In-situ manufacturing process for catalyst for the production of at least one of Tutol, paraxylene and light olefins and reaction process

Abstract

Method for carrying out a reaction I, wherein a raw material comprising methanol and / or dimethyl ether and toluene is contacted in a reactor with a catalyst obtained in an in-situ and in-line process to produce light olefins with a co-product of paroxylol, where reaction I is intended to produce light olefins from methanol and / or dimethyl ether and toluene with the co-product paroxylol, wherein a material stream I is brought into contact with the catalyst in the reaction system to obtain a material stream II, and C4 olefin or C 5+ Chain hydrocarbons are separated from material stream II, and the light olefins and paraxylene separated from material stream II and returned to the reaction system are used as products. the material stream I contains methanol and / or dimethyl ether and toluene, wherein the reaction system comprises: a first reaction zone containing a catalyst A; and a second reaction zone containing a catalyst B; and wherein catalyst A is an HZSM-5 molecular sieve catalyst modified by a phosphorus reagent and a silylation reagent, wherein the specific preparation steps are as follows: (A1) A mixture of the phosphorus reagent, the silylation reagent and toluene is fed into the first reaction zone with the HZSM-5 molecular sieve at a temperature in the range of 130°C to 500°C; (A2) The temperature is increased to over 500°C and the mixture is calcined in an air atmosphere for a period of 1 hour to 6 hours to obtain catalyst A, wherein catalyst B is an HZSM-5 molecular sieve catalyst modified by a silylation reagent, the specific preparation steps being as follows: (B1) A mixture of the silylation reagent and methanol is fed into the second reaction zone with the HZSM-5 molecular sieve at a temperature in the range of 120°C to 250°C; (B2) The temperature is increased to over 500°C and the mixture is calcined in an air atmosphere for a period of time ranging from 1 hour to 6 hours to obtain catalyst B.

Description

Technical field

[0001] The invention relates to an in-situ manufacturing process for catalyst for the production of at least one of toluene, paraxylene and light olefins and a reaction process for the production of at least one of toluene, paraxylene and light olefins, which belongs to the field of chemical engineering. State of the art

[0002] Ethylene and propylene are the cornerstones of the vast petrochemical industry, and most organic chemicals are derived from them. Paraxylene (PX) is a raw material for the production of polyesters such as PET (polyethylene terephthalate), PBT (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). In recent years, the widespread use of polyester in textiles, apparel, beverage packaging, and other applications has driven the rapid growth in the production and consumption of PTA (pure terephthalic acid) and the precursor PX. Currently, PX is primarily produced through disproportionation, isomerization, and adsorption or low-temperature separation using toluene, C9 aromatics, and mixed xylene as feedstocks, which are obtained through naphtha reforming. This process requires significant equipment investment and high operating costs.Since the paraxylene content in the product is thermodynamically controlled, paraxylene constitutes only about 20% of the xylene isomer, and the difference in boiling points between the three xylene isomers is small. Therefore, high-purity paraxylene cannot be obtained by ordinary distillation technology; an expensive adsorption separation process must be employed.

[0003] USP 3,911,041, USP 4,049,573, USP 4,100,219, etc., disclose the reactions for the conversion of methanol to olefins on an HZSM-5 catalyst modified by phosphorus, magnesium, or silicon, etc.; USP 5,367,100 and USP 5,573,990 disclose the reactions for the preparation of light olefins from methanol or dimethyl ether using an HZSM-5 molecular sieve catalyst modified by phosphorus and rhodium from the Dalian Institute of Chemical Physics and Physics of the Chinese Academy of Sciences.Since the 1970s, research has been conducted both domestically and internationally on the technology for producing paraxylene by alkylation of toluene and methanol, utilizing inexpensive and readily available toluene and methanol as raw materials; the selectivity of PX in primary reaction products is high; the production process avoids the need for expensive adsorption separation technology, allowing for the obtaining of highly pure paraxylene through simple crystallization separation; and the benzene content in the products is low.

[0004] Mainly, metallic and / or non-metallic modified HZSM-5 molecular sieve catalysts are used. USP 4,250,345 uses a ZSM-5 molecular sieve catalyst modified by two elements, phosphorus and magnesium, with which the optimal selectivity of paraxylene is approximately 98% at 450°C. Chinese patent CN101485994A discloses a ZSM-5 catalyst jointly modified by Pt, Si, Mg, P, and mixed rare-earth elements, with which the conversion rate of toluene is greater than 20%, the selectivity of PX is greater than 98% when the molar ratio of toluene to methanol is 2:1 and the reaction temperature is 460°C.Chinese patent CN102716763A discloses an HZSM-5 molecular sieve catalyst modified by elements P, Ni and by SiO2 deposition, which is used to realize the alkylation of toluene and methanol in a fixed-bed reactor, with the conversion rate of toluene being approximately 31% and the selectivity of PX being approximately 91%.

[0005] The above reports show that the HZSM-5 molecular sieve catalyst can be used not only for the production of light olefins via methanol conversion, but also for the production of paraxylene via the alkylation of methanol and toluene. However, due to the differences between the two reaction processes, there are also significant differences in the physicochemical properties of the catalysts. Therefore, once a single catalyst capable of simultaneously fulfilling the requirements of both reactions—the production of light olefins via methanol conversion and the production of paraxylene via the alkylation of methanol and toluene—can be produced through a suitable modification process, the simultaneous production of light olefins (ethylene, propylene) and paraxylene using the same catalyst can be achieved.Chinese patent CN101417236A discloses a fluidized bed catalyst for the production of paraxylene and light olefins from methanol and toluene. The catalyst utilizes the HZSM-5 molecular sieve catalyst modified by alkaline earth metal, nonmetal, rare earth metal, and siloxane. The selectivity of PX in the xylene product reaches 99%, and the selectivity of ethylene and propylene in non-condensable C1-C5 gas is greater than 90%. However, the toluene conversion rate is only approximately 20%, and the methanol conversion rate is not specified. Furthermore, the catalyst's manufacturing process is complex, requiring multiple modification and calcination steps.

[0006] US 4088706 A describes a catalytic process for converting lower monohydric alcohols and their ethers, especially methanol and dimethyl ether, into a hydrocarbon mixture rich in C2-C3 olefins and mononuclear aromatics, with high selectivity for para-xylene production by contact under conversion conditions with a catalyst comprising a crystalline aluminosilicate zeolite, wherein the zeolite has a silicon dioxide to aluminum oxide ratio of at least about 12 and a forced index, as defined below, within the approximate range of 1 to 12, wherein the catalyst has been modified by the addition of a minor proportion of a boron or magnesium oxide, either alone or in combination or in further combination with a phosphorus oxide.

[0007] US 5571768 A describes a zeolite, such as ZSM-5, functionalized with at least one organosilicon group of the formula SiRn(OX)4-n, where R is at least one hydrocarbyl group, n is 1 or 2, and X is Si or H. A method for functionalizing a zeolite by treatment with a silicon compound, such as hexamethyldisiloxane, under vapor-phase conditions is also provided. This contacting can be carried out in the presence of hydrogen and an organic support. The functionalized zeolites can provide a catalyst that is both highly active and highly selective for converting aromatic hydrocarbons, especially alkylbenzene compounds, into products comprising the para-isomer of dialkylbenzenes. The disproportionation of toluene is an example of such a reaction.

[0008] Therefore, the development of an easy-to-process and easy-to-handle online manufacturing process of the catalyst for the production of paraxylene or the production of light olefins with a co-product of paraxylene is of great importance and of considerable practical applicability. Description of the invention

[0009] The invention is defined in the main claim. Embodiments of the invention are specified in the dependent claims.

[0010] According to one aspect of the present application, an easy-to-process and easy-to-handle in-situ production method for a catalyst is provided, which is a catalyst for the production of paraxylene, toluene and / or light olefins from raw materials containing methanol and / or dimethyl ether. By directly producing the catalyst in the reaction system, the entire chemical production process is simplified, eliminating the steps of catalyst production and transport, thus simplifying operations.This disrupts the traditional production method in the existing chemical industry, in which finished catalysts are first produced in the catalyst production unit, transported to chemical production units, filled in, and then production is advanced, thereby overcoming the technical prejudices in large-scale industrial production in the field of heterogeneous catalysis.

[0011] In the in-situ catalyst production process, a modifier is brought into contact with the molecular sieve in the reactor, thus producing the catalyst in situ for the production of paraxylene, toluene and / or light olefins from the raw materials containing methanol and / or dimethyl ether;

[0012] The reactor is a reactor in which reactions are carried out to produce paraxylene, toluene and / or light olefins from raw materials containing methanol and / or dimethyl ether.

[0013] Preferably, the modifier comprises at least one of the following: Modifier I: a phosphorus reagent and a silylation reagent; Modifier II: silylation reagent; Modifier III: Silylating reagent and water vapor; Modifier IV: Phosphorus reagent, silylation reagent and water vapor;

[0014] Preferably, the catalyst is a catalyst for at least one of the following reactions: Reaction I: Production of light olefins via co-produced paraxylene from methanol and / or dimethyl ether and toluene; Reaction II: Preparation of at least one of toluene, paraxylene and light olefins from methanol and / or dimethyl ether; Preferably, the reactor is a reactor in which at least one of reactions I or II takes place.

[0015] In a preferred embodiment, reaction I is the production of paraxylene from methanol and / or dimethyl ether, toluene; In another preferred embodiment, reaction I is the production of paraxylene from methanol and toluene.

[0016] In one embodiment, reaction II is the production of toluene with a co-product of paraxylene and light olefins from methanol and / or dimethyl ether and benzene.

[0017] In a preferred embodiment, reaction II is the production of toluene with a co-product of paraxylene and from methanol and / or dimethyl ether and benzene.

[0018] In a preferred embodiment, reaction II is the preparation of paraxylene with a co-product of and light olefins from methanol and / or dimethyl ether and benzene.

[0019] In another preferred embodiment, reaction II is the production of paraxylene from methanol and / or dimethyl ether and benzene.

[0020] In a further preferred embodiment, reaction II is the production of paraxylene from methanol and benzene.

[0021] In one embodiment, the phosphorus reagent is selected from at least one of the organophosphine compounds. Preferably, the phosphorus reagent is selected from at least one of the compounds with the chemical formula of formula I:

[0022] R1, R2 and R3 are independent of each other from the C1~C 10 -Alkyl groups or the C1~C 10 -Alkoxy groups selected.

[0023] R1, R2, R3 in formula I are further preferred independently of each other from the C1~C5 alkyl groups or the C ı ~C5 alkoxy groups selected.

[0024] Preferably, at least one of R1, R2 and R3 is in formula I from C1~C 10 -Alkoxy groups selected. At least one of R1, R2, R3 in formula I from C1~C is further preferred. 10 -Alkoxy groups selected. Even more preferred are R1, R2, R3 in formula I, which are the same alkoxy groups.

[0025] In one embodiment, the phosphorus reagent is at least one reagent selected from trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine and methyldiethoxyphosphine.

[0026] In one embodiment, the silylation reagent is at least one organosilicon compound selected from the group of organosilicon compounds. Preferably, the silylation reagent is at least one compound selected from the group of compounds with the chemical formula of formula II:

[0027] R4, R5, R6 and R7 are independently derived from C1~C 10-Alkyl groups or the C1~C 10 -Alkoxy groups selected.

[0028] R4, R5, R6, R7 in formula II are further preferably selected independently of each other from the C1~C5 alkyl groups or C1~C5 alkoxy groups.

[0029] Preferably, at least one of R4, R5, R6 and R7 in formula II is C1~C 10 -Alkoxy groups selected. More preferably, at least one of R4, R5, R6 and R7 in formula II is selected from C1~C5 alkoxy groups. Even more preferably, R4, R5, R6 and R7 in formula II are the same alkoxy groups.

[0030] In one embodiment, the silylation reagent is at least one reagent selected from tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.

[0031] Preferably, the reactor is at least one reactor selected from a fixed-bed, fluidized-bed and / or moving-bed reactor.

[0032] Preferably, the molecular sieve is a shaped molecular sieve designed according to the reactor type.

[0033] The shaped molecular sieve consists of molecular sieve or the shaped molecular sieve contains molecular sieve and binder.

[0034] As an alternative embodiment, the shaped molecular sieve is produced by a process comprising the following: it is shaped by tablet crushing of a molecular sieve; after the molecular sieve and the binder are mixed and extruded, it is shaped by strip breaking; after the molecular sieve and the binder are mixed, it is shaped by spray drying.

[0035] Preferably, the molecular sieve is at least one molecular sieve selected from the molecular sieve with an MFI framework structure and the molecular sieve with a MEL framework structure.

[0036] Preferably, the molecular sieve is an HZSM-5 molecular sieve and / or an HZSM-11 molecular sieve.

