CN111111759B - Method for preparing toluene and xylene by liquid phase methylation - Google Patents

Method for preparing toluene and xylene by liquid phase methylation Download PDF

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CN111111759B
CN111111759B CN201811275595.6A CN201811275595A CN111111759B CN 111111759 B CN111111759 B CN 111111759B CN 201811275595 A CN201811275595 A CN 201811275595A CN 111111759 B CN111111759 B CN 111111759B
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xylene
liquid phase
toluene
molecular sieve
reaction
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CN111111759A (en
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邹薇
任淑
滕加伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for preparing toluene and dimethylbenzene by liquid phase methylation, which takes benzene and a methylation reagent as raw materials, and the reaction temperature is 100-350 ℃, the reaction pressure is 0.5-5.0 MPa, the molar ratio of benzene to methanol in the raw materials is 0.5-20, and the weight airspeed of benzene is 1-24h ‑1 Taking zeolite molecular sieve with mesoporous volume accounting for 15-60% of the total volume as a catalyst main body, synthesizing toluene and xylene with high selectivity; mainly solves the problems of low utilization rate of methanol, low selectivity of target products, poor service life of catalyst and the like in the production process in the prior art. The method has the advantages of low reaction temperature, high methanol utilization rate and long catalyst lifeThe method has the advantages of effectively reducing the energy consumption, material consumption and the like of the reaction, and can be used in the industrial production of toluene and dimethylbenzene.

Description

Method for preparing toluene and xylene by liquid phase methylation
Technical Field
The invention relates to a method for preparing toluene and dimethylbenzene by liquid phase methylation.
Background
Paraxylene is one of the most important basic organic chemical raw materials, and the demand thereof has shown a strong growth situation in the past five years. By the rapid development of the downstream main product PTA industry, the PX market demand in the next few years will still be in a rapid rising situation, the average demand amount increases by 24.9% in the years, and the annual consumption increase rate reaches 22.4%.
Aromatic methylation is a catalytic reaction of an aromatic compound with a methylating agent to produce para-xylene. The most studied toluene methylation and benzyl methylation reactions are currently performed by using benzene and/or toluene and methanol as reaction raw materials.
U.S. patent 6504072 discloses a process for the preparation of para-xylene comprising reacting toluene with methanol in an alkylation reactor in the presence of a catalyst comprising a porous crystalline material, which reaction may be carried out in a fixed, moving or fluidized reactor. U.S. patent 6642426 discloses a reaction scheme of an alkylation reactant comprising aromatic hydrocarbon and methanol in a fluidized bed reactor, which requires an operating temperature of 500 to 700 ℃ and a density of 300 to 600Kg/m 3 。
Many side reactions of aromatic hydrocarbons may also occur during alkylation. Methanol can polymerize with itself to form olefins, and aromatics can also be over-alkylated to form heavy aromatics. Over time, the catalyst surface acidity sites are covered by these olefins and heavy aromatics and deactivate, and the main cause of catalyst coking is high temperature. U.S. patent 4761513 discloses a reaction process for multistage feed of aromatic alkylation under gas phase conditions wherein the temperature in the reactors is controlled by the proportional addition of gas and liquid phase alkylating agents to each reactor to provide cooling. The addition of recycle hydrogen/nitrogen to the reaction system is also effective in reducing coking. Us patent 4337718 discloses a multistage process for producing para-xylene in a plurality of individual, series-connected, fixed catalyst layers. Wherein toluene is fed into the first stage along with hydrogen and sequentially through each subsequent fixed catalyst layer, the methylating agent is fed into each fixed catalyst layer.
In addition to any co-feed gas, water, which may be in vapor form, may be introduced into the reactor as a co-feed with the alkylation feed to enhance catalyst stability. The water and steam used for the methylation reaction may be introduced into the reactor as co-feeds with the alkylation feed, with or without hydrogen or nitrogen, at the beginning of the alkylation reaction, or it may be introduced after the beginning. In any case liquid water may be added and vaporized before it is mixed with the co-feed gas and the alkylation feed.
