温度为500℃～700℃，焙烧时间为1～6小时。
  41. 一种实现反应I的方法，其特征在于，将含有甲醇和/或二甲醚与甲苯的原料在反应器中与根据权利要求1至40任一项所述方法原位和在线制备得到的反应I的催化剂接触，制低碳烯烃联产对二甲苯；
    反应I为甲醇和/或二甲醚与甲苯制低碳烯烃联产对二甲苯；
    或者所述反应I为甲醇和/或二甲醚与甲苯制对二甲苯；
    或者所述反应I为甲醇与甲苯制对二甲苯。
  42. 根据权利要求41所述的方法，其特征在于，所述原料与所述催化剂接触，反应温度为350℃～650℃。
  43. 根据权利要求41所述的方法，其特征在于，所述原料与所述催化剂接触，反应温度为400℃～500℃。
  44. 根据权利要求41所述的方法，其特征在于，所述含有甲醇和/或二甲醚与甲苯的原料中，甲醇和/或二甲醚与甲苯的比如下：
    甲醇和二甲醚的碳原子数：甲苯的摩尔数＝0.5～10。
  45. 根据权利要求41所述的方法，其特征在于，物流I在反应系统中与催化剂接触，得到物流II，从物流II中分离出C4烯烃或C5+链烃返回所述反应系统，从物流II中分离出低碳烯烃和对二甲苯作为产品；
    所述物流I含有甲醇和/或二甲醚与甲苯。
  46. 根据权利要求45所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，物流I在第一反应区内与催化剂接触得到物流II-A，从物流II-A中分离出C4烯烃或C5+链烃通入第二反应区内与催化剂接触得到物流II-B；
    从物流II-B中分离出C4烯烃或C5+链烃返回第二反应区；
    物流II-A和物流II-B中分离出的低碳烯烃和对二甲苯作为产品。
  47. 根据权利要求46所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述物流I在第一反应区内与催化剂接触得到物流II-A，所述物流II-A通入分离系统并分离出C4烯烃、低碳烯烃和对二甲苯；
    将所述分离系统中分离出的C4烯烃通入第二反应区内与催化剂接触得到物流II-B，将所述物流II-B通 入所述分离系统；
    所述分离系统中分离出的低碳烯烃和对二甲苯作为产品。
  48. 根据权利要求46所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述物流I在第一反应区内与催化剂接触得到物流II-A，所述物流II-A通入分离系统，所述分离系统输出C5+链烃、低碳烯烃和对二甲苯；
    将所述分离系统中分离出的C5+链烃通入第二反应区内与催化剂接触得到物流II-B，将所述物流II-B通入所述分离系统；
    所述分离系统中输出的低碳烯烃和对二甲苯作为产品。
  49. 根据权利要求45所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述第一反应区和第二反应区均含有催化剂A；
    所述催化剂A为磷试剂和硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
    (A1)在130℃～500℃下，将磷试剂和硅烷化试剂引入装有HZSM-5分子筛的第一反应区中；
    (A2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂A。
  50. 根据权利要求45所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述第一反应区含有催化剂A，所述第二反应区含有催化剂B。
  51. 根据权利要求50所述的方法，其特征在于，所述催化剂A为磷试剂和硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
    (A1)在130℃～500℃下，将磷改性试剂、硅烷化试剂和甲苯的混合物引入装有HZSM-5分子筛的第一反应区中；
    (A2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂A。
  52. 根据权利要求50所述的方法，其特征在于，所述催化剂B为硅烷化试剂改性的HZSM-5分子筛催化剂，其具体制备步骤如下：
    (B1)在120℃～250℃下，将硅烷化试剂和甲醇的混合物引入装有HZSM-5分子筛的第二反应区中；
    (B2)升温至500℃以上，空气气氛下焙烧1-6小时，即得所述催化剂B。