[0037] Preferably, the ratio of silicon to aluminum (atomic ratio) in the molecular sieve is Si / Al = 5 ~ 35.

[0038] Preferably, the in-situ manufacturing process of the catalyst comprises at least the following steps: (1) Introducing the shaped molecular sieve into a reactor; (2) Introduction of a material containing a modifier into the reactor; (3) By ceasing the introduction of the modifier-containing material into the reactor, raising the temperature of the reactor to 400 °C or higher and calcining after the introduction of air, the catalyst is obtained.

[0039] Preferably, material A in step (2) contains at least one of the raw materials and a modifier.

[0040] Preferably, material A in step (2) contains toluene and / or benzene.

[0041] Preferably in step (2) the material A containing the modifier I is introduced into the reactor, wherein the modifier I contains a phosphorus reagent and a silylation reagent.

[0042] Preferably, material A in step (2) contains modifier I and toluene.

[0043] Preferably in step (2) the material A, which contains the phosphorus reagent and the silylation reagent, is introduced into the reactor at a temperature of 130 °C ~ 500 °C.

[0044] Preferably, material A contains a phosphorus reagent, a silylation reagent and toluene.

[0045] The mass ratio of the phosphorus reagent to the silylation reagent in material A in step (2) is further preferred: silylation reagent : phosphorus reagent = 1 : 2 to 5 : 1.

[0046] In addition to the phosphorus reagent, the silylation reagent, and the toluene, material A may contain other reagents that can improve the modification efficiency of the molecular sieve by the phosphorus reagent and the silylation reagent without impairing the reaction performance of the catalyst. Preferably, in step (2), the phosphorus reagent constitutes 1 wt. % to 10 wt. % of the total weight of material A; the silylation reagent constitutes 1 wt. % to 40 wt. % of the total weight of material A; and the toluene constitutes 50 wt. % to 98 wt. % of the total weight of material A. Furthermore preferably, the phosphorus reagent in material A in step (2) constitutes 2 wt. %, ~ 10 wt. %, of the total weight of material A, the silylation reagent constitutes 8 wt. %, ~ 40 wt. %, of the total weight of material A, and the toluene constitutes 50 wt. %, ~ 90 wt. %, of the total weight of material A.

[0047] The person skilled in the art can adjust the space velocity and the time of the entry of material A into the reactor in step (2) according to the specific requirements of the actual production process. Preferably, the total weight space velocity of material A, entered into the reactor in step (2), is 0.5 h⁻¹. -1 ~ 2h -1 .

[0048] Preferably, the time for introducing material A into the reactor in step (2) is 30 minutes to 225 minutes.

[0049] Preferably, in step (3), after the introduction of material A into the reactor has ceased, the reactor is first purged with an inert gas, and then the temperature is increased and calcined. More preferably, the inert gas is at least one composed of nitrogen, helium, and argon.

[0050] Preferably the calcination temperature in step (3) is 500 °C ~ 700 °C and the calcination time is 1 ~ 6 hours.

[0051] Preferably in step (2) a material B containing modifier II is introduced into the reactor, wherein the modifier II contains a silylation reagent.

[0052] Further preferably, material B in step (2) contains at least one of methanol, toluene, dimethyl ether and modifier II.

[0053] Preferably in step (2) a material B containing modifier III is introduced into the reactor, wherein the modifier III contains the silylation reagent and the water vapor.

[0054] Preferably, the in-situ manufacturing process of the catalyst comprises at least the following steps: (1) Introducing the shaped molecular sieve into a reactor; (2) Introduction of a material D containing a silylation reagent into the reactor; (3) Cessation of the introduction of material D into the reactor, raising the temperature of the reactor to 500 °C or higher and calcination after the introduction of air; (4) Introduction of the inert gas and purging, followed by raising the reactor temperature to 550 °C or higher and introducing the vapor-containing material G to carry out the vapor treatment. This will obtain the catalyst.

[0055] Preferably, material D in step (2) contains a silylation reagent and benzene.

[0056] Preferably, the mass velocity of material D in step (2) is 0.1h -1 ~1h -1 and the time required to introduce material D is 0.1 ~ 5 hours.

[0057] Preferably, the mass velocity of material D in step (2) is 0.2h -1 ~ 0.4h -1 and the time required to introduce material D is 0.5 ~ 2 hours.

[0058] Furthermore, the material E preferably contains water vapor and benzene in step (4).

[0059] Preferably, the in-situ manufacturing process of the catalyst comprises at least the following steps: (1) Introducing the shaped molecular sieve into a reactor; (2) Introduction of a material F containing a phosphorus reagent and a silylation reagent into the reactor; (3) Cessation of the introduction of material D into the reactor, raising the temperature of the reactor to 500°C or higher and calcination after inflow of air; (4) Introduction of the inert gas and purging, followed by raising the reactor temperature to 550 °C or higher and introducing the vapor-containing material G to carry out the vapor treatment. This will obtain the catalyst.

[0060] The material F preferably contains in step (2) phosphorus reagent, silylation reagent and benzene.

[0061] The mass ratio of the silylation reagent to the phosphorus reagent in material F in step (2) is further preferred: Silylation reagent: Phosphorus reagent = 1:2 ~ 5:1.

[0062] Preferably, the calcination temperature in step (3) is 500 °C ~ 700 °C and the calcination time is 1 ~ 6 hours.

[0063] The inert gas in step (4) is preferably at least one of nitrogen, helium and argon.

[0064] Preferably, the temperature of the steam treatment in step (4) is 550 °C ~ 800 °C and the treatment time is 1 ~ 10 hours.

[0065] Furthermore, the material G in step (4) preferably contains water vapor and benzene.

[0066] Preferably, the mass velocity of the water vapor in the material G in step (4) is 0.5h -1 ~ 5h -1. Further preferably, the mass velocity of the water vapor in the material G in step (4) is 1h -1 ~3h -1 .

[0067] The water vapor-containing material G can be 100% water vapor or can be an inert gas and / or other reagents that can improve (adjust) the modification efficiency of the water vapor without affecting the reaction performance of the catalyst.

[0068] Preferably the temperature of the steam treatment in step (4) is 550 °C ~ 800 °C and the treatment time is 1 ~ 10 hours.

[0069] Preferably, in step (2) the phosphorus reagent constitutes 1 wt. %, ~ 10 wt. %, of the total weight of material A, the silylation reagent constitutes 1 wt. %, ~ 40 wt. %, of the total weight of material A, and the toluene constitutes 50 wt. %, ~ 98 wt. %, of the total weight of material A.

[0070] Preferably, the phosphorus reagent in the material F in step (2) constitutes 1 wt. %, ~ 10 wt. %, of the total weight of the material F, the silylation reagent constitutes 1 wt. %, ~ 40 wt. %, of the total weight of the material F, and the benzene constitutes 50 wt. %, ~ 98 wt. %, of the total weight of the material F.

[0071] Preferably the calcination temperature in step (3) is 500 °C ~ 700 °C and the calcination time is 1 ~ 6 hours.

[0072] Preferably in step (2) the material containing the modifier is introduced into the reactor at a temperature of 130 °C ~ 500 °C.

[0073] Preferably in step (2) the material containing the modifier is introduced into the reactor at a temperature of 200 °C ~ 400 °C.

[0074] According to another aspect of the present application, a process for the production of light olefins with a co-product of paraxylene from methanol and / or dimethyl ether and toluene (Reaction I) is provided, characterized in that the raw materials containing methanol and / or dimethyl ether and toluene are brought into contact with the reactor containing the catalyst for the production of light olefins with a co-product of paraxylene (Reaction I), which is prepared in situ according to one of the above processes, in order to produce light olefins with a co-product of paraxylene. That is to say, after completion of the calcination of the modified catalyst, the temperature is lowered from the calcination temperature to the reaction temperature in order to start the reaction for the production of light olefins with a co-product of paraxylene.Compared to the inherent production method in the chemical field, the washing separation process after catalyst modification, the catalyst cooling process after calcination (in which the catalyst temperature is lowered to room temperature), the catalyst transport step, the catalyst loading step, and the high-temperature pre-activation step required after loading the catalyst into the reactor, etc., are eliminated. This significantly improves production efficiency and avoids the safety issues that can arise during the aforementioned omitted steps. More importantly, once the reactor temperature is lowered from the calcination temperature to the reaction temperature, the reaction can be initiated, thus fully utilizing the thermal energy and significantly reducing energy consumption in production.

[0075] In the process for carrying out reaction I, the raw materials containing methanol and / or dimethyl ether and toluene are brought into contact in a reactor with the catalyst produced in situ and in-line according to the process described in the above aspect, in order to produce light olefins with a co-product of paraxylene.

[0076] Reaction I: Preparation of light olefins with a co-product of paroxylol from methanol and / or dimethyl ether and toluene.

[0077] In a preferred embodiment, reaction I is the production of toluene with a co-product of paroxylol from methanol and / or dimethyl ether.

[0078] In a preferred embodiment, reaction I is the production of paroxylol from methanol and / or toluene. In a preferred embodiment, the phosphorus reagent and the silylation reagent are brought into contact with the molecular sieve in the reactor to produce the catalyst for reaction I in situ; The reactor is a reactor in which reaction I takes place.

[0079] Preferably, the raw material is brought into contact with the catalyst at a reaction temperature of 350 °C ~ 650 °C.

[0080] Preferably, the raw material is brought into contact with the catalyst at a reaction temperature of 400 °C ~ 500 °C.

[0081] Preferably the ratio of methanol and / or dimethyl ether to toluene in the raw materials containing methanol and / or dimethyl ether or toluene is as follows: The number of carbon atoms in methanol and dimethyl ether: Mole of toluene = 0.5 ~ 10.

[0082] In an alternative embodiment, the reaction feedstocks contain methanol and toluene. Since methanol can be converted to dimethyl ether at the catalyst (the effect of methanol and dimethyl ether in the feedstocks is the same), the actual introduced reaction feedstocks contain methanol and toluene, but methanol, dimethyl ether, and toluene are frequently present on the reactor catalyst. Methanol and toluene are mentioned below as examples of feedstocks, but the possibility of dimethyl ether being present in the feedstocks is not excluded. In the calculation, the number of moles of carbon atoms in the dimethyl ether corresponds to the number of moles of methanol.

[0083] In raw materials containing methanol and toluene, the molar ratio of methanol to toluene is methanol:toluene = 0.5 ~ 20:1. Preferably, in raw materials containing methanol and toluene, the molar ratio of methanol to toluene is methanol:toluene = 1 ~ 15:1. More preferably, in raw materials containing methanol and toluene, the molar ratio of methanol to toluene is methanol:toluene = 5 ~ 15:1. In actual production, the ratio of light olefins to paraxylene in the product can be adjusted by modifying the methanol to toluene ratio in the raw materials according to specific production requirements. Generally, increasing the methanol / toluene ratio in the raw materials increases the olefin content in the product, and decreasing the methanol / toluene ratio in the raw materials increases the paraxylene content in the product.

[0084] Preferably, the total mass velocity of the raw materials containing methanol and toluene is 1 h⁻¹. -1 ~ 3h -1 .

[0085] Preferably, current I contacts the catalyst t in a reaction system, thus yielding current II. Then, the C4 olefins or C separated from current II are 5+ Chain hydrocarbons are recycled into the reaction system and the light olefins and paraxylene separated from stream II are accepted as products.

[0086] Stream I contains methanol and / or dimethyl ether, toluene.

[0087] Preferably, the reaction system comprises a first reaction zone and a second reaction zone, in which stream I is brought into contact with the catalyst in the first reaction zone, thus obtaining stream II-A. Then, the C4 olefins or C separated from stream II-A are 5+Chain hydrocarbons are recycled to the second reaction zone and brought into contact with the catalyst, thus yielding current II-B. The C4 olefins or C 5+ Chain hydrocarbons are separated from stream II-B and returned to the second reaction zone.

[0088] The light olefins and paraxylene separated from stream II-A and stream II-B are accepted as the product.

[0089] Preferably, the reaction system comprises a first reaction zone and a second reaction zone. In the first reaction zone, stream I is brought into contact with the catalyst, thus obtaining stream II-A. Stream II-A is then introduced into the separation system, and C4 olefins, light olefins, and paraxylene are separated.

[0090] The C4 olefins separated by the separation system are introduced into the second reaction zone and brought into contact with the catalyst, thus obtaining stream II-B, and stream II-B is introduced into the separation system;

[0091] The light olefins and paraxylene separated by the separation system are accepted as products.

[0092] Preferably, the reaction system comprises a first reaction zone and a second reaction zone. In the first reaction zone, current I is brought into contact with the catalyst, thus obtaining current II-A. Then, current II-A is introduced into the separation system, which leads to C. 5+ Chain hydrocarbons, light olefins and paraxylene.