U.S. patent 7321072 discloses a process for the selective methylation of toluene to para-xylene in a flow reactor wherein the reactants are a mixture of toluene, methanol and water, the reactor may be in the form of a single or a plurality of reactors in series. Other U.S. patent nos. 7060864 and 7186872 also disclose the use of water co-feeds.
From the above review, in recent years, methylation reaction of benzene and methanol has been advanced, but in the reaction system, under the condition of gas phase reaction, recycle hydrogen and/or other inert gases are often required to be added to slow down coking of the catalyst, and prolong the service life of the catalyst. However, under the condition of gas phase reaction, the probability of MTO reaction, self-decomposition and other side reactions of the methanol on the catalyst is higher, so that the stability of the catalyst is reduced, the methanol utilization rate of the catalyst is reduced, the economy of the methylation reaction is insufficient, and the industrial application of the methylation reaction is inhibited to a certain extent.
In addition to the acidity of the catalyst itself, the diffusion of reactants and products also has a very important effect on the reaction. Among them, the internal diffusion is particularly important for the reaction activity, and the factors such as particle size, pore structure, average pore diameter, pore volume, grain size, etc. are beneficial to the activity, selectivity and stability of the catalyst.
If the conventional molecular sieve catalyst is adopted, the occurrence probability of MTO reaction, self-decomposition and other side reactions of the methanol is obviously reduced under the low-temperature reaction condition of a liquid phase, and the utilization rate of the methanol is obviously improved. However, under the condition of liquid phase reaction, the diffusion performance of the reaction raw materials in the pore canal of the zeolite is far lower than that of the gas phase reaction, the difficulty of the raw materials entering the pore canal of the zeolite molecular sieve is high, the accessibility of the acid center on the surface of the zeolite molecular sieve is obviously reduced compared with that of the gas phase reaction, the activity of the catalyst is low, and the reaction cannot be carried out.
By introducing mesopores into the zeolite molecular sieve, the diffusion resistance can be effectively reduced, the diffusion can be accelerated, the raw materials can enter the zeolite molecular sieve pore canal under the liquid phase condition, the accessibility of active centers on the catalyst is improved, the reaction on the acid surface of the catalyst is promoted, the products generated by the reaction can be rapidly diffused out of the inside of the pore canal, the side reactions such as excessive alkylation and the like are avoided, the generation probability of carbon deposition precursors is reduced, and the stability of the catalyst is improved.
The method for synthesizing the mesoporous molecular sieve is to add a microporous template agent for promoting the formation of the zeolite molecular sieve into a synthesis system, and also add a mesoporous template agent for inducing the formation of mesopores, wherein the common mesoporous template agent mainly comprises hard template agents and soft template agents, such as carbon black particles, carbon nano tubes, carbon aerogel, polysaccharide compounds and other hard template agents, and organosilane serving as a soft template and cationic polymers and amphoteric molecules.
Disclosure of Invention
The invention aims to solve the technical problems of low methanol utilization rate of the catalyst, insufficient catalyst stability, high olefin content in the product and the like under the gas phase reaction condition in the prior art. Providing a low-temperature high-pressure reaction condition, and carrying out liquid-phase reaction on benzene and methanol to generate a synthesis method of toluene and dimethylbenzene; meanwhile, the generated toluene can also be recycled to the methylation reaction unit to further react with methanol to generate high-concentration xylene. The mesoporous molecular sieve used in the invention improves the accessibility of raw materials on the active center position of the catalyst, improves the activity and selectivity of the catalyst, simultaneously ensures that alkylbenzene generated by the reaction can be timely diffused, avoids further alkylation, reduces the generation probability of forming larger molecules which are difficult to diffuse, and improves the stability of the catalyst.
The method has the characteristics of high methanol utilization rate, less olefin content in the product, high product selectivity, good catalyst stability and the like.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing toluene and dimethylbenzene by liquid phase methylation uses benzene and a methylation reagent as raw materials, and the raw materials react under the action of a catalyst at the reaction temperature of 100-350 ℃ and the reaction pressure of 0.05-5.0 MPa to obtain a product containing toluene and dimethylbenzene; the catalyst comprises a molecular sieve containing a mesoporous structure.
