CN108786905B

CN108786905B - In-situ preparation method of catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol

Info

Publication number: CN108786905B
Application number: CN201710289011.XA
Authority: CN
Inventors: 于政锡; 刘中民; 朱书魁; 杨越
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2017-04-27
Filing date: 2017-04-27
Publication date: 2020-09-15
Anticipated expiration: 2037-04-27
Also published as: CN108786905A

Abstract

The application discloses an in-situ preparation method of a catalyst for preparing toluene and co-producing p-xylene through benzene and methanol alkylation, which is characterized in that a silanization reagent and water vapor are contacted with a molecular sieve in a reactor, and the catalyst for preparing toluene and co-producing p-xylene through benzene and methanol alkylation is prepared in situ; the reactor is a reactor for preparing toluene and co-producing p-xylene by alkylating benzene and methanol. The in-situ preparation method for the catalyst for preparing toluene and co-producing p-xylene through benzene and methanol alkylation simplifies the whole chemical production process, saves the catalyst preparation and transfer steps and is easy to operate by directly preparing the catalyst in a reaction system.

Description

In-situ preparation method of catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol

Technical Field

The application relates to an in-situ preparation method of a catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, belonging to the field of chemical engineering.

Background

Toluene and p-xylene are basic organic chemical raw materials of modern chemical industry. At present, toluene is mainly obtained by fractionation of coal tar and aromatization of petroleum, and the production process is complex and high in production cost because of the impurities such as alkane and trace methylthiophene. Para-xylene (PX) is mainly used for producing Purified Terephthalic Acid (PTA) and further producing polyester resin, PBT resin and the like. The recent mass application of polyesters in the fields of textile apparel, beverage packaging, etc. has driven a rapid increase in PX yield and consumption. The production of PX mainly adopts toluene, C9 aromatic hydrocarbon and mixed xylene as raw materials, and is made up by using disproportionation, isomerization, adsorption separation or cryogenic separation. Because the content of the paraxylene in the product is controlled by thermodynamics, the paraxylene only accounts for about 20 percent in xylene isomers, the boiling point difference of three xylene isomers is very small, the high-purity paraxylene cannot be obtained by adopting the common distillation technology, and an expensive adsorption separation process is required to be adopted.

At present, benzene and methanol are both abundant in China. Therefore, the benzene and the methanol with excess capacity are directly alkylated to produce the toluene and the p-xylene with better industrial value, which is beneficial to the in-situ conversion of the benzene and the optimization of aromatic hydrocarbon resources and opens up a new utilization way for the methanol. At present, reports on direct alkylation of benzene and methanol are not common. Patent CN102964201A discloses a method for high-selectivity synthesis of xylene by alkylation of benzene and methanol, wherein the catalyst is obtained by modification of ZSM-5, USY, MCM-22 or EU-1 molecular sieve loaded with metal oxides Mo, Ni or La, wherein ZSM-5 is loaded with 8% of La₂O₃When the catalyst is used, the conversion rate of benzene is 42.5%, the conversion rate of methanol is 93.7%, and the selectivity of xylene is 76.5%. Patent CN103418421A discloses a catalyst for selectively synthesizing paraxylene by alkylation of coked benzene and methanol, which uses HZSM-5 molecular sieve or SAPO-11 molecular sieve after heating treatment in steam as carrier to load metal oxide (one or more of iron, zinc, manganese, bismuth, copper and lead), when the catalyst is applied to the alkylation reaction of coked benzene and methanol, the molar selectivity of paraxylene in aromatic hydrocarbon products can reach 67% at most. The above technology adopts transition metal modification method to improve the total selectivity of toluene and xylene in the benzyl alcohol alkylation product, but the total selectivity of p-xylene in C₈Low selectivity (or otherwise) in aromatic hydrocarbons (including three xylenes and ethylbenzene)No mention is made of p-xylene in C₈Selectivity in aromatics) due to: (1) the acidity of the catalyst surface is not suitable; (2) the catalyst outer surface still has a large number of acid sites; (3) the orifice size is larger. However, C₈The boiling point difference of aromatic hydrocarbon is very small, high-purity p-xylene can not be obtained by adopting a common distillation technology, and an expensive adsorption separation process is required to be adopted, so that the production cost of the p-xylene is greatly increased.

Compared with the reaction for preparing p-xylene by alkylating toluene and methanol at high selectivity, the direct high-selectivity production of p-xylene by benzene and methanol is more difficult to realize because of the following reasons: (1) benzene and methanol are subjected to alkylation reaction to produce p-xylene, and the reaction is more complicated because toluene is prepared by benzene and methanol alkylation; (2) in a benzene and methanol alkylation reaction system, raw material benzene can be subjected to alkylation reaction with product ethylene in the self-conversion reaction of methanol to generate ethylbenzene (the boiling points of ethylbenzene and three xylenes have small difference), so that the orifice size needs to be controlled, the acid position on the outer surface needs to be passivated to improve the para-selectivity of para-xylene in three xylene isomers, and the acid property on the inner surface needs to be modified to inhibit the benzene and ethylene alkylation to generate ethylbenzene. Relatively, the benzene content in the toluene and methanol alkylation reaction system is very low, so the ethylbenzene content in the product is very low, the selectivity of the paraxylene in three xylene isomers can be improved only by passivating the acid position of the outer surface and controlling the size of an orifice, and the paraxylene in C is easier to realize₈High selectivity in aromatics. At present, Chinese patent CN104710268A discloses a fluidized bed catalyst for preparing p-xylene by alkylation of benzyl alcohol and a preparation method thereof, wherein a siloxane compound and an alkaline earth metal modified ZSM-5 molecular sieve catalyst are adopted, and the selectivity of p-xylene in three xylene isomers is realized>95 wt%. Although the reported technology also obtains higher PX selectivity, the preparation process of the catalyst is complex, multiple modification and roasting processes are required, a series of catalyst production devices are required to be built, and the investment is huge; in addition, the technology does not mention the content of toluene in the aromatic product and the content of ethylbenzene in C₈Content in aromatic hydrocarbons.

Therefore, the development of the on-line preparation method of the catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, which has a simple process and is easy to operate, has very important significance and obvious practical applicability.

Disclosure of Invention

According to one aspect of the application, an in-situ preparation method of the catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, which is simple in process and easy to operate, is provided. The catalyst is directly prepared in the reaction system, so that the whole process of chemical production is simplified, the steps of catalyst preparation and transfer are saved, the operation is easy, the traditional production mode that finished catalysts are prepared in a catalyst production unit and then transported to a chemical production unit, the catalysts are filled and then the catalyst is started for production in the prior chemical field is broken, and the technical bias in large-scale industrial production in the field of heterogeneous catalysis is overcome.

The in-situ preparation method of the catalyst for preparing toluene and co-producing p-xylene and low-carbon olefin by alkylating benzene and methanol is characterized in that a silylation reagent and water vapor are contacted with a molecular sieve in a reactor, and the catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is prepared in situ;

the reactor is used for preparing toluene and co-producing p-xylene and low-carbon olefin by alkylating benzene and methanol.

In the application, the toluene is prepared from benzene and methanol to co-produce p-xylene and low-carbon olefin, wherein the raw material contains benzene and methanol, and the methanol comprises methanol and/or dimethyl ether. Unless otherwise specified, all or part of the methanol in the present application may be replaced with dimethyl ether, and the amount of methanol may be calculated by converting dimethyl ether into methanol having the same number of carbon atoms.

The feedstock benzene and methanol of the present application, wherein methanol comprises a form of methanol and/or dimethyl ether feed. Because methanol may be converted into dimethyl ether on the catalyst, namely the methanol and the dimethyl ether have communicated functions in the raw materials, the actual reaction raw materials are introduced into the methanol and the toluene, and the methanol, the dimethyl ether and the toluene are always simultaneously 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 materials is not excluded. The number of moles of carbon atoms in dimethyl ether in the calculation corresponds to the number of moles of methanol.