[0093] The C separated from the separation system 5+Chain hydrocarbons are refined into the second reaction zone and brought into contact with the catalyst, thus obtaining stream II-B, and stream II-B is introduced into the separation system;

[0094] The light olefins and paraxylene produced by the separation system are accepted as products.

[0095] Preferably the reaction system comprises a first reaction zone and a second reaction zone, wherein the first reaction zone and the second reaction zone each contain catalyst A; Catalyst A is a HZSM-5 molecular sieve catalyst modified by phosphorus reagent and silylation reagent, the specific preparation steps of which are as follows: (A1) Introducing a phosphorus reagent and a silylation reagent into the first reaction zone, which is filled from the HZSM-5 molecular sieve, at 130 °C ~ 500 °C; (A2) Increase the temperature to 500 °C or higher and cation in an air atmosphere for 1 ~ 6 hours to obtain catalyst A.

[0096] Preferably, the reaction system comprises a first reaction zone containing catalyst A and a second reaction zone containing catalyst B.

[0097] Further preferred is catalyst A, a HZSM-5 molecular sieve catalyst modified by phosphorus reagent and silylation reagent, the specific preparation steps of which are as follows: (A1) Introducing a mixture of the phosphorus reagent, the silylation reagent and toluene into the first reaction zone, which is filled by the HZSM-5 molecular sieve, at 130 °C ~ 500 °C; (A2) Increase the temperature to 500 °C or higher and cation in an air atmosphere for 1 ~ 6 hours to obtain catalyst A.

[0098] Further preferred is catalyst B, a silylation reagent-modified HZSM-5 molecular sieve catalyst, the specific preparation steps of which are as follows: (B1) Introducing a mixture of silylation reagent and methanol into a second reaction zone, filled by the HZSM-5 molecular sieve, at 120 °C ~ 250 °C; (B2) The temperature is increased to 500 °C or higher and cation is carried out in an air atmosphere for 1 ~ 6 hours to obtain catalyst B.

[0099] Preferably, the reaction system comprises one or more reactors connected in series and / or in parallel.

[0100] The reactor is preferably at least one of a fixed bed, fluidized bed or moving bed type.

[0101] Preferably, the reaction system comprises a first reaction zone and a second reaction zone, wherein the first reaction zone and the second reaction zone are located in the same reactor.

[0102] Preferably, the reaction system comprises a first reaction zone and a second reaction zone, wherein the first reaction zone comprises one or more reactors connected in series and / or parallel, and wherein the second reaction zone comprises one or more reactors connected in series and / or parallel.

[0103] Preferably, the first reaction zone and the second reaction zone are connected by series or parallel connection.

[0104] In one embodiment of the present application, the reaction of the conversion of the methanol and the reaction of the alkylation of toluene and methanol are carried out in the first reaction zone, and the reaction of shape-selective aromatization is carried out in the second reaction zone.

[0105] Preferably, the total feed rate of the raw materials is 0.1h. -1 ~ 10h -1 .

[0106] Preferably, the total feed rate of the raw materials is 0.8h. -1 ~ 3h -1 .

[0107] Preferably, the molar content of toluene in the raw materials is 5 mol% ~ 50 mol%.

[0108] Preferably, the molar content of toluene in the raw materials is 20 mol% ~ 40 mol%.

[0109] Preferably, the phosphorus reagent and silylation reagent are brought into contact with the molecular sieve in the reactor to produce the catalyst for the preparation of light olefins with a co-product of paraxylene in situ;

[0110] The reactor is a reactor for the production of light olefins with a co-product of paraxylene.

[0111] According to a further aspect of the present application, a process for the production of at least one of toluene, paraxylene, and light olefins from methanol and / or dimethyl ether and benzene (Reaction II) is provided, characterized in that the raw materials containing methanol and / or dimethyl ether and toluene are contacted in the reactor with the catalyst of Reaction II, which is produced in situ according to one of the above processes, to produce toluene, paraxylene, and light olefins. That is to say, after completion of the modification of Modifiers I to IV, the temperature is directly lowered from the temperature for the modification to the temperature for the reaction in order to initiate the reaction for the production of at least one of toluene, paraxylene, and light olefins from methanol and / or dimethyl ether and benzene.Compared to the inherent production method in the chemical field, the washing separation process after catalyst modification, the catalyst cooling process after calcination (in which the catalyst temperature is lowered to room temperature), the catalyst transport step, the catalyst loading step, the high-temperature pre-activation step required after loading the catalyst into the reactor, etc., are eliminated. This significantly improves production efficiency and avoids the safety issues that can arise during the aforementioned omitted steps. More importantly, once the reactor temperature is lowered from the calcination temperature to the reaction temperature, the reaction can be initiated, thus fully utilizing the thermal energy and significantly reducing energy consumption in production.

[0112] In the process for carrying out reaction I, the raw materials containing methanol and / or dimethyl ether and benzene are brought into contact in a reactor with the catalyst fKa reaction II, which is produced in situ and in-line according to one of claims 1 ~ 40, in order to produce toluene with a co-product of paroxylol.

[0113] Reaction II: Preparation of at least one of toluene, paraxylene, light olefins from methanol and / or dimethyl ether and benzene.

[0114] Preferably, the phosphorus reagent and the water vapor are brought into contact with the molecular sieve in the reactor to produce the catalyst for reaction II in situ; The reactor is a reactor in which reaction II takes place.

[0115] After the steam modification is complete, the temperature is directly lowered from the temperature at which the steam was modified to the temperature at which the reaction began, in order to initiate the reaction for the production of toluene with a co-product of paraxylene via alkylation of methanol and / or dimethyl ether and benzene. Compared to the inherent production method in the chemical industry, the washing separation process after catalyst modification, the cooling process of the catalyst after calcination (in which the catalyst temperature is lowered to room temperature), the step for transporting the catalyst, the step for loading the catalyst, the step requiring high-temperature pre-activation after loading the catalyst into the reactor, etc., are all significantly different.Savings are achieved, which significantly improves production efficiency and avoids the safety problems that can occur in the steps omitted above; more importantly, once the temperature in the reactor is lowered from the calcination temperature to the reaction temperature, the reaction can be started, thus fully utilizing the thermal energy, which significantly reduces energy consumption in production.

[0116] The raw materials of the present application are benzene and methanol, the methanol comprising feed types of methanol and / or dimethyl ether. Since methanol can be converted to dimethyl ether on the catalyst, the effect of methanol and dimethyl ether in the raw material is the same, so that the actual refined reaction feedstocks are methanol and toluene. Consequently, methanol, dimethyl ether, and toluene are frequently present on the reactor catalyst. Methanol and toluene are mentioned below as examples of raw materials, but the possibility of dimethyl ether being present in the raw materials is not excluded. In the calculation, the number of moles of carbon atoms in the dimethyl ether corresponds to the number of moles in the methanol.

[0117] In the present application, toluene is produced from benzene and methanol using co-products of paraxylene and light olefins, wherein the raw materials contain benzene and methanol, and in some cases where the methanol contains methanol and / or dimethyl ether. Unless otherwise specified, the methanol in the present application can be wholly or partially replaced by dimethyl ether, and with regard to the amount of methanol, dimethyl ether can be converted to methanol with the same number of carbon atoms.

[0118] A further preferred reactor is at least one reactor selected from the group consisting of a fixed bed, fluidized bed or moving bed.

[0119] Preferably, the reaction temperature of reaction II is between 350 °C and 600 °C.

[0120] Preferably, the reaction temperature of reaction II is between 400 °C and 500 °C.

[0121] In raw materials containing methanol and benzene, the molar ratio of methanol to benzene is methanol:benzene = 0.5 ~ 10:1. Preferably, in raw materials containing methanol and benzene, the molar ratio of methanol to benzene is methanol:benzene = 1 ~ 5:1. More preferably, in raw materials containing methanol and benzene, the molar ratio of methanol to benzene is methanol:toluene = 1 ~ 2:1. In actual production, the ratio of light olefins and toluene (paraxylene) in the product can be adjusted by modifying the methanol to benzene ratio in the raw material according to specific production requirements. Generally, increasing the methanol / benzene ratio in the raw material increases the olefin content in the product, and decreasing the methanol / toluene ratio in the raw material increases the toluene and paraxylene content in the product.

[0122] Preferably, the molar ratio of methanol to benzene in the raw materials containing methanol and benzene is (0.5-2): 1. Further preferably, the molar ratio of methanol to benzene in the raw materials containing methanol and benzene is (1 ~ 1.5): 1.

[0123] Preferably, the total mass velocity of the raw material containing methanol and benzene is 1 h⁻¹. -1 ~ 4h -1 .

[0124] Preferably, the in-situ preparation process of the catalyst for reaction II comprises at least the following steps: (1) Introducing the shaped molecular sieve into a reactor; (2) Introduction of materials D, which contain a silylation reagent and benzene, into the reactor; (3) Cessation of the introduction of materials D into the reactor, raising the temperature of the reactor to 500 °C or higher and calcination after inflow of air; (4) Introduction of the inert gas and purging, followed by raising the reactor temperature to 500 °C or higher and introducing the vapor-containing material E to carry out the vapor treatment. This will obtain the catalyst for reaction II.

[0125] Preferably, the in-situ preparation process of the catalyst for reaction II comprises at least the following steps: (1) Introducing the shaped molecular sieve into a reactor; (2) Introducing a material F containing a silylation reagent, silylation reagent and benzene into the reactor; (3) Cessation of the introduction of material F into the reactor, raising the temperature of the reactor to above 500 °C and calcination after the air has been drawn in; (4) Introduction of the inert gas and purging, followed by raising the reactor temperature to 500 °C or higher and introducing the vapor-containing material G to carry out the vapor treatment. This will obtain the catalyst for reaction II.

[0126] In the present application, the reaction raw materials contain methanol, with the possibility that the raw materials contain methanol and / or dimethyl ether. Unless otherwise specified, the methanol in the present application can be completely or partially replaced by dimethyl ether, and with regard to the amount of methanol, dimethyl ether can also be converted to methanol with the same number of carbon atoms to carry out the calculation.

[0127] In the present application, the above-mentioned C1 ~ C 10 , C1 ~ C5 etc., each the number of carbon atoms contained in the group.

[0128] In the present application, "alkyl" is a group formed by the loss of one of the hydrogen atoms in the molecule of the alkane compound. The alkane compound includes a linear alkane, a branched alkane, a cycloalkane, and a branched cycloalkane.

[0129] In the present application, the ‘alkoxy group’ is a group formed by the loss of a hydrogen atom at a hydroxyl group in the molecule of the alkyl alcohol compound.

[0130] In the present application, ‘light olefins’ means ethylene and propylene.

[0131] In the present application, ‘methanol and / or dimethyl ether and toluene’ includes three cases: methanol and toluene; or dimethyl ether and toluene; or methanol, dimethyl ether and toluene.

[0132] In the present application, ‘methanol and / or dimethyl ether and benzene’ comprises three cases: methanol and benzene; or dimethyl ether and benzene; or methanol, dimethyl ether and benzene.

[0133] Unless otherwise stated, the methanol in the present application may be wholly or partially replaced by dimethyl ether, and with regard to the amount of methanol, dimethyl ether may also be converted to methanol with the same number of carbon atoms for the purpose of carrying out the calculation.

[0134] The advantages of the application include, but are not limited to: (1) The in-situ production process of the catalyst provided by the present application for the production of at least one of toluene, paraxylene, light olefins breaks with the traditional production method in the existing chemical industry, in which the finished catalyst is first produced in the catalyst production unit, then the catalyst is transported to the chemical production unit, filled in and then production is carried out, thereby overcoming the technical prejudices in large-scale industrial production in the field of heterogeneous catalysis. (2) The in-situ production process of the catalyst provided by the present application for the production of at least one of toluene, paraxylene, light olefins simplifies the entire chemical production process, saves the steps of producing and transporting the catalyst, and is easy to use. (3) In the process provided by the present application for the production of at least one of toluene, paraxylene, light olefins, compared with the inherent production method in the chemical field, the washing separation process after modification of the catalyst, the cooling process of the catalyst after calcination in which the temperature of the catalyst is lowered to room temperature, the step for transporting the catalyst, the step for filling the catalyst, the step for requiring high-temperature pre-activation of the catalyst after filling the reactor, etc.Savings are achieved, which significantly improves production efficiency and avoids the safety problems that can occur in the steps omitted above; more importantly, once the temperature in the reactor is lowered from the calcination temperature to the reaction temperature, the reaction can be started, thus fully utilizing the thermal energy, which significantly reduces energy consumption in production. (4) In the process provided by the present application for the production of at least one of toluene, paraxylene, light olefins, the entire process from the production of the catalyst to the completion of the reaction takes place in a system in situ, which is advantageous in chemical mass production for the recovery and recycling of waste during the production of the catalyst and is environmentally friendly. (5) In the process provided by the present application for the production of at least one of toluene, paraxylene, light olefins from methanol and / or dimethyl ether and toluene, the conversion rate of methanol is 100%, and the selectivity of paraxylene in xylene is 99.6 wt% or more. (6) In the process provided by the present application for the production of at least one of toluene, paraxylene, light olefins from methanol and / or dimethyl ether and toluene, the conversion rate of methanol is 100%, the selectivity of (toluene + paraxylene) in the aromatic product is 85 wt.% or more, the selectivity of paraxylene in the xylene product is 99.6 wt.% or more and the selectivity of paraxylene in the aromatic C8 hydrocarbon is 90 wt.% or more. Brief explanation of the characters Fig. Figure 1 is a process flow diagram of an embodiment of the present application. Fig.Figure 2 is a process flow diagram of an embodiment of the present application. Fig. Figure 3 is a process flow diagram of an embodiment of the present application. Fig. Figure 4 is a process flow diagram of an embodiment of the present application. Fig. Figure 5 is a process flow diagram of an embodiment of the present application. Fig. Figure 6 is a process flow diagram of an embodiment of the present application. Specific forms of implementation

[0135] The present application is described in detail below in conjunction with the embodiments; however, the application is not limited to the embodiments.