In the technical scheme, the molecular sieve containing the mesoporous structure preferably has the mesoporous volume accounting for 10-60% of the total volume; more preferably 15 to 40% by volume.
In the technical scheme, the catalyst is prepared by taking the molecular sieve with the mesoporous structure as a main body, and comprises the following components in percentage by weight:
a) 20-90% of silicon-aluminum zeolite molecular sieve;
b) 10-80% of binder;
c) 0-10% of metal or non-metal oxide.
The zeolite molecular sieve is preferably selected from one or at least one of MFI series molecular sieves, EU-1, SAPO-11, SAPO-34, MCM-22, MCM-56, beta zeolite, mordenite, Y molecule, and X molecular sieve. The Si/Al silicon-aluminum mole ratio of the silicon-aluminum zeolite molecular sieve is 3-150; preferably 5 to 120; more preferably 10 to 50, and the mesoporous molecular sieve can be treated by alkali liquor and/or acid.
In the technical scheme, the preferable reaction temperature is 100-300 ℃; preferably 120-250 ℃; more preferably 140 to 220 ℃;
in the technical scheme, the preferable reaction pressure is 0.1-4.5 MPa; preferably 0.5 to 3.5MPa; more preferably 1.0 to 2.5MPa;
in the technical scheme, the reaction temperature is 130-220 ℃, and the preferable reaction pressure is 1.0-2.5 MPa; the reaction temperature is 130-180 ℃, and the preferable reaction pressure is 1.0-1.7 MPa; when the reaction temperature is increased, a higher reaction pressure is preferred, the reaction temperature is 180-220 ℃, and the reaction pressure is preferably 1.7-2.5 MPa
The molar ratio of benzene to methanol in the raw material is 0.5-20, preferably 1-10, more preferably 2-6; the weight space velocity of benzene is 1.0-24.0 h -1 Preferably 2.0 to 12.0h -1 More preferably 3.0 to 6.0 hours -1 At higher temperatures, the reaction pressure may increase accordingly.
In the technical scheme, the methylation reagent is selected from one or at least one of methanol, dimethyl ether, methylamine, chloromethane and bromomethane, preferably one or at least one of methanol and dimethyl ether, and more preferably the methylation reagent is methanol.
In the technical scheme, the post-treatment mode of the mesoporous zeolite molecular sieve adopts alkali treatment and/or acid treatment, wherein the treatment mode is that the concentration of alkali liquor and/or acid solution is 0.5-10wt%, the treatment temperature is 30-90 ℃, the treatment time is 3-25 hours, and the weight ratio of the alkali liquor and/or acid liquor to the molecular sieve is 10-30. The alkali liquor is at least one selected from sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonia water, potassium hydroxide, potassium carbonate, potassium bicarbonate, tetrapropylammonium bromide, tetrapropylammonium hydroxide or tetramethylammonium hydroxide; the acid solution is at least one selected from hydrochloric acid, sulfuric acid, oxalic acid, citric acid, lactic acid, nitric acid and tartaric acid.
In the technical scheme, the binder is selected from one or at least one of alumina, pseudo-boehmite, silica, clay, silica sol, titanium oxide or zirconium oxide.
In the technical scheme, the metal or nonmetal metal oxide is selected from one or at least one of oxides of magnesium, lanthanum, bismuth, nickel, phosphorus, tungsten, molybdenum, platinum and palladium elements. The compound preferably used is at least one of oxides, chlorides, sulfates, acetates, ammonium salts and nitrates of magnesium, lanthanum, bismuth, nickel, phosphorus, tungsten, molybdenum, platinum, palladium elements. The indexes of comparative interest in the aromatic methylation reaction comprise xylene selectivity, methyl utilization rate, inactivation speed and the like, wherein the xylene selectivity refers to the weight percentage of the xylene in the product; methyl utilization refers to the proportion of alkylating agent converted to methyl groups on the aromatic ring relative to the total alkylating agent feed, and deactivation rate refers to the average hourly decrease in methanol conversion over the reaction time.