As an embodiment, the silylating agent is selected from at least one of the organosilicon compounds. Preferably, the silylating agent is at least one selected from compounds having the formula shown in formula I:

R₁，R₂，R₃，R₄independently selected from C₁～C₁₀Alkyl of (C)₁～C₁₀Alkoxy group of (2).

Further preferably, R in the formula I₁，R₂，R₃，R₄Independently selected from C₁～C₅Alkyl of (C)₁～C₅Alkoxy group of (2).

Preferably, R in the formula I₁，R₂，R₃，R₄At least one of them is selected from C₁～C₁₀Alkoxy group of (2). Further preferably, said R₁，R₂，R₃，R₄At least one of them is selected from C₁～C₅Alkoxy group of (2). Even more preferably, R in said formula I₁，R₂，R₃，R₄Are the same alkoxy groups.

In one embodiment, the silylating agent is at least one member selected from the group consisting of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.

As an alternative embodiment, the reactor is selected from at least one of a fixed bed, a fluidized bed, a moving bed reactor.

As an embodiment, the molecular sieve is a shaped molecular sieve shaped according to reactor type;

the formed molecular sieve is composed of a molecular sieve; or

The formed molecular sieve contains a molecular sieve and a binder.

As an alternative embodiment, the formed molecular sieve is prepared by one method of crushing and forming a molecular sieve tablet, mixing and extruding the molecular sieve and a binder, then cutting and forming the molecular sieve into strips, and mixing and spray drying and forming the molecular sieve and the binder.

Preferably, the molecular sieve is selected from at least one of a molecular sieve having MFI framework structure, a molecular sieve having MEL framework structure. Further preferably, the molecular sieve is an HZSM-5 molecular sieve and/or an HZSM-11 molecular sieve.

Preferably, the silicon-aluminum ratio (atomic ratio) Si/Al in the molecular sieve is 5-35.

As an embodiment, the in-situ preparation method of the catalyst for toluene and p-xylene co-production by benzene and methanol alkylation at least comprises the following steps:

(1) placing the shaped molecular sieve in a reactor;

(2) introducing a material D containing a silanization reagent into the reactor;

(3) stopping introducing the material D into the reactor, raising the temperature of the reactor to over 500 ℃, and introducing air for roasting;

(4) and after inert gas is introduced for purging, raising the temperature of the reactor to be more than 550 ℃, introducing a material E containing water vapor for water vapor treatment, and obtaining the catalyst for preparing toluene and co-producing p-xylene by benzene and methanol alkylation.

As a preferred embodiment, the material D in the step (2) contains a silylation agent and benzene.

In the material D, except for the silanization reagent, other reagents which can improve the modification efficiency of the silanization reagent on the molecular sieve and do not influence the reaction performance of the catalyst are not excluded.

Preferably, in the step (2), the material D containing the silylation reagent is introduced into the reactor at the temperature of 130-500 ℃.

The person skilled in the art can adjust the space velocity and the time for feeding the material D into the reactor in step (2) according to the specific requirements of the actual production.

Preferably, the weight space velocity of the material D in the step (2) is0.1h^-1～1h^-1And the time for introducing the material D is 0.1-5 hours. Further preferably, the weight space velocity of the material D in the step (2) is 0.2h^-1～0.4h^-1And the time for introducing the material D is 0.5-2 hours.

Preferably, the roasting temperature in the step (3) is 500-700 ℃, and the roasting time is 1-6 hours.

Preferably, the inactive gas in step (4) is selected from at least one of nitrogen, helium and argon.

The material E containing water vapor can be 100% water vapor, and can also be inactive gas and/or other reagents which can improve (adjust) the water vapor modification efficiency and do not influence the reaction performance of the catalyst.

Preferably, the temperature of the water vapor treatment in the step (4) is 550-800 ℃, and the treatment time is 1-10 hours.

Preferably, the weight space velocity of the water vapor in the material E in the step (4) is 0.5h^-1～5h^-1. Further preferably, the weight space velocity of the water vapor in the material E in the step (4) is 1h^-1～3h^-1。

According to another aspect of the application, a method for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is provided, which is characterized in that a raw material containing methanol and benzene is contacted with the catalyst for preparing toluene and co-producing p-xylene by alkylating the benzene and the methanol, which are prepared in situ according to any method, in a reactor to prepare the toluene and co-producing p-xylene. Namely, after the steam modification is finished, the temperature is directly reduced from the steam modification temperature to the reaction temperature, and the reaction for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is started. Compared with the inherent production mode in the chemical field, the washing and separating process after the catalyst modification, the catalyst cooling process after the roasting to the room temperature, the catalyst transportation step, the catalyst filling step, the step of high-temperature pre-activation after the catalyst is filled into a reactor and the like are saved, the production efficiency is greatly improved, and the safety problem possibly occurring in the saved steps is avoided; more importantly, the reactor can start to react after being cooled from the roasting temperature to the reaction temperature, the heat energy is fully utilized, and the energy consumption in the production is greatly saved.

Preferably, the reaction temperature for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is 350-600 ℃. Further preferably, the reaction temperature for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is 400-500 ℃.

In the raw materials containing methanol and benzene, the molar ratio of methanol to benzene is methanol: and (3) benzene is 0.5-2: 1. Preferably, in the raw material containing methanol and benzene, the molar ratio of methanol to benzene is methanol: and (3) benzene is 1-1.5: 1.

In the present application, C₁～C₁₀、C₁～C₅And the like refer to the number of carbon atoms that the group contains.

In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound. The alkane compound comprises straight-chain alkane, branched-chain alkane, cycloalkane and cycloalkane with branched chain.

In the present application, the "alkoxy group" is a group formed by losing a hydrogen atom on a hydroxyl group on the molecule of an alkyl alcohol compound.

In this application, "methanol and/or dimethyl ether" means that methanol in the feed can be replaced in whole or in part by dimethyl ether, including three cases: only methanol; or only dimethyl ether; or both methanol and dimethyl ether. For example, "containing methanol and/or dimethyl ether, benzene" includes three cases: containing methanol and benzene; or dimethyl ether and benzene; or methanol, dimethyl ether and benzene.

Benefits of the present application include, but are not limited to:

(1) the in-situ preparation method for the catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol breaks through the traditional production mode that finished catalyst is prepared in a catalyst production unit and then transported to a chemical production unit, the catalyst is filled and then the catalyst is started to produce in the prior chemical field, and overcomes the technical bias in large-scale industrial production in the heterogeneous catalysis field.

(2) The in-situ preparation method for the catalyst for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol simplifies the whole chemical production process, saves the catalyst preparation and transfer steps, and is easy to operate.

(3) Compared with the inherent production mode in the chemical field, the method for preparing toluene and co-producing p-xylene by alkylating benzene and methanol saves the washing and separating process after catalyst modification, the catalyst cooling process after roasting and cooling to room temperature, the catalyst transportation step, the catalyst filling step, the step of high-temperature pre-activation after the catalyst is filled into a reactor and the like, greatly improves the production efficiency, and avoids the safety problem possibly occurring in the saved steps; more importantly, the reactor can start to react after being cooled from the roasting temperature to the reaction temperature, the heat energy is fully utilized, and the energy consumption in the production is greatly saved.

(4) The method for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is completed in situ in one system from catalyst preparation to reaction, is beneficial to recycling and cyclic utilization of wastes in the catalyst preparation process in large-scale chemical production, and is environment-friendly.

(5) The method for preparing toluene and co-producing p-xylene by alkylating benzene and methanol has the advantages of 100% methanol conversion rate and (toluene + p-xylene) selectivity in aromatic hydrocarbon products>85 wt% selectivity to para-xylene in xylene product>99.6wt％，C₈Selectivity to p-xylene in aromatics>90wt％。

Drawings

FIG. 1 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

FIG. 2 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

FIG. 3 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

FIG. 4 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

FIG. 5 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

FIG. 6 is a process flow diagram of an embodiment of a reaction for producing light olefins and co-producing p-xylene using the catalyst prepared by the present invention.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.