[0136] Unless otherwise stated, the raw materials and reagents used in this application are all commercially available and used without treatment; the equipment used conforms to the schemes and parameters recommended by the manufacturer.

[0137] In the exemplary embodiments, the wear index of the catalyst is measured using a wear indexer of type MS-C from Shenyang Hexing Machinery & Electronics Co., Ltd.

[0138] In the exemplary embodiments, the fixed-bed reactor has an inner diameter of 1.5 cm, the fixed fluidized-bed reactor has an inner diameter of 3 cm, and the circulating fluidized-bed reactor has an inner diameter of 12 cm. Example 1: Production of a shaped molecular sieve sample HZSM-5 for the fixed bed

[0139] 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 30) is calcined in an air atmosphere at 550°C for 4 hours, then tableted, crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 mesh, which are designated as FXHZSM-5-A.

[0140] 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 5) is calcined in an air atmosphere at 550 °C for 4 hours, then tableted, crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 mesh, which are designated as FXHZSM-5-B.

[0141] 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 10) is calcined in an air atmosphere at 550 °C for 4 hours, then tableted, crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 mesh, which are referred to as FXHZSM-5-C. Example 2: Production of a shaped molecular sieve sample HZSM-11 for the fixed bed

[0142] 100 g of HZSM-11 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 35) is calcined in an air atmosphere at 550°C for 4 hours, then tableted, crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 mesh, which are designated as FXHZSM-11-A.

[0143] 100 g of HZSM-11 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 12) is calcined in an air atmosphere at 550°C for 4 hours, then tableted, crushed and sieved to obtain shaped molecular sieve particles with a particle size of 40 to 60 mesh, which are designated as FXHZSM-11-B. Example 3: Production of a shaped molecular sieve sample HZSM-5 for the fluidized bed

[0144] 100 g of HZSM-5 zeolite molecular sieve raw powder (Nankai University Catalyst Factory, Si / Al = 30) is mixed with an amorphous binder containing aluminum or silicon and spray-dried; the specific steps are: HZSM-5 zeolite molecular sieve raw powder, pseudoboehmite, silica sol, xanthan gum (biogel) and water are mixed uniformly, then the slurry is obtained by beating, grinding and defoaming; the parts by weight of each component in the slurry are: HZSM-5 40 parts of weight A12O3 20 parts of weight SiO2 40 parts of weight H2O 240 parts by weight Xanthan gum 1 weight part

[0145] The resulting slurry is formed by spray drying, thus obtaining a sample of microsphere particles with a particle size distribution of 20 ~ 100µm; and the sample of microsphere particles is calcined for 3 hours at 550 °C in a muffle furnace to obtain a formed molecular sieve HZSM-5 with a wear index of 1.2, which is designated FLHZSM-5-A. Example 4: Production of a shaped molecular sieve sample HZSM-5 for the fluidized bed

[0146] The specific manufacturing conditions and steps are the same as in the third embodiment, and the differences between them are that the raw material HZSM-5 zeolite molecular sieve raw powder is used in a quantity of 10 kg, the obtained sample of microsphere particles has a particle size distribution of 20 ~ 120 µm, the wear index is 1.2, and the sample is designated as FXHZSM-5-C. Example 5: Production and reaction evaluation of the FXCAT-1 catalyst for fixed bed

[0147] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is prepared online, and then the reaction performance is evaluated.

[0148] The conditions for the online production of a catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1The reaction temperature is at atmospheric pressure. After 90 minutes of charging, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-1. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the production of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: The raw materials are fed using a micro-feed pump, the raw material methanol:toluene (molar ratio) = 10:1, the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 60 minutes after the reaction. The reaction results are shown in Table 1. Table 1 catalyst FXCAT-1 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 36.09 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.64 product distribution (wt%) chain hydrocarbon 77.74 benzene 0.06 Ethylbenzene 0.25 Paraxylene 19.26 Meta-xylene 0.04 O-Xylene 0.03 C 9+ - Aromas 2.61 the product distribution of chain hydrocarbons (wt%) CH4 1.26 C2H4 39.84 C2H6 0.1 C3H6 35.32 C3H8 0.89 C4 11.99 C5 5.06 C 6+ 5.53 C2H4 + C3H6 75.16 Example 6: Production and reaction evaluation of the FXCAT-2 catalyst for fixed bed

[0149] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0150] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 10:40:50. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the process is initiated. After a 45-minute charging period, the charging is stopped, and after purging with nitrogen, the temperature is raised to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-2. Subsequently, the process is cooled under a nitrogen atmosphere to a reaction temperature of 450 °C to carry out the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the overall mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 2. Table 2 catalyst FXCAT-2 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 36.68 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.64 product distribution (wt%) chain hydrocarbon 77.59 benzene 0.08 Ethylbenzene 0.29 Paraxylene 19.18 Meta-xylene 0.04 O-Xylene 0.03 C 9+ - Aromas 2.79 the product distribution of chain hydrocarbons (wt%) CH4 1.23 C2H4 39.76 C2H6 0.13 C3H6 35.25 C3H8 0.96 C4 12.06 C5 5.11 C 6+ 5.5 C2H4 + C3H6 75.01 Example 7: Production and reaction evaluation of the FXCAT-3 catalyst for fixed bed

[0151] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0152] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 2:8:90. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the process is initiated. After 225 minutes of charging, the charging process is stopped, and after purging with nitrogen, the temperature is raised to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-3. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the overall mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 3. Table 3 catalyst FXCAT-3 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 35.59 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.69 product distribution (wt%) chain hydrocarbon 77.9 benzene 0.06 Ethylbenzene 0.21 Paraxylene 19.19 Meta-xylene 0.03 O-Xylene 0.03 C 9+ - Aromas 2.58 the product distribution of chain hydrocarbons (wt%) CH4 1.31 C2H4 39.91 C2H6 0.09 C3H6 35.46 C3H8 0.83 C4 11.91 C5 5.01 C 6+ 5.48 C2H4 + C3H6 75.37 Example 8: Production and reaction evaluation of the FXCAT-4 catalyst for fixed bed

[0153] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0154] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the feed is stopped after 90 minutes, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-4. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the production of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material methanol:toluene (molar ratio) = 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 4. Table 4 catalyst FXCAT-4 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 35.20 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.90 product distribution (wt%) chain hydrocarbon 77.58 benzene 0.09 Ethylbenzene 0.35 Paraxylene 20.33 Meta-xylene 0.01 O-Xylene 0.01 C 9+ - Aromas 1.63 the product distribution of chain hydrocarbons (wt%) CH4 1.11 C2H4 41.57 C2H6 0.1 C3H6 36.98 C3H8 1.18 C4 12.21 C5 3.43 C 6+ 3.42 C2H4 + C3H6 78.55 Example 9: Production and reaction evaluation of the FXCAT-5 catalyst for fixed bed

[0155] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is prepared online, and then the reaction performance is evaluated.

[0156] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 450 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus:tetraethyl silicate:toluene (weight ratio) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure. After 90 minutes of charging, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-5. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material methanol:toluene (molar ratio) = 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 5. Table 5 catalyst FXCAT-5 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 35.80 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.63 product distribution (wt%) chain hydrocarbon 75.29 benzene 0.07 Ethylbenzene 0.35 Paraxylene 21.32 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 2.89 the product distribution of chain hydrocarbons (wt%) CH4 1.08 C2H4 40.96 C2H6 0.11 C3H6 36.49 C3H8 1.41 C4 12.65 C5 3.76 C 6+ 3.54 C2H4 + C3H6 77.45 Exemplary embodiment 10: Production and reaction evaluation of the FXCAT-6 catalyst for fixed bed

[0157] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0158] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 150 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus:tetraethyl silicate:toluene (weight ratio) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the feed is stopped after 90 minutes, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-6. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 6. Table 6 catalyst FXCAT-6 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 34.79 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.95 product distribution (wt%) chain hydrocarbon 78.37 benzene 0.08 Ethylbenzene 0.21 Paraxylene 19.98 Meta-xylene 0 O-Xylene 0.01 C 9+ - Aromas 1.35 the product distribution of chain hydrocarbons (wt%) CH4 0.96 C2H4 41.03 C2H6 0.11 C3H6 37.96 C3H8 1.03 C4 11.01 C5 4.08 C 6+ 3.82 C2H4 + C3H6 78.99 Exemplary embodiment 11: Production and reaction evaluation of the FXCAT-7 catalyst for the fixed bed

[0159] In a micro fixed-bed reactor, a catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0160] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-11-A is loaded into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the feed is stopped after 90 minutes, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-7. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 7. Table 7 catalyst FXCAT-7 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 33.58 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.90 product distribution (wt%) chain hydrocarbon 77.79 benzene 0.07 Ethylbenzene 0.28 Paraxylene 19.88 Meta-xylene 0.01 O-Xylene 0.01 C 9+ - Aromas 1.96 the product distribution of chain hydrocarbons (wt%) CH4 0.85 C2H4 40.51 C2H6 0.11 C3H6 37.79 C3H8 0.83 C4 10.57 C5 4.53 C 6+ 4.81 C2H4 + C3H6 78.30 Exemplary embodiment 12: Production and reaction evaluation of the catalyst FXCAT-1 for the fluidized bed

[0161] In a solid fluidized bed reactor, a catalyst for the production of paraxylene with a co-product of light olefins from methanol and toluene is produced online, and then the reaction performance is evaluated.

[0162] The conditions for the online production of the catalyst are as follows: after loading 10 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A produced in Implementation Example 3 into a closed fluidized bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus:tetraethyl silicate:toluene (weight ratio) is 5:20:75, and the total mass space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the feed is stopped after 90 minutes, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FLCAT-1. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 8. Table 8 catalyst FLCAT-1 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 31.33 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.61 product distribution (wt%) chain hydrocarbon 76.56 benzene 0.09 Ethylbenzene 0.31 Paraxylene 20.25 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 2.71 the product distribution of chain hydrocarbons (wt%) CH4 1.37 C2H4 40.78 C2H6 0.12 C3H6 35.72 C3H8 1.5 C4 11.94 C5 4.52 C 6+ 4.05 C2H4 + C3H6 76.50 Example 13: Production and reaction of the FXCAT-8 catalyst for the fixed bed

[0163] A micro fixed-bed reactor was used to produce light olefins with a co-product of paraxylene, using methanol and toluene as raw materials.

[0164] The conditions for in-situ catalyst preparation are as follows: after loading 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A into a micro fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the reactor using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 5:20:75. The total weight-space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h. -1At atmospheric pressure, the feed is stopped after 90 minutes, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-8. The reaction is then cooled to a reaction temperature of 450 °C under a nitrogen atmosphere to carry out the reaction for the production of light olefins with a co-product of paraxylene from methanol and toluene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio (methanol:toluene) is 10:1, and the overall mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 60 minutes after the reaction. The reaction results are shown in Table 9. Table 9 catalyst FXCAT-8 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 35.20 the selectivity of (C2H4+C3H6) in the chain hydrocarbon products (wt%) 73.55 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.71 The product distribution of hydrocarbons (wt%) CH4 0.84 C2H4 30.09 C2H6 0.08 C3H6 25.84 C3H8 0.90 C4 olefins 9.25 C4 alkane 1.55 C 5+ -chain hydrocarbons 7.49 benzene 0.09 Ethylbenzene 0.35 Paraxylene 20.33 Meta-xylene 0.04 O-Xylene 0.02 C 9+ - Aromas 3.14 Example 14: Production and reaction of the FXCAT-9 catalyst for the fixed bed

[0165] According to one embodiment of the present application, as in Fig. Figure 1 shows that stream I comprises methanol and toluene, and the methanol and toluene are used as raw materials for the production of light olefins with a co-product of paraxylo.