The specific expression of each index is as follows:
Figure BDA0001846905060000051
Figure BDA0001846905060000052
Figure BDA0001846905060000053
in the expression of the above methyl utilization ratio, we can find that the index contains methyl in toluene, xylene and trimethylbenzene, and the trimethylbenzene expression multiplied by a factor of 3 is because trimethylbenzene is a benzene ring of raw material benzene added with three methyl groups, tetramethylbenzene and other heavier aromatic hydrocarbons, the composition of which is complex, the accurate analysis is difficult, and the generation amount of the substance is small, so that the methyl utilization ratio is neglected in calculation.
The invention adopts the liquid-phase methylation reaction method, and the probability of methanol to generate MTO reaction, self-decomposition and other side reactions is obviously reduced compared with the gas-phase reaction condition under the conditions of low temperature and high pressure, so that the catalyst stability is improved and the service life of the catalyst is prolonged while the utilization rate of the methanol is improved.
Description of characterization methods
The morphology and size of the samples were observed using a Bruker type Scanning Electron Microscope (SEM). The acceleration voltage was measured at 2kV. Before measurement, the sample to be measured is uniformly dispersed on a sample table with double-sided conductive adhesive, metal spraying is carried out on the sample, and then high-resolution scanning electron microscope image testing is carried out.
Nitrogen physical adsorption and desorption tests were performed using a Tristar II 3020 type physical adsorption and desorption instrument from Micromeritics. For analysis, the sample was degassed under vacuum at 300 ℃ for 6.0h, and then isothermal adsorption-desorption data of the sample to nitrogen were determined at liquid nitrogen temperature. The specific surface area and the total pore volume of the sample are calculated by using a BET method, the mesoporous distribution and pore volume of the sample are calculated by using a BJH method, and the micropore volume and the micropore specific surface area of the sample are calculated by using a t-plot method.
Drawings
Fig. 1 and 2 are high-resolution scanning electron microscope images of the SAPO-34 molecular sieve prepared in example 2 before and after mesoporous treatment, respectively, and after the treatment, mesoporous channels of the molecular sieve are clearly visible by comparing fig. 1 and 2.
Fig. 3 and 4 are pore structure spectra of the SAPO-34 molecular sieve prepared in example 2 before and after the mesoporous treatment, respectively, and as can be seen from fig. 3 and 4, the mesoporous state of the molecular sieve is obvious after the etching treatment.
The invention is further illustrated by the following examples.
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Comparative example 1
10g of conventional hydrogen-type ZSM-5 molecular sieve catalyst CX without mesoporous structure and SiO of molecular sieve are filled by using a fixed bed reactor 2 /Al 2 O 3 The benzene vapor phase methylation reaction performance was evaluated at a molar ratio of 50. Benzene and methanol liquids were evaluated in a molar ratio of 2:1, uniformly stirring, heating, vaporizing, introducing into the top of reactor, dispersing and preheating by upper layer porcelain ball, introducing into catalyst bed, and at weight space velocity WHSV4.0hr -1 Under the gas phase reaction condition of 420 ℃ and 0.5Mpa, the reaction product is cooled from the lower end of the reactor and is introduced into a gas-liquid separator for separation, the liquid product is sampled and analyzed,the technical index is shown in Table 2.
Comparative example 2
SiO 2 /Al 2 O 3 70 g of sodium ZSM-5 molecular sieve powder with the molar ratio of 150 and 550 ℃ and burning weight loss of 10 percent and 5g of dry EU-1 molecular sieve are treated by 3000 g of 10wt% sodium carbonate solution and 1500 g of 10wt% hydrochloric acid solution respectively at 80 ℃ for 10 hours to obtain a mesoporous molecular sieve with 40 percent (volume) of mesoporous volume, and the mesoporous molecular sieve is exchanged to Na by ammonium nitrate solution 2 The O content is less than 0.1% by weight. 42.2 g of silica sol (SiO 2 ) Kneading, baking and calcining, and using 40 wt% analytical pure lanthanum nitrate La (NO) 3 ) 3 ·nH 2 O]Soaking the solution in equal amount, oven drying, and roasting. The weight ratio of the preparation is as follows: la/Hydrogen molecular sieves/SiO 2 Impregnating precursor =15/80/20; to a solution of 0.2g chloroplatinic acid and 15 ml water, the solution was immersed for 2 hours and then dried at 110 ℃. The dried residue was warmed to 538℃in a muffle furnace at a rate of 1℃per minute, left to cool naturally after 3 hours, catalyst CY.