  53. 根据权利要求45所述的方法，其特征在于，所述反应系统包括一个反应器，或多个通过串联和/或并联方式连接的反应器。
  54. 根据权利要求53所述的方法，其特征在于，所述反应器为固定床、流化床或移动床中的至少一种。
  55. 根据权利要求45所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述第一反应区和所述第二反应区在同一个反应器内。
  56. 根据权利要求45所述的方法，其特征在于，所述反应系统包括第一反应区和第二反应区，所述第一反应区包含一个反应器或多个通过串联和/或并联方式连接的反应器，所述第二反应区包含一个反应器或多个通过串联和/或并联方式连接的反应器。
  57. 根据权利要求56所述的方法，其特征在于，所述第一反应区和所述第二反应区之间通过串联或并联方式连接。
  58. 根据权利要求41所述的方法，其特征在于，所述原料总进料空速为0.1h-1～10h-1。
  59. 根据权利要求41所述的方法，其特征在于，所述原料总进料空速为0.8h-1～3h-1。
  60. 根据权利要求41所述的方法，其特征在于，所述原料中甲苯的摩尔含量为5mol％～50mol％。
  61. 根据权利要求41所述的方法，其特征在于，所述原料中甲苯的摩尔含量为20mol％～40mol％。
  62. 根据权利要求41所述的方法，其特征在于，将磷试剂和硅烷化试剂与反应器中的分子筛接触，原位制备所述反应II的催化剂；
    所述反应器为制低碳烯烃联产对二甲苯的反应器。
  63. 一种实现反应II的方法，其特征在于，将含有甲醇和/或二甲醚与苯的原料在反应器中与根据权利要求1至40任一项所述方法原位和在线制备得到的反应II的催化剂接触，制甲苯联产对二甲苯；
    反应II：甲醇和/或二甲醚与制甲苯、对二甲苯、低碳烯烃中至少一种。
  64. 根据权利要求63所述的方法，其特征在于，将硅烷化试剂和水蒸气与反应器中的分子筛接触，原位制备所述反应II的催化剂；
    所述反应器为所述反应II的反应器。
  65. 根据权利要求64所述的方法，其特征在于，所述反应器选自固定床、流化床、移动床反应器中的至少一种。
  66. 根据权利要求63所述的方法，其特征在于，所述反应II的反应温度为350℃～600℃。
  67. 根据权利要求63所述的方法，其特征在于，所述反应II的反应温度为400℃～500℃。
  68. 根据权利要求63所述的方法，其特征在于，所述含有甲醇和苯的原料中，甲醇与苯的摩尔比为甲醇：苯＝(0.5～2):1。
  69. 根据权利要求63所述的方法，其特征在于，所述反应II的催化剂的原位制备方法至少包括如下步骤：
    (1)将成型分子筛置于反应器中；
    (2)向反应器中通入含有硅烷化试剂和苯的物料D；
    (3)停止向反应器中通入物料D，将反应器温度升至500℃以上并通入空气焙烧；
    (4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料E进行水蒸气处理后，即得到所述反应II的催化剂。
  70. 根据权利要求63所述的方法，其特征在于，所述反应II的催化剂的原位制备方法至少包括如下步骤：
    (1)将成型分子筛置于反应器中；
    (2)向反应器中通入含有磷试剂、硅烷化试剂和苯的物料F；
    (3)停止向反应器中通入物料F，将反应器温度升至500℃以上并通入空气焙烧；
    (4)通入非活性气体吹扫后，将反应器温度升至550℃以上，通入含有水蒸气的物料G进行水蒸气处理后，即得所述反应II的催化剂。
  71. 根据权利要求63所述的方法，其特征在于，所述反应II为甲醇和/或二甲醚与苯制甲苯联产对二甲苯和低碳烯烃。
  72. 根据权利要求63所述的方法，其特征在于，所述反应II为甲醇和/或二甲醚与苯制甲苯联产对二甲苯。
  73. 根据权利要求63所述的方法，其特征在于，所述反应II为甲醇和/或二甲醚与苯制对二甲苯联产低碳烯烃。
  74. 根据权利要求63所述的方法，其特征在于，所述反应II为甲醇和/或二甲醚与苯制对二甲苯。
  75. 根据权利要求63所述的方法，其特征在于，所述反应II为甲醇与苯制对二甲苯。
PCT/CN2017/082222 2017-04-27 2017-04-27 制甲苯、对二甲苯、低碳烯烃中至少一种的催化剂的原位制备方法及反应工艺 WO2018195865A1 (zh)

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