[0166] In a reaction system, 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A, prepared in Implementation Example 1, are loaded. They are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethyl silicate, and toluene is fed into the system using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethyl silicate to toluene (weight ratio) is 5:20:75. The overall mass space velocity of the trimethoxyphosphorus, tetraethyl silicate, and toluene is 1 h⁻¹. -1 At atmospheric pressure, the process is initiated. After a 90-minute charging period, the charging is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and the mixture is calcined in an air atmosphere for 4 hours to produce the catalyst for the synthesis of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-9.

[0167] Stream I is introduced into the reaction system and comes into contact with the catalyst FXCAT-9, where it reacts. Stream II, containing the product, leaves the reaction system and enters the separation system, separating light olefins (ethylene and propylene), C4 olefins, paraxylene, and other components. Of these, C4 olefins are recycled back into the reaction system, and light olefins (ethylene and propylene) and paraxylene are accepted as products. Other components are accepted as byproducts.

[0168] The conditions for the reaction are as follows: the raw materials are fed with a microfeed pump, the raw material methanol: toluene (molar ratio) = 10:1, the total mass space velocity of methanol and toluene 2 h -1The reaction temperature is 450 °C at atmospheric pressure. The products are analyzed by online Agilent 7890 gas chromatography, and the sample is examined 60 minutes after the reaction. The reaction results are shown in Table 10. Table 10 catalyst FXCAT-9 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 37.01 the selectivity of (C2H4+C3H6) in the chain hydrocarbon products (wt%) 82.19 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.62 the product distribution of hydrocarbons (wt%) CH4 0.99 C2H4 31.87 C2H6 0.19 C3H6 27.54 C3H8 1.87 C4 alkanes 1.62 C 5+ -chain hydrocarbons 8.2 benzene 0.58 Ethylbenzene 0.46 Paraxylene 23.1 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 3.5 Example 15: Production and reaction of the FXCAT-10 catalyst for the fixed bed

[0169] According to one embodiment of the present application, as in Fig. 2 shown, stream I comprises dimethyl ether and toluene, and dimethyl ether and toluene are used as raw materials for the production of light olefins with a co-product of paraxylene.

[0170] The difference from Example 14 lies in the separation system; otherwise, it is the same as Example 14 for producing the fixed-bed catalyst, and the catalyst is designated FXCAT-10. The separation system of this embodiment separates C 1~3-chain hydrocarbons, C4 olefins, C4 alkanes, C5 chain hydrocarbons, aromatics are removed, with the C4 olefins being recycled to the reaction system. From the C 1~3 From the chain hydrocarbons, ethylene and propylene are separated, which are assumed to be products of light olefins. Paraxylene is separated from the aromatics, which is assumed to be the product. Other components are assumed to be byproducts. The reaction results agreed with Example 14 (the deviation did not exceed ± 1%). Example 16: Production and reaction of the fixed-bed catalyst FXCAT-11 and the fluidized-bed catalyst FXCAT-12

[0171] According to one embodiment of the present application, as in Fig.The process flow diagram shown in Figure 3 includes stream I dimethyl ether and toluene, and dimethyl ether and toluene are used as raw materials for the production of light olefins with a co-product of paraxylene.

[0172] The first reaction zone consists of 10 parallel fixed beds and the second reaction zone is a fluidized bed.

[0173] 50 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A prepared in Example 1 is loaded into 10 fixed beds in the first reaction zone, each bed being loaded with 5 g. Each fixed bed is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethylsilica, and toluene is fed by a microfeed pump. The ratio of trimethoxyphosphorus:tetraethylsilica:toluene (by weight) is 5:20:75. The total weight space velocity of the trimethoxyphosphorus, tetraethylsilica, and toluene is 1 h. -1At atmospheric pressure, the process is carried out. After 90 minutes of charging, the charging is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-11.

[0174] 50 g (40-60 mesh) of the microsphere molecular sieve sample FLHZSM-5-B prepared in Example 4 is loaded into a fluidized bed of the second reaction zone. It is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of tetraethyl silicate and methanol is fed into the fluidized bed of the second reaction zone via a microfeed pump. After evaporation, the mixture enters the fluidized bed of the second reaction zone. The tetraethyl silicate:methanol weight ratio is 40:60, and the total mass space velocity of the tetraethyl silicate and methanol is 2 h. -1The temperature is at atmospheric pressure. After 3 hours of charging, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours to produce the catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-12.

[0175] In the first reaction zone, the conversion reaction of methanol and the alkylation reaction of toluene and methanol are carried out. The reaction conditions are as follows: The raw materials are fed using a microfeed pump, the raw material methanol:toluene (molar ratio) = 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction temperature is 450 °C at atmospheric pressure. Stream I is loaded into the fixed bed of the first reaction zone and brought into contact with the catalyst FXCAT-11, thus obtaining stream II-A. Stream II-A exits the first reaction zone and enters the separation system. Ethylene, propylene, C4 olefins, and paraxylene are separated from the separation system. The C4 olefins separated from the separation system are introduced into the fluidized bed of the second reaction zone and brought into contact with the catalyst FXCAT-12. Thus, the shape-selective fluidized bed aromatization reaction is carried out in the second reaction zone at a reaction temperature of 450 °C. Stream II-B is thus obtained in the second reaction zone, which exits the first reaction zone and enters the separation system. The ethylene and propylene separated from the separation system are considered products of light olefins, and paraxylene is considered a product.Other components are assumed to be byproducts.

[0176] The analysis of the hydrocarbon product from the second reaction zone is performed by online Agilent 7890 gas chromatography, as shown in Table 11. The product distribution after subtraction of the C4 olefin component is shown in Table 12. The analysis of the mixed hydrocarbon product from the first and second reaction zones is performed by online Agilent 7890 gas chromatography, and the product distribution after subtraction of the C4 olefins is shown in Table 13. Table 11 the conversion rate of C4 olefins (%) 83.25 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.56 the product distribution of hydrocarbons (wt%) CH4 0.74 C2H4 0.60 C2H6 1.02 C3H6 0.26 C3H8 9.55 C4 olefins 16.76 C4 alkanes 0.04 C 5+ -chain hydrocarbons 0.23 benzene 4.94 toluene 35.74 Ethylbenzene 0.90 Paraxylene 27.07 Meta-xylene 0.07 O-Xylene 0.05 C 9+ - Aromas 2.03 Table 12 the conversion rate of C4 olefins (%) 83.25 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.56 the product distribution of hydrocarbons (wt%) CH4 0.89 C2H4 0.72 C2H6 1.22 C3H6 0.31 C3H8 11.47 C4 alkanes 0.05 C 5+ -chain hydrocarbons 0.28 benzene 5.93 toluene 42.94 Ethylbenzene 1.08 Paraxylene 32.52 Meta-xylene 0.08 O-Xylene 0.06 C 9+ - Aromas 2.44 Table 13 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 38.08 the selectivity of (C2H4+C3H6) in the chain hydrocarbon products (wt%) 82.44 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.69 the product distribution of hydrocarbons (wt%) CH4 0.94 C2H4 31.68 C2H6 0.19 C3H6 27.18 C3H8 1.85 C4 alkanes 1.64 C 5+ -chain hydrocarbons 7.90 benzene 0.58 Ethylbenzene 0.46 Paraxylene 24.00 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 3.50 Example 17: Production and reaction of the catalysts FXCAT-13 and FXCAT-14

[0177] According to one embodiment of the present application, as in Fig.4 shown, stream I comprises dimethyl ether, methanol and toluene, which are used as raw materials for the production of light olefins with a co-product of paraxylene.

[0178] The difference from Example 16 is that the first reaction zone is a fixed bed filled with 50 g of the molecular sieve sample FXHZSM-5-A. Furthermore, the separation systems are different; the separation system of the present embodiment separates C 1~3 -hydrocarbons, C4 olefins, C4 alkanes, C 5+ hydrocarbons and aromatics are removed, with the C4 olefins being recycled back to the reaction system. From the C 1~3From the α-chain hydrocarbons, ethylene and propylene are separated and taken as products of light olefins. Paraxylene is separated from the aromatics and is considered a product. Other components are considered byproducts. Otherwise, the reaction is the same as in Example 23; the fixed-bed catalyst is designated FXCAT-13 and the fluidized-bed catalyst is designated FXCAT-14. The reaction results were consistent with Example 16 (the deviation did not exceed ± 1%). Example 18: Production and reaction of the catalyst FXCAT-15

[0179] According to one embodiment of the present application, as in Fig. In the process flow diagram shown in section 3, dimethyl ether and toluene are used as raw materials for the production of light olefins with paraxylene as a coproduct. Stream I comprises dimethyl ether and toluene.

[0180] The reaction system consists of two fixed beds, which are arranged as in the Fig. The reaction systems shown in section 5 are arranged in series at the top and bottom. Single-stage feeding is used, whereby current I is fed into the upper fixed bed, and the returned C 5+ -Chain hydrocarbons enter the lower fixed bed.

[0181] 10 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A produced in Example 1 is loaded into two fixed beds, with each bed receiving an equal amount of 5 g. Catalyst preparation process: each fixed bed is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethylsilica, and toluene is fed into the beds using a microfeed pump. The ratio of trimethoxyphosphorus to tetraethylsilica to toluene (by weight) is 5:20:75, and the total mass space velocity of the trimethoxyphosphorus, tetraethylsilica, and toluene is 1 h⁻¹. -1At atmospheric pressure, the process is carried out. After a 90-minute charging cycle, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and the mixture is calcined in an air atmosphere for 4 hours to produce the fixed-bed catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene. The catalyst is designated FXCAT-15.

[0182] Current I is fed into the fixed-bed reactor in the upper part of the reaction system and brought into contact with the catalyst FXCAT-15, thus realizing a conversion reaction of methanol and a shape-selective alkylation reaction of toluene and methanol. The reaction conditions are as follows: The raw materials are fed by means of a microfeed pump, the raw material methanol:toluene (molar ratio) = 10:1 and the total mass space velocity of methanol and toluene 2 h -1The reaction temperature is 450 °C at atmospheric pressure.

[0183] Stream II containing the products leaves the reaction system and enters the separation system, where C 1~4 -chain hydrocarbons, C 5+ -chain hydrocarbons and aromatics are separated, whereby the C 5+ Chain hydrocarbons are recycled to the fixed bed in the lower part of the reaction system and contacted with the catalyst FXCAT-15 to carry out a reaction such as cracking and shape-selective aromatization, and the reaction temperature of the fixed bed in the lower part of the reaction system is 630 °C. Ethylene and propylene are produced as products of the light olefins from the C 1~4 Chain hydrocarbons are separated. Paraxylene is separated from the aromatics as a product. Other components are considered byproducts.

[0184] The product analysis was performed using online Agilent 7890 gas chromatography, as shown in Table 14. Table 14 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 36.55 the selectivity of (C2H4+C3H6) in the chain hydrocarbon products (wt%) 80.83 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 the product distribution of hydrocarbons (wt%) CH4 1.11 C2H4 33.02 C2H6 0.31 C3H6 27.25 C3H8 1.17 C4 11.7 benzene 0.65 Ethylbenzene 0.39 Paraxylene 21.05 Meta-xylene 0.04 O-Xylene 0.02 C 9+ - Aromas 3.29 Example 19: Production and reaction of the FXCAT-16 catalyst for the fixed bed

[0185] According to one embodiment of the present application, as in Fig. In the process flow diagram shown in section 6, dimethyl ether and toluene are used as raw materials for the production of light olefins with paraxylene as a coproduct. Stream I comprises dimethyl ether and toluene.

[0186] 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A prepared in Example 1 is loaded into the fixed bed in the first reaction zone and into the fixed bed in the second reaction zone. The catalyst preparation procedures are identical: the catalyst in each fixed bed is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A liquid mixture of trimethoxyphosphorus, tetraethylsilica, and toluene is fed by a microfeed pump. The ratio of trimethoxyphosphorus to tetraethylsilica to toluene (weight ratio) is 5:20:75. The total mass space velocity of trimethoxyphosphorus, tetraethylsilica, and toluene is 1 h. -1At atmospheric pressure, the process is carried out. After 90 minutes of charging, the charging is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined for 4 hours in an air atmosphere. According to the above procedure, the catalysts for the online production of light olefins with a co-product of paraxylene from methanol and toluene are prepared in the first and second fixed-bed reaction zones, respectively. The catalyst is designated FXCAT-16.