Benzene gas phase methylation reaction performance evaluation was performed by filling 10g of catalyst CY using a fixed bed reactor, and benzene and methanol liquids were mixed in a molar ratio of 2:1 into raw materials, uniformly stirring, heating, vaporizing, introducing into the top of a reactor, dispersing and preheating by an upper porcelain ball, introducing into a catalyst bed, and at a weight space velocity WHSV of 4.0hr -1 Under the condition of gas phase reaction at 420 ℃ and 0.5Mpa, the reaction product is cooled from the lower end of the reactor and is introduced into a gas-liquid separator for separation, and the liquid product is sampled and analyzed, and the technical indexes are shown in table 2.
Comparative example 3
Weighing SiO 2 /Al 2 O 3 60g of SAPO-34 molecular sieve with the molar ratio of 6, and the ammonium nitrate solution is exchanged to Na 2 The O content is less than 0.1% by weight. And Na (Na) 2 O content of less than 0.1 wt.% SiO 2 /Al 2 O 3 5g of ammonium type X molecular sieve with a molar ratio of 3 and SiO 2 /Al 2 O 3 10g of ammonium type Y molecular sieve with a molar ratio of 5.8 and Na 2 The O content is less than 0.15 percent (weight), and the ignition weight loss is 30 percent at 550 DEG CPseudo-boehmite (alpha-Al) 2 O 3 ·H 2 O) 24.1 g, kneading, extruding, shaping, drying, calcining, granulating, and adding analytically pure cerous nitrate [ Ce (NO) 3 ) 3 ·6H 2 O]Dipping in solution, drying, roasting, dipping in analytically pure ammonium phosphomolybdate solution, drying and roasting. The weight ratio of the preparation is as follows: ce/Mo/P/hydrogen molecular sieve/alumina = 0.5/1/3/80/20 catalyst; to a solution of 0.2g chloroplatinic acid and 15 ml water, the solution was immersed for 2 hours and then dried at 110 ℃. The dried residue was heated to 538℃in a muffle furnace at a rate of 1℃per minute, and left to cool naturally after 3 hours to give catalyst CZ.
The benzene liquid phase methylation reaction performance of the catalyst CZ was evaluated on a fixed bed reaction evaluation device. At the reaction temperature of 100-300 ℃, the reaction pressure of 0.5-5.0 MPa, the molar ratio of benzene to methanol in the raw materials of 0.5-20.0, and the weight space velocity of benzene of 1-24h -1 The reaction was carried out under the conditions shown in Table 1. The reaction results are shown in Table 2.
[ example 1 ]
SiO 2 /Al 2 O 3 70 g of sodium ZSM-5 molecular sieve powder with the molar ratio of 150 and 550 ℃ and burning weight loss of 10 percent and 5g of dry EU-1 molecular sieve are treated by 3000 g of 10 weight percent sodium carbonate solution and 1500 g of 10 weight percent hydrochloric acid solution respectively at 80 ℃ for 10 hours to obtain a mesoporous molecular sieve with mesoporous accounting for 40 percent of the total volume, and the mesoporous molecular sieve is exchanged to Na by ammonium nitrate solution 2 The O content is less than 0.1% by weight. 42.2 g of silica sol (SiO 2 40% by weight) analytically pure lanthanum nitrate [ La (NO) 3 ) 3 ·nH 2 O]Soaking the solution in equal amount, oven drying, and roasting. The weight ratio of the preparation is as follows: la/Hydrogen molecular sieves/SiO 2 Catalyst a=15/80/20.