In the examples, the catalyst attrition index is determined on an attrition index measuring instrument, model MS-C, of Shenyang Accord mechanical electronics, Inc.

In the examples, the fixed bed reactor had an internal diameter of 1.5 cm; the inner diameter of the fixed fluidized bed reactor is 3 cm; the internal diameter of the circulating fluidized bed reactor was 12 cm.

EXAMPLE 1 preparation of HZSM-5 shaped molecular sieve sample for fixed bed

100g of HZSM-5 zeolite molecular sieve raw powder (catalyst factory of southern Kai university, Si/Al ═ 30) is calcined for 4 hours at 550 ℃ in an air atmosphere, and then the calcined powder is tableted, molded, crushed and sieved to obtain molded molecular sieve particles with the particle size of 40-60 meshes, and the particles are marked as FXHZSM-5-A.

100g of HZSM-5 zeolite molecular sieve raw powder (Si/Al-5 in Nankai university catalyst works) is calcined for 4 hours at 550 ℃ in an air atmosphere, and then the calcined powder is tableted, molded, crushed and sieved to obtain molded molecular sieve particles with the particle size of 40-60 meshes, wherein the molded molecular sieve particles are marked as FXHZSM-5-B.

100g of HZSM-5 zeolite molecular sieve raw powder (catalyst factory of southern Kai university, Si/Al ═ 10) is calcined for 4 hours at 550 ℃ in air atmosphere, and then the calcined powder is tableted, molded, crushed and sieved to obtain molded molecular sieve particles with the particle size of 40-60 meshes, and the particles are marked as FXHZSM-5-C.

EXAMPLE 2 preparation of HZSM-11 molded molecular sieve sample for fixed bed

100g of HZSM-11 zeolite molecular sieve raw powder (Nankai university catalyst factory, Si/Al ═ 35) is calcined at 550 ℃ for 4 hours in air atmosphere, and then the calcined powder is tableted, molded, crushed and sieved to obtain molded molecular sieve particles with the particle size of 40-60 meshes, and the particles are marked as FXHZSM-11-A.

100g of HZSM-11 zeolite molecular sieve raw powder (catalyst factory of southern Kai university, Si/Al ═ 12) is calcined for 4 hours at 550 ℃ in an air atmosphere, and then the calcined powder is tableted, molded, crushed and sieved to obtain molded molecular sieve particles with the particle size of 40-60 meshes, and the particles are marked as FXHZSM-11-B.

EXAMPLE 3 preparation of HZSM-5 molded molecular sieve sample for fluidized bed

Mixing 100g of HZSM-5 zeolite molecular sieve raw powder (Nankai university catalyst factory, Si/Al is 30) and an amorphous binder containing aluminum or silicon, and spray-drying and forming, wherein the method comprises the following specific steps:

uniformly mixing HZSM-5 zeolite molecular sieve raw powder, pseudo-boehmite, silica sol, xanthan gum (biogum) and water, pulping, colloid milling and defoaming to obtain slurry; the slurry comprises the following components in parts by weight:

spray drying and forming the obtained slurry to obtain a microsphere particle sample with the particle size distribution of 20-100 mu m; roasting the microsphere particle sample in a muffle furnace at 550 ℃ for 3 hours to obtain the HZSM-5 molded molecular sieve with the abrasion index of 1.2, and marking the molecular sieve as FLHZSM-5-A.

EXAMPLE 4 preparation of HZSM-5 molded molecular sieve sample for fluidized bed

The specific preparation conditions and steps are the same as those of example 3, except that the amount of the raw material HZSM-5 zeolite molecular sieve powder is 10kg, the particle size distribution of the obtained microsphere particle sample is 20-120 μm, the abrasion index is 1.2, and the sample is marked as FLHZSM-5-B.

The specific preparation conditions and steps are the same as those in example 3, except that the silica-alumina ratio Si/Al of the raw material HZSM-5 zeolite molecular sieve powder is 10, the particle size distribution of the obtained microspherical particle sample is 20-100 μm, the attrition index is 1.2, and the sample is marked as FLHZSM-5-C.

EXAMPLE 5 preparation of fixed bed catalyst FXCAT-1 and reaction evaluation

After the low-carbon olefin co-production p-xylene fixed bed catalyst prepared by methanol and toluene is prepared on line in a micro fixed bed reaction device, the reaction performance is evaluated.

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour and then cooled to 200 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 90min, after nitrogen purging, heating to 550 ℃, and roasting for 4 hours in air atmosphere to obtain the fixed bed catalyst for co-production of low-carbon olefin and p-xylene from methanol and toluene, which is named as FXCAT-1. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in table 1.

TABLE 1

Catalyst and process for preparing same	FXCAT-1
		Reaction temperature (. degree.C.)	450
MethanolConversion (%)	100
		Toluene conversion (%)	36.09
Selectivity (wt%) of p-xylene in xylene isomers	99.64
		Product distribution (wt%)
Chain hydrocarbons	77.74
		Benzene and its derivatives	0.06
Ethylbenzene production	0.25
		Para-xylene	19.26
Meta-xylene	0.04
		Ortho-xylene	0.03
C₉₊Aromatic hydrocarbons	2.61
		Distribution of chain hydrocarbon products (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

EXAMPLE 6 preparation and reaction evaluation of fixed bed catalyst FXCAT-2

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is loaded into a micro fixed bed reactor, treated with 50mL/min nitrogen at 550 ℃ for 1 hour, and then cooled to 200 ℃ in a nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 10:40:50, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Feeding is stopped after 45min, nitrogen purging is carried out, the temperature is raised to 550 ℃, and roasting is carried out for 4 hours in the air atmosphere, so as to prepare the fixed bed catalyst for co-production of low-carbon olefin and p-xylene from methanol and toluene, which is named as FXCAT-2. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in table 2.

TABLE 2

Catalyst and process for preparing same	FXCAT-2
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	36.68
Selectivity (wt%) of p-xylene in xylene isomers	99.64
		Product distribution (wt%)
Chain hydrocarbons	77.59
		Benzene and its derivatives	0.08
Ethylbenzene production	0.29
		Para-xylene	19.18
Meta-xylene	0.04
		Ortho-xylene	0.03
C₉₊Aromatic hydrocarbons	2.79
		Distribution of chain hydrocarbon products (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

Example 7 preparation of fixed bed catalyst FXCAT-3 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 200 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 2:8:90, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 225min, purging with nitrogen, heating to 550 deg.C, and calcining in air atmosphere for 4 hr to obtain final productThe fixed bed catalyst for preparing low-carbon olefin and co-producing p-xylene by using alcohol toluene is named as FXCAT-3. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 3.

TABLE 3

Catalyst and process for preparing same	FXCAT-3
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	35.59
Selectivity (wt%) of p-xylene in xylene isomers	99.69
		Product distribution (wt%)
Chain hydrocarbons	77.9
		Benzene and its derivatives	0.06
Ethylbenzene production	0.21
		Para-xylene	19.19
Meta-xylene	0.03
		Ortho-xylene	0.03
C₉₊Aromatic hydrocarbons	2.58
		Distribution of chain hydrocarbon products (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

EXAMPLE 8 preparation and reaction evaluation of fixed bed catalyst FXCAT-4

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, which is named as FXCAT-4. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 4Shown in the figure.

TABLE 4

Example 9 preparation of fixed bed catalyst FXCAT-5 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 450 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, which is named as FXCAT-5. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 5.

TABLE 5

Catalyst and process for preparing same	FXCAT-5
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	35.80
Selectivity (wt%) of p-xylene in xylene isomers	99.63
		Product distribution (wt%)
Chain hydrocarbons	75.29
		Benzene and its derivatives	0.07
Ethylbenzene production	0.35
		Para-xylene	21.32
Meta-xylene	0.05
		Ortho-xylene	0.03
C₉₊Aromatic hydrocarbons	2.89
		Distribution of chain hydrocarbon products (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

Example 10 preparation of fixed bed catalyst FXCAT-6 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 150 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetramethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetramethyl silicate to toluene is 5:20:75, and the total weight space velocity of the trimethoxy phosphorus to the tetramethyl silicate and the toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, which is named as FXCAT-6. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 6.