[0187] Stream I is fed into the fixed-bed reactor in the upper part of the reaction system and brought into contact with the catalyst FXCAT-16, thus realizing a conversion reaction of methanol and a shape-selective alkylation reaction of toluene and methanol. The reaction conditions are as follows: The raw materials are fed by a microfeed pump, the raw material methanol:toluene molar ratio is 10:1, and the total mass space velocity of methanol and toluene is 2 h⁻¹ at atmospheric pressure and a reaction temperature of 450 °C. Stream II-A, containing the products, leaves the reaction system and enters the separation system, where C 1~4 -chain hydrocarbons, C 5+ -Chain hydrocarbons and aromatics are separated from the separation system.

[0188] The C separated from the separation system 5+Chain hydrocarbons enter the fixed bed of the second reaction zone, contact the catalyst FXCAT-16, and undergo reactions such as cracking and shape-selective aromatization, etc., with a reaction temperature of 630 °C in the fixed bed of the second reaction zone. Afterwards, stream II-B containing the products leaves the fixed bed of the second reaction zone and enters the separation system.

[0189] From the C separated from the separation system 1~4 From the chain hydrocarbons, ethylene and propylene are separated as products of the light olefins. Paraxylene is separated from the aromatics as a product. Other components are taken as byproducts.

[0190] The analysis of the hydrocarbon product of the second reaction zone is carried out by online Agilent 7890 gas chromatography, as shown in Table 15, the product distribution after subtraction of the C 5+The chain hydrocarbons are shown in Table 16. The analysis of the mixed hydrocarbon product of the first and second reaction zones was performed by online Agilent 7890 gas chromatography, and the product distribution after subtraction of the C 5+ Chain hydrocarbons are shown in Table 17. Table 15 the conversion of C 5+ -Chain hydrocarbons (%) 93.92 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 the product distribution of hydrocarbons (wt%) CH4 4.32 C2H4 20.83 C2H6 3.02 C3H6 23.37 C3H8 3.45 C4 8.51 C 5+ 6.08 benzene 7.46 toluene 11.07 Ethylbenzene 0.52 Paraxylene 9.96 Meta-xylene 0.03 O-Xylene 0.02 C 9+ - Aromas 1.36 Table 16 the conversion of C 5+ -Chain hydrocarbons (%) 93.92 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 the product distribution of hydrocarbons (wt%) CH4 4.60 C2H4 22.18 C2H6 3.22 C3H6 24.88 C3H8 3.67 C4 9.06 benzene 7.94 toluene 11.79 Ethylbenzene 0.55 Paraxylene 10.60 Meta-xylene 0.03 O-Xylene 0.02 C 9+ - Aromas 1.45 Table 17 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 37.11 the selectivity of (C2H4+C3H6) in the chain hydrocarbon products (wt%) 80.81 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 the product distribution of hydrocarbons (wt%) CH4 1.18 C2H4 32.06 C2H6 0.31 C3H6 27.95 C3H8 1.17 C4 11.59 benzene 0.65 Ethylbenzene 0.39 Paraxylene 21.35 Meta-xylene 0.04 O-Xylene 0.02 C 9+ - Aromas 3.29 Example 20: Production and reaction of the catalyst FXCAT-17 for fluidized bed

[0191] According to one embodiment of the present application, the process flow diagram is the same as embodiment 19, as shown in Fig. 6 shown. The difference lies in the raw materials and reactors.

[0192] In the present embodiment, the stream I comprises dimethyl ether, methanol and toluene, and the dimethyl ether, methanol and toluene are used as raw materials for the production of light olefins with a co-product of paraxylene.

[0193] In the present embodiment, the first reaction zone is a fluidized bed filled with 1 kg of the molecular sieve sample FLHZSM-5-C from Example 4. The second reaction zone is also a fluidized bed, also filled with 1 kg of the molecular sieve sample FLHZSM-5-C from Example 4.

[0194] The catalyst manufacturing process: the catalyst is treated in a fluidized bed reactor with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. Otherwise, it is the same as in Example 19; the resulting fixed-bed catalyst is designated FLCAT-17. The reaction results were consistent with Example 19 (the deviation did not exceed ± 1%). Example 21: Production and reaction evaluation of the catalyst FXCAT-18 for the fixed bed

[0195] In a micro fixed-bed reactor, the fixed-bed catalyst for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0196] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 1-hour feed, the feed is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-18. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 10:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 60 minutes after the reaction. The results of the reaction are shown in Table 18. Table 18 catalyst FXCAT-18 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.93 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.63 the selectivity of paraxylene in C8 aromatics (wt%) 91.06 the selectivity of paraxylene in the products of aromatics (wt%) 94.16 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.72 toluene 53.09 Ethylbenzene 2.57 Paraxylene 27.21 Meta-xylene 0.06 O-Xylene 0.04 C 9+ - Aromas 2.31 Example 22: Production and reaction evaluation of the catalyst FXCAT-19 for the fixed bed

[0197] In a micro fixed-bed reactor, the fixed-bed catalyst for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0198] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1 After a 2-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 1-hour feed, the feed is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-19. The temperature is then cooled to the reaction temperature of 450°C under a nitrogen atmosphere to test the reaction for the production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 10:1, the total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 60 minutes after the reaction. The results of the reaction are shown in Table 19. Table 19 catalyst FXCAT-19 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.43 the selectivity of paraxylene in the products of xylene isomers 99.78 (wt%) The selectivity of paraxylene in the products of C8 aromatics (wt%) 91.33 the selectivity of paraxylene in the products of aromatics (wt%) 94.37 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.81 toluene 53.32 Ethylbenzene 2.51 Paraxylene 27.07 Meta-xylene 0.04 O-Xylene 0.02 C 9+ - Aromas 2.23 Example 23: Production and reaction evaluation of the FXCAT-20 catalyst for the fixed bed

[0199] In a micro fixed-bed reactor, the fixed-bed catalyst for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0200] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.4 h⁻¹. -1 After a 0.5-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-20. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450°C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 20. Table 20 catalyst FXCAT-20 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 36.37 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.67 The selectivity of paraxylene in the products of C8 aromatics (wt%) 90.95 the selectivity of paraxylene in the products of aromatics (wt%) 93.99 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.61 toluene 52.92 Ethylbenzene 2.63 Paraxylene 27.34 Meta-xylene 0.05 O-Xylene 0.04 C 9+ - Aromas 2.41 Example 24: Production and reaction evaluation of the FXCAT-21 catalyst for fixed bed

[0201] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0202] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, designated FXCAT-21. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450°C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 21. Table 21 catalyst FXCAT-21 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.37 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 The selectivity of paraxylene in the products of C8 aromatics (wt%) 90.48 the selectivity of paraxylene in aromatic products 93.09 (wt%) product distribution (wt%) C1-C 6+ -chain hydrocarbons 13.62 toluene 53.41 Ethylbenzene 2.76 Paraxylene 26.99 Meta-xylene 0.04 O-Xylene 0.04 C 9+ - Aromas 3.13 Example 25: Production and reaction evaluation of the FXCAT-22 catalyst for the fixed bed

[0203] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0204] The conditions for online catalyst production are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 450 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a micro-feed pump; the bulk velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. After 1 hour of feeding, the feeding is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is fed using a micro-feed pump; the bulk velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-22. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 22. Table 22 catalyst FXCAT-22 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 36.71 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.63 The selectivity of paraxylene in the products of C8 aromatics (wt%) 90.28 the selectivity of paraxylene in the products of aromatics (wt%) 92.88 product distribution (wt%) C1-C 6+ -chain hydrocarbons 13.33 toluene 53.65 Ethylbenzene 2.79 Paraxylene 26.85 Meta-xylene 0.06 O-Xylene 0.04 C 9+ - Aromas 3.28 Example 26: Production and reaction evaluation of the FXCAT-23 catalyst for the fixed bed

[0205] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0206] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 800 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After reaching 2 sphere pressure, the feed is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-23. Subsequently, under a nitrogen atmosphere, the temperature is raised to the reaction temperature of 450°C. To test the reaction for the production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, the reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total weight space velocity of methanol and toluene is 2 h⁻¹. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 23. Table 23 catalyst FXCAT-23 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 33.26 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.65 The selectivity of paraxylene in the products of C8 aromatics (wt%) 91.19 the selectivity of paraxylene in the products of aromatics (wt%) 93.68 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.57 toluene 54.35 Ethylbenzene 2.39 Paraxylene 25.68 Meta-xylene 0.05 O-Xylene 0.04 C 9+ - Aromas 2.92 Exemplary embodiment 27: Production and reaction evaluation of the FXCAT-24 catalyst for fixed bed

[0207] In a micro fixed-bed reactor, the fixed-bed catalyst for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0208] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a micro-feeding pump; the bulk velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. After 1 hour of feeding, the feed is stopped, and after purging with nitrogen, the temperature is raised to 550 °C and calcined in an air atmosphere for 4 hours.The temperature is raised to 600 °C under a nitrogen atmosphere, and water is fed in using a micro-feed pump. The mass space velocity of water at atmospheric pressure is 2 h⁻¹. After 8 hours of feeding, the feed is stopped. This process generates the catalyst for the fixed-bed reaction, known as FXCAT-24, for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The catalyst is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed in using a micro-feed pump. The raw material ratio is methanol:toluene (molar ratio) = 1:1, and the mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 24. Table 24 catalyst FXCAT-24 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 36.97 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 The selectivity of paraxylene in the products of C8 aromatics (wt%) 91.48 the selectivity of paraxylene in the products of aromatics (wt%) 93.42 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.07 toluene 53.96 Ethylbenzene 2.37 Paraxylene 26.31 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 3.20 Example 28: Production and reaction evaluation of the catalyst FXCAT-25 for the fixed bed

[0209] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0210] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, which is designated FXCAT-25. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450°C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 25. Table 25 catalyst FXCAT-25 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.56 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.82 The selectivity of paraxylene in the products of C8 aromatics (wt%) 91.40 the selectivity of paraxylene in the products of aromatics (wt%) 94.39 product distribution (wt%) C1-C 6+ -chain hydrocarbons 15.31 toluene 52.72 Ethylbenzene 2.51 Paraxylene 27.22 Meta-xylene 0.03 O-Xylene 0.02 C 9+ - Aromas 2.19 Example 29: Production and reaction evaluation of the FXCAT-26 catalyst for the fixed bed

[0211] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0212] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 150 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding period, the feeding process is stopped, thus producing the fixed-bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, designated FXCAT-26. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450°C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of methanol and toluene is 2 h. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 26. Table 26 catalyst FXCAT-26 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.87 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.89 The selectivity of paraxylene in the products of C8 aromatics (wt%) 91.38 the selectivity of paraxylene in the products of aromatics (wt%) 94.44 product distribution (wt%) C1-C 6+ -chain hydrocarbons 15.11 toluene 52.91 Ethylbenzene 2.54 Paraxylene 27.26 Meta-xylene 0.02 O-Xylene 0.01 C 9+ - Aromas 2.15 Example 30: Production and reaction evaluation of the catalyst FXCAT-27 for the fluidized bed

[0213] In a fixed fluidized bed reactor, the catalyst for the fixed bed is produced online for the production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0214] The conditions for the online production of the catalyst are as follows: After 10 g (40-60 mesh) of shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a micro-feeding pump; the bulk velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. After 1 hour of feeding, the feed is stopped, and after purging with nitrogen, the temperature is raised to 550 °C and calcined in an air atmosphere for 4 hours.The temperature is raised to 700 °C under a nitrogen atmosphere, and water is fed in using a micro-feed pump. The mass space velocity of water at atmospheric pressure is 2 h⁻¹. After reaching 4 spherical pressure, the feed is stopped. Thus, the fluidized bed catalyst for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene, designated FXCAT-27, is produced. Subsequently, under a nitrogen atmosphere, the temperature is raised to the reaction temperature of 450 °C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. The reaction conditions are as follows: the raw materials are fed in using a micro-feed pump. The raw material ratio is methanol:toluene (molar ratio) = 1:1. The total mass space velocity of methanol and toluene is 2 h⁻¹. -1The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 27. Table 27 catalyst FLCAT-27 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 32.71 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.66 The selectivity of paraxylene in the products of C8 aromatics (wt%) 90.79 the selectivity of paraxylene in the products of aromatics (wt%) 94.03 product distribution (wt%) C1-C 6+ -chain hydrocarbons 17.41 toluene 51.05 Ethylbenzene 2.61 Paraxylene 26.61 Meta-xylene 0.05 O-Xylene 0.04 C 9+ - Aromas 2.23 Example 31: Production and reaction evaluation of the FXCAT-28 catalyst for the fixed bed

[0215] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with a co-product of paraxylene is produced online by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0216] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-C are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed using a microfeed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1After a 1-hour feed, the feed is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. This process generates the catalyst for the fixed-bed reactor, designated FXCAT-28, for the online production of toluene with a co-product of paraxylene via the alkylation of methanol and / or dimethyl ether and benzene. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with a co-product of paraxylene via the alkylation of methanol and benzene. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material ratio is benzene : methanol (molar ratio) = 1:1, and the total mass space velocity of benzene and methanol is 2 h⁻¹. -1The reaction was carried out at atmospheric pressure. The reaction product was analyzed by online Agilent 7890 gas chromatography, and the sample was examined 120 minutes after the reaction. The results of the reaction are shown in Table 28. Table 28 catalyst FXCAT-28 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 38.01 the selectivity of paraxylene in the products of xylene isomers (wt%) 93.60 The selectivity of paraxylene in the products of C8 aromatics (wt%) 80.64 the selectivity of paraxylene in the products of aromatics (wt%) 82.91 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.06 toluene 44.92 Ethylbenzene 4.52 Paraxylene 26.33 Meta-xylene 0.99 O-Xylene 0.81 C 9+ - Aromas 8.37 Example 32: Production and reaction evaluation of the catalyst FXCAT-29 for the fixed bed

[0217] In a micro fixed-bed reactor, the catalyst for the fixed bed is used to produce toluene with co-products of paraxylene and light olefins from benzene and methanol online, after which the reaction performance is evaluated.