[ example 2 ]
Weighing SiO 2 /Al 2 O 3 60g of SAPO-34 molecular sieve with the molar ratio of 6 is treated with 1.8g of oxalic acid and 1500 g of 3wt percent tetrapropylammonium bromide solution at 50 ℃ for 3 hours to obtain the mesoporous molecular sieve with mesoporous accounting for 60 percent of the total volume, and the ammonium nitrate solution is exchanged to Na 2 The O content is less than 0.1% by weight. And Na (Na) 2 O content of less than 0.1 wt.% SiO 2 /Al 2 O 3 5g of ammonium type X molecular sieve with a molar ratio of 3 and SiO 2 /Al 2 O 3 10g of ammonium type Y molecular sieve with a molar ratio of 5.8 and Na 2 Pseudoboehmite (alpha-Al) with O content less than 0.15% by weight and loss on ignition at 550℃ of 30% 2 O 3 ·H 2 O) 24.1 g, kneading, extruding, shaping, drying, calcining, granulating, and adding analytically pure cerous nitrate [ Ce (NO) 3 ) 3 ·6H 2 O]Dipping in solution, drying, roasting, dipping in analytically pure ammonium phosphomolybdate solution, drying and roasting. The weight ratio of the preparation is as follows: ce/Mo/P/hydrogen molecular sieve/alumina = 0.5/1/3/80/20 catalyst B.
[ example 3 ]
SiO 2 /Al 2 O 3 75.0 g of sodium mordenite powder with the molar ratio of 28 and the weight loss by burning of 10 percent is treated with 7000 g of 0.5wt percent ammonia water solution at 50 ℃ for 25 hours to obtain the mesoporous molecular sieve with mesoporous accounting for 15 percent of the total volume, and the ammonium nitrate solution is exchanged to Na 2 The O content is less than 0.1% by weight. 64.3 g of pseudo-boehmite (. Alpha. -Al) of the same specification as in example 2 was added 2 O 3 ·H 2 O), fully and uniformly mixing, kneading, extruding, forming, drying, roasting, granulating, firstly using analytically pure lanthanum nitrate [ La (NO) 3 ) 3 ·nH 2 O]Soaking in the same amount, stoving, roasting, and magnesium acetate [ Mg (CH) 3 COO) 2 ·4H 2 O]Soaking in the same amount of solution, oven drying, roasting, and finally adding calcium nitrate (Ca (NO) 3 ) 2 ·4H 2 O]Soaking the solution in equal amount, oven drying, and roasting. The weight ratio of the preparation is as follows: la/Mg/Ca/hydrogen type molecular sieve/Al 2 O 3 Catalyst c= 20/6/2/60/40.
[ example 4 ]
SiO is made of 2 /Al 2 O 3 55.0 g of sodium MCM-22 molecular sieve powder with the molar ratio of 50 and the ignition weight loss of 10 percent is treated for 3 hours at the temperature of 90 ℃ by 4500 g of sodium hydroxide solution with the weight percent of 3 percent, thus obtaining the mesoporous molecular sieve with the mesoporous accounting for 25 percent of the total volume, and the ammonium nitrate solution is exchanged to Na 2 The O content is less than 0.1% by weight. Na and Na 2 O content of less than 0.1 wt.% SiO 2 /Al 2 O 3 20.0 g of ammonium beta zeolite powder with the molar ratio of 35 and the ignition weight loss of 10 percent is added with 24.1 g of pseudo-boehmite with the same specification as that of the example 2, uniformly mixed, kneaded, extruded and formed, dried and baked to form granules. Lanthanum nitrate [ La (NO) 3 ) 3 ·nH 2 O]The solution is exchanged in water bath at 95 ℃ for 0.5 hour, dried, roasted and then used for 0.2N magnesium acetate [ Mg (CH) 3 COO) 2 ·4H 2 O]The solution is exchanged in water bath at 95 ℃ for 0.5 hour, dried and roasted. The weight ratio of the preparation is as follows: la/Mg/hydrogen molecular sieve/alumina = 15/3/80/20 catalyst D.
[ example 5 ]
75.0 g of ammonium MCM-56 molecular sieve powder is treated for 3 hours at 90 ℃ by 1500 g of mixed solution of hydrochloric acid and oxalic acid with the weight percentage of 0.5 percent, then a mesoporous molecular sieve with mesoporous accounting for 35 percent of the total volume is obtained, 24.1 g of pseudo-boehmite with the same specification as that of the example 2 is added, and the mixture is uniformly mixed, kneaded, extruded into strips, molded, dried and baked to obtain the composite material with the weight percentage of: hydrogen form molecular sieve/alumina = 75/25 catalyst E.