TABLE 6

Catalyst and process for preparing same	FXCAT-6
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	34.79
Selectivity (wt%) of p-xylene in xylene isomers	99.95
		Product distribution (wt%)
Chain hydrocarbons	78.37
		Benzene and its derivatives	0.08
Ethylbenzene production	0.21
		Para-xylene	19.98
Meta-xylene	0
		Ortho-xylene	0.01
C₉₊Aromatic hydrocarbons	1.35
		Distribution of chain hydrocarbon products (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

EXAMPLE 11 preparation and reaction evaluation of fixed bed catalyst FXCAT-7

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-11-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ in nitrogen atmosphere. Trimethoxy phosphorus and silicic acidFeeding a mixed solution of tetraethyl ester and toluene by using a trace feed pump, wherein the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total space velocity of the trimethoxy phosphorus to the tetraethyl silicate to the toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, which is named as FXCAT-7. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 7.

TABLE 7

EXAMPLE 12 preparation of fluidized bed catalyst FLCAT-1 and reaction evaluation

After the catalyst of the fluidized bed for preparing the p-xylene and co-producing the low-carbon olefin by the methanol and the toluene is prepared on line in a fixed fluidized bed reaction device, the reaction performance is evaluated.

The catalyst is prepared on line under the following conditions: 10g of the molded molecular sieve sample FLHZSM-5-A prepared in example 3 was charged into a fixed fluidized bed reactor, treated with 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ in a nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in air atmosphere to obtain methanol and toluene for preparing low-carbon olefin and co-producing p-xyleneThe fluidized bed catalyst is named as FLCAT-1. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing the low-carbon olefin and co-producing the p-xylene from the methanol and the toluene are tested, and the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 60min of reaction. The reaction results are shown in Table 8.

TABLE 8

EXAMPLE 13 preparation and reaction of fixed bed catalyst FXCAT-8

A miniature fixed bed reaction device is adopted, and methanol and toluene are used as raw materials to prepare low-carbon olefin and co-produce p-xylene.

The in situ preparation of the catalyst was carried out under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a micro fixed bed reactor, treated by 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ in nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. Stopping feeding after 90min, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, which is named as FXCAT-8. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and carrying out the reaction of preparing low-carbon olefin from methanol and toluene and co-producing p-xylene, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in the tableShown at 9.

TABLE 9

Catalyst and process for preparing same	FXCAT-8
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	35.20
In the chain hydrocarbon product (C)₂H₄+C₃H₆) Selectivity (wt%)	73.55
		Selectivity (wt%) of p-xylene in xylene isomers	99.71
Hydrocarbon product distribution (wt%)
		CH₄	0.84
C₂H₄	30.09
		C₂H₆	0.08
C₃H₆	25.84
		C₃H₈	0.90
C₄Olefins	9.25
		C₄Alkane(s)	1.55
C₅₊Chain hydrocarbons	7.49
		Benzene and its derivatives	0.09
Ethylbenzene production	0.35
		Para-xylene	20.33
Meta-xylene	0.04
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	3.14

EXAMPLE 14 preparation and reaction of fixed bed catalyst FXCAT-9

According to one embodiment of the present application, as shown in fig. 1, stream I includes methanol and toluene, and the methanol and toluene are used as raw materials to produce low-carbon olefins and co-produce p-xylene.

The reaction system was charged with 5g (40-60 mesh) of the molded molecular sieve sample FXHZSM-5-A prepared in example 1, treated with 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ under nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. And stopping feeding after 90 minutes, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, wherein the fixed bed catalyst is named as FXCAT-9.

And introducing the material flow I into a reaction system to contact and react with a catalyst FXCAT-9. The material flow II containing the product leaves the reaction system and enters a separation system to separate out low-carbon olefin (ethylene and propylene) and C₄Olefins, para-xylene, and other components. Wherein, C₄The olefin is returned to the reaction system, and the low-carbon olefin (ethylene and propylene) and the paraxylene are taken as products. Other components as by-products.

The reaction conditions were as follows: the raw material is fed by a trace feed pump, the raw material methanol of the material flow I to toluene (molar ratio) is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1The reaction temperature is 450 ℃, and the reaction pressure is normal pressure. The product was analyzed by on-line Agilent7890 gas chromatography as shown in table 10.

Watch 10

Catalyst and process for preparing same	FXCAT-9
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Toluene conversion (%)	37.01
In the chain hydrocarbon product (C)₂H₄+C₃H₆) Selectivity (wt%)	82.19
		Selectivity (wt%) of p-xylene in xylene isomers	99.62
Hydrocarbon product distribution (wt%)
		CH₄	0.99
C₂H₄	31.87
		C₂H₆	0.19
C₃H₆	27.54
		C₃H₈	1.87
C₄Alkane(s)	1.62
		C₅₊Chain hydrocarbons	8.2
Benzene and its derivatives	0.58
		Ethylbenzene production	0.46
Para-xylene	23.1
		Meta-xylene	0.05
Ortho-xylene	0.03
		C₉₊Aromatic hydrocarbons	3.5

EXAMPLE 15 preparation and reaction of fixed bed catalyst FXCAT-10

According to one embodiment of the application, as shown in fig. 2, the stream I comprises dimethyl ether and toluene, and the dimethyl ether and toluene are used as raw materials to prepare low-carbon olefins and co-produce p-xylene.

The difference from example 14 was that in the separation system, the fixed bed catalyst was obtained and named FXCAT-10, except that it was the same as in example 14. Separation System of this example separates out C_1～3Chain hydrocarbons, C₄Olefin, C₄Alkane, C₅₊Chain hydrocarbons, aromatic hydrocarbons. Wherein, C₄The olefin is returned to the reaction system. From C_1～3Separating ethylene and propylene from the chain hydrocarbon as low carbonAn olefin product. Separating p-xylene from aromatic hydrocarbon to obtain the product. Other components as by-products. The reaction results were consistent with example 14 (deviation not exceeding. + -. 1%).

EXAMPLE 16 preparation and reaction of fixed bed catalyst FXCAT-11 and fluidized bed FLCAT-12

According to one embodiment of the present application, according to the process flow diagram shown in fig. 3, stream I includes methanol and toluene, and the methanol and toluene are used as raw materials to prepare low-carbon olefins and co-produce p-xylene.

The first reaction zone is 10 fixed beds connected in parallel, and the second reaction zone is a fluidized bed.

50g (40-60 mesh) of the molded molecular sieve sample FXHZSM-5-A prepared in example 1 was charged in 10 fixed beds in the first reaction zone, each fixed bed was charged with 5g, each fixed bed was treated with 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ under a nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. And stopping feeding after 90 minutes, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, wherein the fixed bed catalyst is named as FXCAT-11.

50g (40-60 mesh) of the microspherical molecular sieve sample FLHZSM-5-B prepared in example 4 was charged into the fluidized bed of the second reaction zone, treated with 500mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 200 ℃ under nitrogen atmosphere. Feeding the mixed solution of tetraethyl silicate and methanol by using a trace feed pump, vaporizing the mixed solution and then feeding the vaporized mixed solution into a fluidized bed of a second reaction zone, wherein the weight ratio of the tetraethyl silicate to the methanol is 40:60, and the total weight space velocity of the tetraethyl silicate and the methanol is 2h^-1And normal pressure. And stopping feeding after 3 hours, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene, wherein the fixed bed catalyst is named as FLCAT-12.