[0218] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feeding is stopped, thus producing the catalyst for the fixed bed for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-29. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene:methanol (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 29. Table 29 catalyst FXCAT-29 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.51 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.74 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.31 the selectivity of paraxylene in the products of aromatics (wt%) 95.20 product distribution (wt%) C1-C 6+ -chain hydrocarbons 16.81 toluene 52.17 Ethylbenzene 1.56 Paraxylene 27.03 Meta-xylene 0.04 O-Xylene 0.03 C 9+ - Aromas 2.36 Product distribution of chain hydrocarbons (wt%) CH4 1.03 C2H4 39.66 C2H6 0.12 C3H6 31.63 C3H8 1.92 C4 13.43 C5 7.07 C 6+ 5.13 C2H4 + C3H6 71.29 Example 33: Production and reaction evaluation of the FXCAT-30 catalyst for the fixed bed

[0219] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0220] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After 1.5 hours of charging, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-30. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene : methanol (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 30. Table 30 catalyst FXCAT-30 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 36.01 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.66 The selectivity of paraxylene in the products of 93.24 C8 aromatics (wt%) the selectivity of paraxylene in the products of aromatics (wt%) 94.58 product distribution (wt%) C1-C 6+ -chain hydrocarbons 16.57 toluene 52.31 Ethylbenzene 1.84 Paraxylene 26.60 Meta-xylene 0.05 O-Xylene 0.04 C 9+ - Aromas 2.59 Product distribution of chain hydrocarbons (wt%) CH4 1.12 C2H4 37.13 C2H6 0.16 C3H6 33.02 C3H8 2.17 C4 14.52 C5 7.14 C 6+ 4.74 C2H4 + C3H6 70.15 Example 34: Production and reaction evaluation of the catalyst FXCAT-31 for the fixed bed

[0221] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0222] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 1. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After 1.5 hours of charging, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-31. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene:methanol (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 31. Table 31 catalyst FXCAT-31 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 33.68 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.71 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.72 the selectivity of paraxylene in the products of aromatics (wt%) 95.35 product distribution (wt%) C1-C 6+ -chain hydrocarbons 17.64 toluene 51.46 Ethylbenzene 1.43 Paraxylene 27.07 Meta-xylene 0.04 O-Xylene 0.04 C 9+ - Aromas 2.32 Product distribution of chain hydrocarbons (wt%) CH4 0.91 C2H4 38.18 C2H6 0.11 C3H6 34 C3H8 1.75 C4 12.97 C5 6.82 C 6+ 5.26 C2H4 + C3H6 72.18 Example 35: Production and reaction evaluation of the FXCAT-32 catalyst for the fixed bed

[0223] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0224] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 250 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feeding is stopped, thus producing the catalyst for the fixed bed reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-32. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene : methanol molar ratio = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 32. Table 32 catalyst FXCAT-32 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.32 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.82 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.60 the selectivity of paraxylene in the products of aromatics (wt%) 95.39 product distribution (wt%) C1-C 6+ -chain hydrocarbons 17.15 toluene 52.05 Ethylbenzene 1.49 Paraxylene 26.98 Meta-xylene 0.03 O-Xylene 0.02 C 9+ - Aromas 2.28 Product distribution of chain hydrocarbons (wt%) CH4 0.97 C2H4 37.92 C2H6 0.1 C3H6 33.95 C3H8 1.83 C4 13.07 C5 6.93 C 6+ 5.23 C2H4 + C3H6 71.87 Example 36: Production and reaction evaluation of the FXCAT-33 catalyst for the fixed bed

[0225] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0226] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 300 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-33. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene:methanol (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 33. Table 33 catalyst FXCAT-33 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.95 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.63 The selectivity of paraxylene in the products of C8 aromatics (wt%) 93.09 the selectivity of paraxylene in the products of aromatics (wt%) 94.18 product distribution (wt%) C1-C 6+ -chain hydrocarbons 16.39 toluene 51.94 Ethylbenzene 1.89 Paraxylene 26.80 Meta-xylene 0.06 O-Xylene 0.04 C 9+ - Aromas 2.88 Product distribution of chain hydrocarbons (wt%) CH4 0.95 C2H4 36.92 C2H6 0.18 C3H6 33.39 C3H8 2.22 C4 13.57 C5 6.95 C 6+ 5.82 C2H4 + C3H6 70.31 Example 37: Production and reaction evaluation of the FXCAT-34 catalyst for the fixed bed

[0227] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0228] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1 After a 1-hour charging process, the charging is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 800 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h.-1 After a 2-hour feeding process, the feeding is stopped, thus producing the fixed-bed catalyst for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, designated FXCAT-34. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material benzene:methanol molar ratio is 1:1, the total mass space velocity of benzene and methanol is 2 h⁻¹, at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 34. Table 34 catalyst FXCAT-34 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 32.17 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.88 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.69 the selectivity of paraxylene in the products of aromatics (wt%) 95.50 product distribution (wt%) C1-C 6+ -chain hydrocarbons 18.23 toluene 52.05 Ethylbenzene 1.43 Paraxylene 26.04 Meta-xylene 0.02 O-Xylene 0.01 C 9+ - Aromas 2.22 Product distribution of chain hydrocarbons (wt%) CH4 1.09 C2H4 39.52 C2H6 0.11 C3H6 32.09 C3H8 1.83 C4 13.19 C5 6.95 C 6+ 5.22 C2H4 + C3H6 71.61 Example 38: Production and reaction evaluation of the FXCAT-35 catalyst for the fixed bed

[0229] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0230] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed using a microfeed pump, tetraethylsilica:trimethoxyphosphine (mass ratio) = 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1 After a 1-hour charging process, the charging is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 600 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h.-1 After an 8-hour feeding process, the feeding is stopped, thus producing the catalyst for the fixed bed reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-35. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene : methanol molar ratio = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 35. Table 35 catalyst FXCAT-35 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.59 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.74 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.23 the selectivity of paraxylene in the products of aromatics (wt%) 95.07 product distribution (wt%) C1-C 6+ -chain hydrocarbons 16.15 toluene 52.94 Ethylbenzene 1.57 Paraxylene 26.78 Meta-xylene 0.04 O-Xylene 0.03 C 9+ - Aromas 2.49 Product distribution of chain hydrocarbons (wt%) CH4 1.01 C2H4 39.25 C2H6 0.13 C3H6 31.55 C3H8 1.93 C4 13.51 C5 7.27 C 6+ 5.35 C2H4+C3H6 70.80 Example 39: Production and reaction evaluation of the FXCAT-36 catalyst for the fixed bed

[0231] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0232] The conditions for the online production of the catalyst are as follows: After 5 g (40-60 mesh) of the shaped molecular sieve sample of catalyst FXHZSM-11-A has been tableted, ground to 40-60 mesh, and sieved, and 5 g (40-60 mesh) of catalyst has been loaded into a fixed-bed reactor, it is first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feeding is stopped, thus producing the catalyst for the fixed bed reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-36. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene : methanol molar ratio = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 36. Table 36 catalyst FXCAT-36 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 34.17 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.85 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.49 the selectivity of paraxylene in the products of aromatics (wt%) 95.46 product distribution (wt%) C1-C 6+ -chain hydrocarbons 18.13 toluene 51.89 Ethylbenzene 1.49 Paraxylene 26.26 Meta-xylene 0.03 O-Xylene 0.01 C 9+ - Aromas 2.19 Product distribution of chain hydrocarbons (wt%) CH4 0.91 C2H4 38.61 C2H6 0.09 C3H6 34.07 C3H8 1.6 C4 12.23 C5 6.85 C 6+ 5.64 C2H4+C3H6 72.68 Example 40: Production and reaction evaluation of the catalyst FXCAT-37 for the fixed bed

[0233] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0234] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feed is stopped, thus producing the fixed-bed catalyst for the synthesis of toluene with the co-product of paraxylene and light olefins from benzene and methanol, designated FXCAT-37. The temperature is then cooled to the reaction temperature of 450 °C under a nitrogen atmosphere to test the reaction for the synthesis of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed using a micro-feed pump, the raw material benzene:methanol molar ratio is 1:1, the total mass space velocity of benzene and methanol is 2 h⁻¹, at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 37. Table 37 catalyst FXCAT-37 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 33.86 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.85 The selectivity of paraxylene in the products of C8 aromatics (wt%) 94.59 the selectivity of paraxylene in the products of aromatics (wt%) 95.51 product distribution (wt%) C1-C 6+ -chain hydrocarbons 18.67 toluene 51.46 Ethylbenzene 1.46 Paraxylene 26.22 Meta-xylene 0.02 O-Xylene 0.02 C 9+ - Aromas 2.15 Product distribution of chain hydrocarbons (wt%) CH4 1.05 C2H4 37.59 C2H6 0.1 C3H6 34.03 C3H8 1.69 C4 13.02 C5 6.77 C 6+ 5.75 C2H4+C3H6 71.62 Example 41: Production and reaction evaluation of the FXCAT-18 catalyst for the fluidized bed

[0235] In a solid fluidized bed reactor, the catalyst for the fluidized bed is produced online for the production of toluene with a co-product of paraxylene by alkylation of methanol and / or dimethyl ether and benzene, after which the reaction performance is evaluated.

[0236] The conditions for the online production of the catalyst are as follows: After 10 g (40-60 mesh) of shaped molecular sieve sample FXHZSM-5-A are loaded into a solid fluidized bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour charging period, the charging process is stopped, and then the temperature is increased to 550 °C under an air atmosphere and calcined for 4 hours. Afterwards, under a nitrogen atmosphere, the temperature is increased to 700 °C, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h. -1After a 4-hour feeding process, the feeding is stopped, thus producing the fluidized bed catalyst for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-38. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with the co-product of paraxylene and light olefins by alkylation of methanol and / or dimethyl ether with benzene. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene:methanol (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 38. Table 38 catalyst FLCAT-38 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 30.18 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.70 The selectivity of paraxylene in the products of C8 aromatics (wt%) 93.30 the selectivity of paraxylene in the products of aromatics (wt%) 94.56 product distribution (wt%) C1-C 6+ -chain hydrocarbons 17.43 toluene 51.48 Ethylbenzene 1.83 Paraxylene 26.60 Meta-xylene 0.05 O-Xylene 0.03 C 9+ - Aromas 2.58 Product distribution of chain hydrocarbons (wt%) CH4 1.01 C2H4 36.73 C2H6 0.11 C3H6 34.09 C3H8 1.93 C4 13.55 C5 7.20 C 6+ 5.38 C2H4+C3H6 70.82 Example 42: Production and reaction evaluation of the catalyst FXCAT-39 For the fixed bed

[0237] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0238] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, they are first treated with 50 ml / min of nitrogen at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. A mixture of trimethoxyphosphine and tetraethylsilica is fed into the reactor using a microfeed pump. The tetraethylsilica:trimethoxyphosphine mass ratio is 2. The total mass space velocity of the trimethoxyphosphine and tetraethylsilica at atmospheric pressure is 0.1 h⁻¹. -1After a 1-hour feed, the feed is stopped. Following nitrogen purging, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. This produces the catalyst for the fixed bed reaction of toluene with the co-product of paraxylene and light olefins from benzene and methanol, designated FXCAT-39. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material benzene:methanol (molar ratio) = 1:1, and the total mass space velocity of benzene and methanol is 2 h⁻¹. -1The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 39. Table 39 catalyst FXCAT-39 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 37.97 the selectivity of paraxylene in the products of xylene isomers (wt%) 95.28 The selectivity of paraxylene in the products of C8 aromatics (wt%) 83.25 the selectivity of paraxylene in the products of aromatics (wt%) 88.45 product distribution (wt%) C1-C 6+ -chain hydrocarbons 15.91 toluene 48.53 Ethylbenzene 3.92 Paraxylene 25.85 Meta-xylene 0.71 O-Xylene 0.57 C 9+ - Aromas 4.51 Product distribution of chain hydrocarbons (wt%) CH4 0.98 C2H4 33.21 C2H6 0.23 C3H6 31.15 C3H8 2.62 C4 16.99 C5 8.94 C 6+ 5.88 C2H4+C3H6 64.36 Example 43: Production and reaction evaluation of the FXCAT-40 catalyst for the fixed bed

[0239] In a micro fixed-bed reactor, the catalyst for the fixed bed for the production of toluene with co-product of paraxylene and light olefins from benzene and methanol is produced online, then the reaction performance is evaluated.