Examples 6 to 10
20 g of catalysts A to E were taken, respectively, and added to a solution of chloroplatinic acid, nickel nitrate, palladium nitrate and 15 ml of water, followed by impregnation for 2 hours and drying at 110 ℃. Heating the dried residues to 538 ℃ in a muffle furnace at a speed of 1 ℃/min, keeping for 3 hours, and naturally cooling to obtain catalysts F-J, wherein catalysts A, B are treated with 0.2g of chloroplatinic acid to obtain catalysts F, G; treating the catalyst C with 1.0 g of nickel nitrate to obtain a catalyst H; catalyst D, E was treated with 0.3 g palladium nitrate to give catalysts I and J, respectively.
Examples 11 to 20
Catalysts A to J were examined for the activity and selectivity of the benzene liquid phase methylation reaction on a fixed bed reaction evaluation device. At the reaction temperature of 100-300 ℃, the reaction pressure of 0.5-5.0 MPa, the molar ratio of benzene to methanol in the raw materials of 0.5-20.0, and the weight space velocity of benzene of 1-24h -1 The reaction was carried out under the conditions shown in Table 1. The reaction results are shown in Table 2.
TABLE 1
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Figure BDA0001846905060000101
TABLE 2
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Claims (16)

1. A method for preparing toluene and dimethylbenzene by liquid phase methylation uses benzene and a methylation reagent as raw materials, and the raw materials react under the action of a catalyst at the reaction temperature of 100-300 ℃ and the reaction pressure of 0.05-5.0 MPa to obtain a product containing toluene and dimethylbenzene; the catalyst comprises a molecular sieve containing a mesoporous structure, wherein the volume of mesopores in the molecular sieve containing the mesoporous structure accounts for 10-60% of the total volume;
the catalyst comprises the following components in percentage by weight:
a) 20-90% of a silicon-aluminum zeolite molecular sieve;
b) 10-80% of a binder;
c) 0-10% of metal or nonmetal oxide.
2. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the volume of mesopores in the molecular sieve containing the mesoporous structure is 15 to 40% by volume of the total volume.
3. The method for producing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the reaction temperature is 120 to 250 ℃.
4. The method for producing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the reaction temperature is 140 to 220 ℃.
5. The method for producing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the reaction pressure is 0.1 to 4.5 MPa.
6. The method for producing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the reaction pressure is 0.5 to 3.5 MPa.
7. The method for producing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the reaction pressure is 1.0 to 2.5 MPa.
8. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the reaction temperature is 130-220 ℃ and the reaction pressure is 1.0-2.5 MPa.
9. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the reaction temperature is 130-180 ℃ and the reaction pressure is 1.0-1.7 MPa.
10. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the reaction temperature is 180-220 ℃ and the reaction pressure is 1.7-2.5 MPa.
11. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the aluminosilicate zeolite molecular sieve is at least one selected from MFI series molecular sieves, EU-1, SAPO-11, SAPO-34, MCM-22, MCM-56, zeolite beta, mordenite, Y molecules, and X molecular sieves; the Si/Al silicon-aluminum mole ratio of the silicon-aluminum zeolite molecular sieve is 3-150; the mesoporous molecular sieve adopts alkali liquor treatment and/or acid treatment.
12. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the Si/ai silica alumina molar ratio of the silica alumina zeolite molecular sieve is 5 to 120.
13. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, characterized in that the Si/Al silica-alumina molar ratio of the silica-alumina zeolite molecular sieve is 10 to 50.
14. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the weight space velocity of benzene is 1.0 to 24.0 hours -1 。
15. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the weight space velocity of benzene is 2.0 to 12.0 hours -1 。
16. The method for preparing toluene and xylene by liquid phase methylation according to claim 1, wherein the weight space velocity of benzene is 3.0 to 6.0 hours -1 。
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