The first reaction zone is subjected to a methanol conversion reaction and a toluene methanol alkylation reaction under conditions such asThe following: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1The reaction temperature is 450 ℃, and the reaction pressure is normal pressure. And introducing the material flow I into a fixed bed of the first reaction zone to contact with a catalyst FXCAT-11 to obtain a material flow II-A, and leaving the first reaction zone and entering a separation system. Separating ethylene, propylene and C from the separation system₄Olefins and para-xylene. Separating C from the separation system₄Olefin is introduced into a fluidized bed of the second reaction zone to contact with a catalyst FXCAT-12, and the second reaction zone carries out shape-selective aromatization reaction of the fluidized bed at the reaction temperature of 450 ℃. The second reaction zone produces stream II-B which leaves the second reaction zone and enters a separation system. The ethylene and propylene separated from the separation system are used as low-carbon olefin products, and the paraxylene is used as a product. Other components as by-products.

The hydrocarbon products of the second reaction zone were analyzed by on-line Agilent7890 gas chromatography, as shown in table 11; deduction C₄The product distribution after olefin composition is shown in Table 12. The mixed hydrocarbon products of the first reaction zone and the second reaction zone were analyzed by on-line Agilent7890 gas chromatography, minus C₄The product distribution after olefin composition is shown in Table 13.

TABLE 11

C₄Olefin conversion (%)	83.25
		Selectivity (wt%) of p-xylene in xylene isomers	99.56
Hydrocarbon product distribution (wt%)
		CH₄	0.74
C₂H₄	0.60
		C₂H₆	1.02
C₃H₆	0.26
		C₃H₈	9.55
C₄Olefins	16.76
		C₄Alkane(s)	0.04
C₅₊	0.23
		Benzene and its derivatives	4.94
Toluene	35.74
		Ethylbenzene production	0.90
Para-xylene	27.07
		Meta-xylene	0.07
Ortho-xylene	0.05
		C₉₊Aromatic hydrocarbons	2.03

TABLE 12

C₄Olefin conversion (%)	83.25
		Selectivity (wt%) of p-xylene in xylene isomers	99.56
Hydrocarbon product distribution (wt%)
		CH₄	0.89
C₂H₄	0.72
		C₂H₆	1.22
C₃H₆	0.31
		C₃H₈	11.47
C₄Alkane(s)	0.05
		C₅₊Chain hydrocarbons	0.28
Benzene and its derivatives	5.93
		Toluene	42.94
Ethylbenzene production	1.08
		Para-xylene	32.52
Meta-xylene	0.08
		Ortho-xylene	0.06
C₉₊Aromatic hydrocarbons	2.44

Watch 13

Methanol conversion (%)	100
		Toluene conversion (%)	38.08
In the chain hydrocarbon product (C)₂H₄+C₃H₆) Selectivity (wt%)	82.44
		Selectivity (wt%) of p-xylene in xylene isomers	99.69
Hydrocarbon product distribution (wt%)
		CH₄	0.94
C₂H₄	31.68
		C₂H₆	0.19
C₃H₆	27.18
		C₃H₈	1.85
C₄Alkane(s)	1.64
		C₅₊Chain hydrocarbons	7.90
Benzene and its derivatives	0.58
		Ethylbenzene production	0.46
Para-xylene	24.00
		Meta-xylene	0.05
Ortho-xylene	0.03
		C₉₊Aromatic hydrocarbons	3.50

EXAMPLE 17 preparation and reaction of the catalysts FXCAT-13 and FLCAT-14

According to one embodiment of the present application, as shown in fig. 4, the stream I includes dimethyl ether, methanol and toluene, and the dimethyl ether, methanol and toluene are used as raw materials to prepare low-carbon olefins and co-produce p-xylene.

The difference from example 16 is that the first reaction zone is 1 fixed bed and is packed with 50g of molecular sieve sample FXHZSM-5-A. In addition, the separation system of this embodiment separates C_1～3Chain hydrocarbons, C₄Olefin, C₄Alkane, C₅₊Chain hydrocarbons, aromatic hydrocarbons. Wherein, C₄The olefin is returned to the second reaction zone. From C_1～3Separating ethylene and propylene from the chain hydrocarbon to obtain the product of low-carbon olefin. Separating p-xylene from aromatic hydrocarbon as productAnd (5) preparing the product. Other components as by-products. Otherwise, in the same manner as in example 23, a fixed bed catalyst was prepared and designated as FXCAT-13, and a fluidized bed catalyst was prepared and designated as FLCAT-14. The reaction results were consistent with example 16 (deviation not exceeding. + -. 1%).

EXAMPLE 18 preparation and reaction of fixed bed catalyst FXCAT-15

According to one embodiment of the present application, a process flow diagram shown in fig. 5 is provided for preparing low-carbon olefins and co-producing p-xylene from methanol and toluene. Stream I comprises methanol and toluene.

The reaction system is composed of two fixed beds arranged in series from top to bottom, as shown in FIG. 5, and adopts a sectional feeding mode, wherein the material flow I is fed from the fixed bed at the upper part, and the recycled material C is₅₊The chain hydrocarbons enter the lower fixed bed.

10g (40-60 mesh) of the molded molecular sieve sample FXHZSM-5-A prepared in example 1 was charged in each of two fixed beds, each of which was charged in an amount of 5 g. The preparation process of the catalyst comprises the following steps: each fixed bed was treated with 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ under a nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. And stopping feeding after 90 minutes, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. The fixed bed catalyst for preparing low-carbon olefin and co-producing p-xylene from methanol and toluene is prepared in situ and is marked as FXCAT-15.

The material flow I enters a fixed bed reactor at the upper part of a reaction system, contacts with a catalyst FXCAT-15, and carries out a methanol conversion reaction and a toluene methanol shape-selective alkylation reaction under the following reaction conditions: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1The reaction temperature is 450 ℃, and the reaction pressure is normal pressure.

The product-containing stream II leaves the reaction system and enters a separation system, C is separated_1～4Chain hydrocarbons, C₅₊Chain hydrocarbons and aromatic hydrocarbons. Wherein, C₅₊Chain hydrocarbon return reaction systemThe fixed bed at the lower part of the system is contacted with a catalyst FXCAT-15 to carry out reactions such as cracking, shape-selective aromatization and the like, and the reaction temperature of the fixed bed at the lower part of the reaction system is 630 ℃. From C_1～4Separating ethylene and propylene from the chain hydrocarbon to obtain the product of low-carbon olefin. Separating p-xylene from aromatic hydrocarbon to obtain the product. Other components as by-products.

The product was analyzed by on-line Agilent7890 gas chromatography as shown in table 14.

TABLE 14

Methanol conversion (%)	100
		Toluene conversion (%)	36.55
In chain hydrocarbon (C)₂H₄+C₃H₆) Selectivity is	80.83
		Selectivity (wt%) of p-xylene in xylene isomers	99.70
Hydrocarbon product distribution (wt%)
		CH₄	1.11
C₂H₄	33.02
		C₂H₆	0.31
C₃H₆	27.25
		C₃H₈	1.17
C₄	11.7
		Benzene and its derivatives	0.65
Ethylbenzene production	0.39
		Para-xylene	21.05
Meta-xylene	0.04
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	3.29

EXAMPLE 19 preparation and reaction of fixed bed catalyst FXCAT-16

According to an embodiment of the present application, the process flow chart shown in fig. 6 is used for preparing low-carbon olefins and co-producing p-xylene from methanol and toluene. Stream I comprises methanol and toluene.

The first reaction zone is a fixed bed and the second reaction zone is a fixed bed.

5g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A prepared in example 1 was charged into the fixed bed of the first reaction zone and the fixed bed of the second reaction zone, respectively, and the catalyst preparation procedures were the same: the catalyst in each fixed bed reactor was treated with 50mL/min of nitrogen at 550 ℃ for 1 hour, and then cooled to 300 ℃ under a nitrogen atmosphere. The mixed liquid of trimethoxy phosphorus, tetraethyl silicate and toluene is fed by a micro-feed pump, the weight ratio of trimethoxy phosphorus to tetraethyl silicate to toluene is 5:20:75, and the total weight space velocity of trimethoxy phosphorus, tetraethyl silicate and toluene is 1h^-1And normal pressure. And stopping feeding after 90 minutes, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. And respectively preparing the fixed bed catalyst for preparing the low-carbon olefin co-production p-xylene from the methanol and the toluene in the first fixed bed reaction zone and the second fixed bed reaction zone on line according to the processes, and marking the fixed bed catalyst as FXCAT-16.