[0240] The conditions for the online production of the catalyst are as follows: after 5 g (40-60 mesh) of the shaped molecular sieve sample FXHZSM-5-A are loaded into a fixed-bed reactor, it is first treated with 50 ml / min of air at 550 °C for 1 hour and then cooled to 200 °C under a nitrogen atmosphere. Tetraethylsilica is fed in using a micro-feed pump; the mass space velocity of tetraethylsilica at atmospheric pressure is 0.2 h⁻¹. -1 After a 1-hour charging period, the charging process is stopped, and after purging with nitrogen, the temperature is increased to 550 °C and calcined in an air atmosphere for 4 hours. The temperature is then increased to 700 °C under a nitrogen atmosphere, and water is charged using a micro-charge pump. The mass velocity of water at atmospheric pressure is 2 h⁻¹. -1After a 4-hour feeding process, the feeding is stopped, thus producing the catalyst for the fixed bed for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol, which is designated FXCAT-40. Subsequently, under a nitrogen atmosphere, the temperature is cooled to the reaction temperature of 450 °C to test the reaction for the production of toluene with the co-product of paraxylene and light olefins from benzene and methanol. The reaction conditions are as follows: the raw materials are fed with a micro-feed pump, the raw material methanol:toluene (molar ratio) = 1:1, the total mass space velocity of benzene and methanol 2 h -1 The reaction temperature is at atmospheric pressure. The reaction product is analyzed by online Agilent 7890 gas chromatography, and the sample is examined 120 minutes after the reaction. The results of the reaction are shown in Table 40. Table 40 catalyst FXCAT-40 the reaction temperature (°C) 450 the conversion rate of methanol (%) 100 the conversion rate of benzene (%) 35.93 the selectivity of paraxylene in the products of xylene isomers (wt%) 99.49 The selectivity of paraxylene in the products of C8 aromatics (wt%) 90.93 the selectivity of paraxylene in the products of aromatics (wt%) 94.11 product distribution (wt%) C1-C 6+ -chain hydrocarbons 14.72 toluene 53.09 Ethylbenzene 2.57 Paraxylene 27.17 Meta-xylene 0.09 O-Xylene 0.05 C 9+ - Aromas 2.31 Product distribution of chain hydrocarbons (wt%) CH4 1.31 C2H4 11.73 C2H6 0.98 C3H6 20.65 C3H8 11.31 C4 29.13 C5 14.86 C 6+ 10.03 C2H4+C3H6 32.38 Example 44: Production and reaction evaluation of the catalyst FXCAT-41 for the fixed bed

[0241] The apparatus, operation, and conditions remain unchanged as in embodiment 5, except that the trimethoxyphosphorus is replaced by methyldiethoxyphosphorus during the catalyst preparation, and the rest is unchanged to prepare the fixed-bed catalyst for the production of light olefins with a co-product of paraxylene from methanol and toluene, which is designated FXCAT-41. The reaction evaluation conditions are the same as in Example 5, and the reaction results were consistent with Example 5 (the deviation did not exceed ± 1%). Example 45: Production and reaction evaluation of the FXCAT-42 catalyst for the fluidized bed

[0242] In a solid fluidized bed reactor, the catalyst for the fluidized bed is produced online for the production of paraxylene by alkylation of benzene and methanol, after which the reaction performance is evaluated.

[0243] The conditions for the online production of the catalyst are as follows: 1 kg of shaped molecular sieve sample FXHZSM-5-B was placed in a fixed-bed reactor, the reactor temperature was set to 300 °C, the tetraethyl silicate content in a mixture of tetraethyl silicate, toluene, and methanol was 10 wt%, and the toluene:methanol molar ratio was 2:1. The mass space velocity of the mixture of tetraethyl silicate, toluene, and methanol was 2 h⁻¹. -1 After 10 hours of charging, the charging is stopped, thus producing the catalyst for the production of paraxylene by alkylation of benzene and methanol, which is called FLCAT-42.

[0244] After FLCAT-42 is prepared online, the reaction proceeds to the alkylation reaction of toluene and methanol. The reaction conditions are as follows: reaction temperature: 450 °C, raw material toluene:methanol (molar ratio) = 2:1, and the mass space velocity of the toluene-methanol mixture is 2 h⁻¹. -1 The reaction product is analyzed by online Agilent 7890 gas chromatography at atmospheric pressure. The reaction results are shown in Table 41. Table 41 catalyst FLCAT-42 the reaction temperature (°C) 450 Loading time (min) 120 the conversion rate of methanol (%) 100 the conversion rate of toluene (%) 27.15 the selectivity of paraxylene in the products of xylene isomers (wt%) 95.08 product distribution (wt%) C1-C 6+ -chain hydrocarbons 17.22 benzene 0.51 Ethylbenzene 0.18 Paraxylene 73.85 Meta-xylene 2.03 O-Xylene 1.79 C 9+ - Aromas 4.42

[0245] The above description presents only some examples of the present application and is not intended to limit the scope of protection of the application. The present application is disclosed in preferred embodiments, but this is not intended to limit the application. It is within the scope of technical solutions to slightly amend or modify the technical content disclosed above to produce an equivalent embodiment without deviating from the technical scope of the present application.

Claims

[1] A process for carrying out a reaction I, wherein a raw material comprising methanol and / or dimethyl ether and toluene is contacted in a reactor with a catalyst obtained in an in-situ and in-line process to produce light olefins with a co-product of paroxylol, where reaction I is intended to produce light olefins from methanol and / or dimethyl ether and toluene with the co-product paroxylol, wherein a material stream I is brought into contact with the catalyst in the reaction system to obtain a material stream II, and C4 olefin or C 5+ Chain hydrocarbons are separated from material stream II, and the light olefins and paraxylene separated from material stream II and returned to the reaction system are used as products. the material stream I contains methanol and / or dimethyl ether and toluene, wherein the reaction system comprises: a first reaction zone containing a catalyst A; and a second reaction zone containing a catalyst B; and wherein catalyst A is an HZSM-5 molecular sieve catalyst modified by a phosphorus reagent and a silylation reagent, wherein the specific preparation steps are as follows: (A1) A mixture of the phosphorus reagent, the silylation reagent and toluene is fed into the first reaction zone with the HZSM-5 molecular sieve at a temperature in the range of 130°C to 500°C; (A2) The temperature is increased to over 500°C and the mixture is calcined in an air atmosphere for a period of 1 hour to 6 hours to obtain catalyst A, wherein catalyst B is an HZSM-5 molecular sieve catalyst modified by a silylation reagent, the specific preparation steps being as follows: (B1) A mixture of the silylation reagent and methanol is fed into the second reaction zone with the HZSM-5 molecular sieve at a temperature in the range of 120°C to 250°C; (B2) The temperature is increased to over 500°C and the mixture is calcined in an air atmosphere for a period of time ranging from 1 hour to 6 hours to obtain catalyst B. [2] Method according to claim 1, characterized by that the raw material is brought into contact with the catalyst at a reaction temperature of 350 °C to 650 °C. [3] Method according to claim 1, characterized by that the raw material is brought into contact with the catalyst at a reaction temperature of 400 °C to 500 °C. [4] Method according to claim 1, characterized by , that the ratio of methanol and / or dimethyl ether to toluene in the raw material containing methanol and / or dimethyl ether or toluene is as follows: The number of carbon atoms in methanol and dimethyl ether: mol toluene = 0.5 to 10. [5] Method according to claim 1, characterized by , that material stream I in the reaction system is brought into contact with the catalyst to obtain material stream II, and the C4 olefin or the C 5+ Chain hydrocarbons are separated from material stream II and recycled into the reaction system, and the light olefins and paraxylene separated from material stream II are used as products, wherein The current contains methanol and / or dimethyl ether and toluene. [6] Method according to claim 5, characterized by , that the reaction system comprises a first reaction zone and a second reaction zone, the material stream I in the first reaction zone is brought into contact with the catalyst to obtain the material stream II-A, then the C4 olefins or C separated from the material stream II-A 5+Chain hydrocarbons are recycled to the second reaction zone and brought into contact with the catalyst to obtain material stream II-B, the C4 olefins or C 5+ Chain hydrocarbons are separated from stream II-B and returned to the second reaction zone, The light olefins and paraxylene separated from material stream II-A and material stream II-B are used as products. [7] Method according to claim 6, characterized by , that the reaction system comprises a first reaction zone and a second reaction zone, and that material stream I in the first reaction zone is brought into contact with the catalyst to obtain material stream II-A, that material stream II-A is introduced into the separation system, and that C4 olefins, light olefins, and paraxylene are separated. the C4 olefins separated in the separation system are introduced into the second reaction zone to be brought into contact with the catalyst in order to obtain a material stream II-B, with the material stream II-B being introduced into the separation system; The light olefins and paraxylene separated in the separation system are used as products. [8] Method according to claim 6, characterized by , that the reaction system comprises a first reaction zone and a second reaction zone, material stream I in the first reaction zone is brought into contact with the catalyst to obtain material stream II-A, material stream II-A is introduced into the separation system, and the C 5+ -Chain hydrocarbons, light olefins and paraxylene are removed from the separation system, the C separated in the separation system 5+Chain hydrocarbons are introduced into the second reaction zone to be brought into contact with the catalyst in order to obtain material stream II-B, where material stream II-B is introduced into the separation system and The light olefins and paraxylene produced by the separation system are used as products. [9] Method according to claim 5, characterized by that the reaction system comprises one or more reactors connected in series and / or parallel. [10] Method according to claim 9, characterized by that the reactor is at least one of a fixed bed, fluidized bed or moving bed reactor. [11] Method according to claim 5, characterized by that the reaction system comprises a first reaction zone and a second reaction zone, wherein the first reaction zone and the second reaction zone are located in the same reactor. [12] Method according to claim 5, characterized bythat the reaction system comprises a first reaction zone and a second reaction zone, wherein the first reaction zone comprises one or more reactors connected in series and / or parallel, and wherein the second reaction zone comprises one or more reactors connected in series and / or parallel. [13] Method according to claim 6, characterized by that the first reaction zone and the second reaction zone are connected by series or parallel connection. [14] Method according to claim 1, characterized by , that the total feed rate of the raw materials is 0.1h -1 ~10h -1 amounts. [15] Method according to claim 1, characterized by , that the total feed rate of the raw materials is 0.8h -1 ~3h- 1 amounts. [16] Method according to claim 1, characterized by that the molar content of toluene in the raw material is 5 mol% - 50 mol%. [17] Method according to claim 1, characterized by that the molar content of toluene in the raw material is 20 mol% - 40 mol%. [18] Method according to claim 1, characterized by , that the phosphorus reagent is at least one selected from the compounds with the following formula I: where R1, R2 and R3 are independently selected from a C 1-10 -Alkyl group or a C 1-10 -Alkoxy group selected. [19] Method according to claim 1, characterized by , that at least one of R1, R2 and R3 in formula I is selected from C 1-10 -Alkoxy groups. [20] Method according to claim 1, characterized by , that the phosphorus reagent is at least one selected from trimethoxyphosphine, triethoxyphosphine, tripropoxyphosphine, tributoxyphosphine and methyldiethoxyphosphine. [21] Method according to claim 1, characterized by, that the silylation reagent is at least one selected from compounds with the following formula II: where R4, R5, R6, R7 are independently selected from C 1-10 -Alkyl groups or C 1-10 -Alkoxy groups. [22] Method according to claim 1, characterized by , that at least one of R4, R5, R6 and R7 in Formula II from C 1-10 -Alkoxy groups are selected. [23] Method according to claim 1, characterized by , that the silylation reagent is at least one selected from tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate and tetrabutyl silicate.

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