The material flow I enters a fixed bed of a first reaction zone to contact with a catalyst FXCAT-16 and carry out methanol conversion reaction and shape-selective alkylation reaction of toluene and methanol under the following reaction conditions: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials methanol to toluene is 10:1, and the total weight space velocity of the methanol and the toluene is 2h^-1The reaction temperature is 450 ℃, and the reaction pressure is normal pressure. The product-containing stream II-A leaves the fixed bed of the first reaction zone and enters a separation system. Separation system separates out C_1～4Chain hydrocarbons, C₅₊Chain hydrocarbons and aromatic hydrocarbons.

C separated from the separation system₅₊The chain hydrocarbon enters a fixed bed of the second reaction zone, contacts with a catalyst FXCAT-16 and carries out cracking, shape-selective aromatization and other reactions, the reaction temperature of the fixed bed of the second reaction zone is 630 ℃, and a material flow II-B containing products leaves the fixed bed of the second reaction zone and enters a separation system.

C separated from the separation system_1～4Separating ethylene and propylene from the chain hydrocarbon to obtain the product of low-carbon olefin. Separating p-xylene from aromatic hydrocarbon to obtain the product. Other components as by-products.

The hydrocarbon product of the second reaction zone is passed on-lineAgilent7890 gas chromatography analysis as shown in table 15; deduction C₅₊The product distribution after chain hydrocarbon composition is shown in Table 16. The mixed hydrocarbon products of the first reaction zone and the second reaction zone were analyzed by on-line Agilent7890 gas chromatography, minus C₅₊The product distribution after chain hydrocarbon composition is shown in Table 17.

Watch 15

TABLE 16

C₅₊Chain hydrocarbon conversion (%)	93.92
		Selectivity (wt%) of p-xylene in xylene isomers	99.70
Hydrocarbon product distribution (wt%)
		CH₄	4.60
C₂H₄	22.18
		C₂H₆	3.22
C₃H₆	24.88
		C₃H₈	3.67
C₄	9.06
		Benzene and its derivatives	7.94
Toluene	11.79
		Ethylbenzene production	0.55
Para-xylene	10.60
		Meta-xylene	0.03
Ortho-xylene	0.02
		C₉₊Aromatic hydrocarbons	1.45

TABLE 17

Methanol conversion (%)	100
		Toluene conversion (%)	37.11
In chain hydrocarbon (C)₂H₄+C₃H₆) Selectivity is	80.81
		Selectivity (wt%) of p-xylene in xylene isomers	99.70
Hydrocarbon product distribution (wt%)
		CH₄	1.18
C₂H₄	32.06
		C₂H₆	0.31
C₃H₆	27.95
		C₃H₈	1.17
C₄	11.59
		Benzene and its derivatives	0.65
Ethylbenzene production	0.39
		Para-xylene	21.35
Meta-xylene	0.04
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	3.29

EXAMPLE 20 preparation and reaction of fluid bed catalyst FXCAT-17

According to an embodiment of the present application, the flowchart is the same as in example 19, as shown in fig. 6. The difference lies in the difference of raw materials and reactors.

In this embodiment, the material flow I includes dimethyl ether, methanol and toluene, and dimethyl ether, methanol and toluene are used as raw materials to prepare low-carbon olefin and co-produce p-xylene.

The first reaction zone in this example was a fluidized bed packed with 1kg of the molecular sieve sample FLHZSM-5-C of example 4. The second reaction zone was a fluidized bed packed with 1kg of the same molecular sieve sample FLHZSM-5-C of example 4. The preparation process of the catalyst comprises the following steps: the catalyst in each fluidized bed reactor was treated with 10L/min of nitrogen at 550 ℃ for 1 hour and then cooled to 300 ℃ under a nitrogen atmosphere. The same procedure as in example 19 was repeated to obtain a fixed bed catalyst designated FLCAT-17. The reaction results were consistent with example 19 (deviation not exceeding. + -. 1%).

Example 21 preparation of fixed bed catalyst FXCAT-18 and reaction evaluation

After the toluene and the paraxylene fixed bed catalyst are prepared on line in a miniature fixed bed reaction device by alkylation of benzene and methanol and the reaction performance is evaluated.

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-18. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 18.

Watch 18

Catalyst and process for preparing same	FXCAT-18
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.93
Selectivity (wt%) of p-xylene in xylene product	99.63
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.06
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.16
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.72
		Toluene	53.09
Ethylbenzene production	2.57
		Para-xylene	27.21
Meta-xylene	0.06
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	2.31

EXAMPLE 22 preparation and reaction evaluation of fixed bed catalyst FXCAT-19

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding tetraethyl silicate by using a trace feed pump, wherein the weight space velocity of the tetraethyl silicate is 0.1h^-1And normal pressure. Stopping feeding after 2 hours, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-19. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 19.

Watch 19

Catalyst and process for preparing same	FXCAT-19
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.43
Selectivity (wt%) of p-xylene in xylene product	99.78
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.33
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.37
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.81
		Toluene	53.32
Ethylbenzene production	2.51
		Para-xylene	27.07
Meta-xylene	0.04
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	2.23

EXAMPLE 23 preparation of fixed bed catalyst FXCAT-20 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding tetraethyl silicate by using a trace feed pump, wherein the weight space velocity of the tetraethyl silicate is 0.4h^-1And normal pressure. And stopping feeding after 0.5 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-20. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 20.

Watch 20

Catalyst and process for preparing same	FXCAT-20
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	36.37
Selectivity (wt%) of p-xylene in xylene product	99.67
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	90.95
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	93.99
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.61
		Toluene	52.92
Ethylbenzene production	2.63
		Para-xylene	27.34
Meta-xylene	0.05
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	2.41

EXAMPLE 24 preparation of fixed bed catalyst FXCAT-21 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 300 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-21. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 21.

TABLE 21

Catalyst and process for preparing same	FXCAT-21
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.37
Selectivity (wt%) of p-xylene in xylene product	99.70
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	90.48
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	93.09
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	13.62
		Toluene	53.41
Ethylbenzene production	2.76
		Para-xylene	26.99
Meta-xylene	0.04
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	3.13

EXAMPLE 25 preparation and reaction evaluation of fixed bed catalyst FXCAT-22

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 450 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-22. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 22.

TABLE 22

Example 26 preparation of fixed bed catalyst FXCAT-23 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 300 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 800 ℃ under the nitrogen atmosphere, feeding water by using a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 2 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-23. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 23.

TABLE 23

Catalyst and process for preparing same	FXCAT-23
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	33.26
Selectivity (wt%) of p-xylene in xylene product	99.65
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.19
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	93.68
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.57
		Toluene	54.35
Ethylbenzene production	2.39
		Para-xylene	25.68
Meta-xylene	0.05
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	2.92

Example 27 preparation of fixed bed catalyst FXCAT-24 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 300 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 600 ℃ under the nitrogen atmosphere, feeding water by using a trace feed pump, wherein the water weight space velocity is 2h^-1And stopping feeding after feeding for 8 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, which is named as FXCAT-24. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in the tableAs shown at 24.

Watch 24

Catalyst and process for preparing same	FXCAT-24
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	36.97
Selectivity (wt%) of p-xylene in xylene product	99.70
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.48
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	93.42
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.07
		Toluene	53.96
Ethylbenzene production	2.37
		Para-xylene	26.31
Meta-xylene	0.05
		Ortho-xylene	0.03
C₉₊Aromatic hydrocarbons	3.20

EXAMPLE 28 preparation of fixed bed catalyst FXCAT-25 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-11-B is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare a fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, wherein the fixed bed catalyst is named as FXCAT-25. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested, and the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 25.

TABLE 25

Catalyst and process for preparing same	FXCAT-25
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.56
Selectivity (wt%) of p-xylene in xylene product	99.82
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.40
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.39
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	15.31
		Toluene	52.72
Ethylbenzene production	2.51
		Para-xylene	27.22
Meta-xylene	0.03
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	2.19

Example 29 preparation of fixed bed catalyst FXCAT-26 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 150 ℃ in nitrogen atmosphere. The tetramethyl silicate is fed by a trace feed pump, and the weight space velocity of the tetramethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1At normal pressure, the feeding was stopped 4 hours laterThe fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is named as FXCAT-26. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 26.

Watch 26

Catalyst and process for preparing same	FXCAT-26
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.87
Selectivity (wt%) of p-xylene in xylene product	99.89
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	91.38
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.44
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	15.11
		Toluene	52.91
Ethylbenzene production	2.54
		Para-xylene	27.26
Meta-xylene	0.02
		Ortho-xylene	0.01
C₉₊Aromatic hydrocarbons	2.15

EXAMPLE 30 preparation of fluidized bed catalyst FLCAT-27 and reaction evaluation

The method is characterized in that a fluidized bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is prepared on line in a fixed fluidized bed reaction device.

The catalyst is prepared on line under the following conditions: 10g of the formed molecular sieve sample FLHZSM-5-C is put into a fixed fluidized bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air, and then cooled to 200 ℃ in a nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hourThe mixture is purged by nitrogen, heated to 550 ℃ and roasted for 4 hours in air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fluidized bed catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, which is named as FLCAT-27. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzene and methanol are tested as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 27.

Watch 27

EXAMPLE 31 preparation and reaction evaluation of fixed bed catalyst FXCAT-28

After the fixed bed catalyst for co-production of toluene from benzene and methanol and paraxylene is prepared on line in a micro fixed bed reaction device, the reaction performance is evaluated.

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-C is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. The tetraethyl silicate is fed by a micro-feed pump, and the weight space velocity of the tetraethyl silicate is 0.2h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in air atmosphere to obtain the fixed bed catalyst for preparing toluene and co-producing p-xylene by alkylation of benzene and methanol, which is named as FXCAT-28. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene and co-producing p-xylene through alkylation of benzyl alcohol are tested as follows: the raw material is fed by a trace feed pump, and the raw material benzene and methanol (molar ratio) are1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken at 120min of reaction for analysis, and the reaction results are shown in Table 28.

Watch 28

Catalyst and process for preparing same	FXCAT-28
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	38.01
Selectivity (wt%) of p-xylene in xylene product	93.60
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	80.64
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	82.91
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.06
		Toluene	44.92
Ethylbenzene production	4.52
		Para-xylene	26.33
Meta-xylene	0.99
		Ortho-xylene	0.81
C₉₊Aromatic hydrocarbons	8.37

EXAMPLE 32 preparation of fixed bed catalyst FXCAT-29 and reaction evaluation

After the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin is prepared on line in a micro fixed bed reaction device, the reaction performance is evaluated.

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1The pressure of the mixture is controlled at normal pressure,and stopping feeding after 4 hours to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-29. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 29.

Watch 29

Example 33 preparation of fixed bed catalyst FXCAT-30 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 4, and the space velocity of the total weight of the trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. Feeding is stopped after 1.5 hours, the temperature is raised to 550 ℃ under the air atmosphere, and roasting is carried out for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene low-carbon olefin, which is named as FXCAT-30. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, and the test is carried out to prepare toluene from benzene and methanol and co-produce p-xylene and low-carbon olefinThe reaction conditions were as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 30.

Watch 30

Example 34 preparation of fixed bed catalyst FXCAT-31 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 1, and the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. Feeding is stopped after 1.5 hours, the temperature is raised to 550 ℃ under the air atmosphere, and roasting is carried out for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-31. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product is analyzed by an on-line Agilent7890 gas chromatography, and the reaction product is sampled and analyzed when reacting for 120min. The reaction results are shown in Table 31.

Watch 31

Catalyst and process for preparing same	FXCAT-31
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	33.68
Selectivity (wt%) of p-xylene in xylene product	99.71
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	94.72
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	95.35
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	17.64
		Toluene	51.46
Ethylbenzene production	1.43
		Para-xylene	27.07
Meta-xylene	0.04
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	2.32
		Distribution of chain hydrocarbon products (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

Example 35 preparation of fixed bed catalyst FXCAT-32 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 250 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-32. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1At normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 32.

Watch 32

Catalyst and process for preparing same	FXCAT-32
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.32
Selectivity (wt%) of p-xylene in xylene product	99.82
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	94.60
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	95.39
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	17.15
		Toluene	52.05
Ethylbenzene production	1.49
		Para-xylene	26.98
Meta-xylene	0.03
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	2.28
		Distribution of chain hydrocarbon products (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

EXAMPLE 36 preparation and reaction evaluation of fixed bed catalyst FXCAT-33

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 300 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-33. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: trace feed pump for raw materialsFeeding, raw material benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 33.

Watch 33

Catalyst and process for preparing same	FXCAT-33
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.95
Selectivity (wt%) of p-xylene in xylene product	99.63
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	93.09
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.18
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	16.39
		Toluene	51.94
Ethylbenzene production	1.89
		Para-xylene	26.80
Meta-xylene	0.06
		Ortho-xylene	0.04
C₉₊Aromatic hydrocarbons	2.88
		Distribution of chain hydrocarbon products (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

EXAMPLE 37 preparation of fixed bed catalyst FXCAT-34 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 800 ℃ under the nitrogen atmosphere, feeding water by using a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 2 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-34. Then, the temperature is reduced to 450 ℃ under the nitrogen atmosphere, and benzene and toluene are testedThe method comprises the following steps of (1) carrying out reaction for preparing toluene by alcohol and co-producing p-xylene and low-carbon olefin, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 34.

Watch 34

Example 38 preparation of fixed bed catalyst FXCAT-35 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 600 ℃ under the nitrogen atmosphere, feeding water by using a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 8 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-35. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was subjected to an on-line Agilent7890 gas chromatographThe analysis was carried out by sampling at 120min of reaction. The reaction results are shown in Table 35.

Watch 35

Example 39 preparation of fixed bed catalyst FXCAT-36 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-11-A catalyst is tableted and formed, crushed and sieved to 40-60 meshes, 5g (40-60 meshes) of the catalyst is loaded into a fixed bed reactor, the fixed bed reactor is firstly treated by 50mL/min of air at 550 ℃ for 1 hour, and then the temperature is reduced to 200 ℃ under the nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-36. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 36.

Watch 36

Catalyst and process for preparing same	FXCAT-36
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	34.17
Selectivity (wt%) of p-xylene in xylene product	99.85
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	94.49
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	95.46
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	18.13
		Toluene	51.89
Ethylbenzene production	1.49
		Para-xylene	26.26
Meta-xylene	0.03
		Ortho-xylene	0.01
C₉₊Aromatic hydrocarbons	2.19
		Distribution of chain hydrocarbon products (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

EXAMPLE 40 preparation and reaction evaluation of fixed bed catalyst FXCAT-37

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetramethyl silicate by using a trace feed pump, wherein the weight ratio of the tetramethyl silicate: trimethoxy phosphine (mass ratio) is 2, and the total weight space velocity of the trimethoxy phosphine and the tetramethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-37. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 37.

Watch 37

Catalyst and process for preparing same	FXCAT-37
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	33.86
Selectivity (wt%) of p-xylene in xylene product	99.85
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	94.59
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	95.51
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	18.67
		Toluene	51.46
Ethylbenzene production	1.46
		Para-xylene	26.22
Meta-xylene	0.02
		Ortho-xylene	0.02
C₉₊Aromatic hydrocarbons	2.15
		Distribution of chain hydrocarbon products (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

EXAMPLE 41 preparation of fluidized bed catalyst FLCAT-38 and reaction evaluation

The fluidized bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin is prepared on line in a fixed fluidized bed reaction device.

The catalyst is prepared on line under the following conditions: 10g of the formed molecular sieve sample FLHZSM-5-A is put into a fixed fluidized bed reactor, treated by 50mL/min of air at 550 ℃ for 1 hour, and then cooled to 200 ℃ under the nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. After feeding for 1 hour, stopping feeding, raising the temperature to 550 ℃ under the air atmosphere, and roasting for 4 hours. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fluidized bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FLCAT-38. Then, the temperature is reduced to 450 ℃ in the nitrogen atmosphere, the reaction conditions for preparing toluene by alkylating benzene and methanol and co-producing p-xylene and low-carbon olefin are tested as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product passes through the on-line Agilent7890 gas phaseThe chromatography is carried out, and samples are taken for analysis when the reaction time is 120 min. The reaction results are shown in Table 38.

Watch 38

EXAMPLE 42 preparation and reaction evaluation of fixed bed catalyst FXCAT-39

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding a mixed solution of trimethoxy phosphine and tetraethyl silicate by using a trace feed pump, wherein the weight ratio of tetraethyl silicate: the mass ratio of trimethoxy phosphine to 2, the space velocity of the total weight of trimethoxy phosphine and tetraethyl silicate is 0.1h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere to obtain the fixed bed catalyst for co-production of p-xylene and low-carbon olefin from toluene prepared from benzene and methanol, which is named as FXCAT-39. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, and the raw materials of benzene: methanol (molar ratio) is 1:1, and the total weight space velocity of benzene and methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 39.

Watch 39

EXAMPLE 43 preparation of fixed bed catalyst FXCAT-40 and reaction evaluation

The catalyst is prepared on line under the following conditions: 5g (40-60 meshes) of formed molecular sieve sample FXHZSM-5-A is put into a fixed bed reactor, treated for 1 hour at 550 ℃ by 50mL/min of air and then cooled to 200 ℃ in nitrogen atmosphere. Feeding tetraethyl silicate by using a trace feed pump, wherein the weight space velocity of the tetraethyl silicate is 0.067h^-1And normal pressure. Stopping feeding after 1 hour, purging with nitrogen, heating to 550 ℃, and roasting for 4 hours in an air atmosphere. Heating to 700 ℃ under the nitrogen atmosphere, feeding water by a trace feed pump, wherein the water weight space velocity is 2h^-1And (3) stopping feeding after feeding for 4 hours at normal pressure to prepare the fixed bed catalyst for preparing toluene from benzene and methanol and co-producing p-xylene and low-carbon olefin, which is named as FXCAT-40. Then, cooling to the reaction temperature of 450 ℃ in the nitrogen atmosphere, and testing the reaction of co-producing p-xylene and low-carbon olefin by using toluene prepared from benzene and methanol, wherein the reaction conditions are as follows: the raw materials are fed by a trace feed pump, the molar ratio of the raw materials benzene to methanol is 1:1, and the total weight space velocity of the benzene and the methanol is 2h^-1And normal pressure. The reaction product was analyzed by on-line Agilent7890 gas chromatography, and samples were taken for analysis at 120min of reaction. The reaction results are shown in Table 40.

Watch 40

Catalyst and process for preparing same	FXCAT-40
		Reaction temperature (. degree.C.)	450
Methanol conversion (%)	100
		Benzene conversion (%)	35.93
Selectivity (wt%) of p-xylene in xylene product	99.49
		C₈Selectivity (wt%) of p-xylene in aromatic hydrocarbon product	90.93
Selectivity (wt%) of (toluene + p-xylene) in aromatic product	94.11
		Product distribution (wt%)
C₁-C₆₊Chain hydrocarbons	14.72
		Toluene	53.09
Ethylbenzene production	2.57
		Para-xylene	27.17
Meta-xylene	0.09
		Ortho-xylene	0.05
C₉₊Aromatic hydrocarbons	2.31
		Distribution of chain hydrocarbon products (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

Example 44 preparation of fixed bed catalyst FXCAT-41 and reaction evaluation

The device, operation and conditions are the same as those in example 5, except that the trimethoxy phosphorus is replaced by methyl diethoxy phosphorus in the catalyst preparation process, and the other components are unchanged, so that the fixed bed catalyst for preparing the low-carbon olefin by methanol and toluene and co-producing the p-xylene is prepared and named as FXCAT-41. The reaction evaluation conditions were the same as in example 5, and the reaction results were the same as in example 5 (deviation not more than. + -. 1%).

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims

1. An in-situ preparation method of a catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is characterized in that a silylation reagent and water vapor are contacted with a molecular sieve in a reactor, and the catalyst for preparing toluene and co-producing p-xylene by alkylating benzene and methanol is prepared in situ;

the reactor is a reactor for preparing toluene and co-producing p-xylene by alkylating benzene and methanol;

the molecular sieve is a molded molecular sieve molded according to the type of the reactor;

the formed molecular sieve is composed of a molecular sieve; or

The formed molecular sieve contains a molecular sieve and a binder;

the in-situ preparation method at least comprises the following steps:

(1) placing the shaped molecular sieve in a reactor;

2. The method according to claim 1, wherein the silylating agent is at least one selected from the group consisting of compounds having the formula shown in formula I:

3. The method of claim 2, wherein R in formula I₁，R₂，R₃，R₄At least one of them is selected from C₁～C₁₀Alkoxy group of (2).

4. The method of claim 1, wherein the silylating agent is selected from at least one of tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, and tetrabutyl silicate.

5. The method of claim 1, wherein the reactor is selected from at least one of a fixed bed, a fluidized bed, and a moving bed reactor.

6. The method of claim 1, wherein the molded molecular sieve is prepared by one of crushing and molding a molecular sieve tablet, mixing and extruding the molecular sieve with a binder, cutting the molecular sieve into strips, mixing the molecular sieve with the binder, and spray drying and molding the molecular sieve and the binder.

7. The process of claim 1, wherein the molecular sieve is selected from at least one of a molecular sieve having an MFI framework structure and a molecular sieve having an MEL framework structure.

8. The process of claim 1, wherein the molecular sieve is an HZSM-5 molecular sieve and/or an HZSM-11 molecular sieve.

9. The method of claim 1, wherein the material D in step (2) comprises a silylating agent and benzene.

10. The method of claim 1, wherein the step (2) comprises introducing the material D containing the silylation agent into the reactor at a temperature of 130 ℃ to 500 ℃.

11. The method of claim 1, wherein the weight space velocity of the material D in the step (2) is 0.1h^-1～1h^-1And the time for introducing the material D is 0.1-5 hours.

12. The method of claim 1, wherein the weight space velocity of the material D in the step (2) is 0.2h^-1～0.4h^-1And the time for introducing the material D is 0.5-2 hours.

13. The method according to claim 1, wherein the calcination temperature in the step (3) is 500 ℃ to 700 ℃ and the calcination time is 1 to 6 hours.

14. The method according to claim 1, wherein the inert gas in step (4) is at least one selected from nitrogen, helium and argon.

15. The method according to claim 1, wherein the temperature of the steam treatment in the step (4) is 550 to 800 ℃ and the treatment time is 1 to 10 hours.

16. A method for preparing toluene and co-producing p-xylene by alkylating benzene and methanol, which is characterized in that a raw material containing methanol and benzene is contacted with a catalyst for preparing toluene and co-producing p-xylene by alkylating the benzene and the methanol, which are prepared in situ according to the method of any one of claims 1 to 15, in a reactor to prepare the toluene and co-producing the p-xylene.

17. The method of claim 16, wherein the reaction temperature for co-production of p-xylene from toluene by alkylation of benzene and methanol is 350-600 ℃.

18. The method of claim 16, wherein the reaction temperature for the co-production of p-xylene from toluene by alkylation of benzene and methanol is 400-500 ℃.

19. The process of claim 16, wherein the molar ratio of methanol to benzene in the feed comprising methanol and benzene is methanol: and (3) benzene is 0.5-2: 1.