CN106316740B - Aromatization method - Google Patents

Aromatization method Download PDF

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Publication number
CN106316740B
CN106316740B CN201510345647.2A CN201510345647A CN106316740B CN 106316740 B CN106316740 B CN 106316740B CN 201510345647 A CN201510345647 A CN 201510345647A CN 106316740 B CN106316740 B CN 106316740B
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molecular sieve
grams
silica alumina
zsm
raw material
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CN106316740A (en
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郑均林
宋奇
孔德金
祁晓岚
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to US15/738,063 priority patent/US10358606B2/en
Priority to PCT/CN2016/000315 priority patent/WO2016201955A1/en
Priority to ES16810696T priority patent/ES2880326T3/en
Priority to BR112017027347-0A priority patent/BR112017027347B1/en
Priority to EP16810696.1A priority patent/EP3312153B1/en
Priority to KR1020187001728A priority patent/KR102454225B1/en
Priority to DK16810696.1T priority patent/DK3312153T3/en
Priority to JP2017565948A priority patent/JP6877367B2/en
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to a kind of aromatization methods, under aromatization conditions, contact raw material with molecular sieve catalyst and generate the arene stream containing benzene, toluene and dimethylbenzene；Wherein, the raw material has structure formula (I):In formula (I), R1For the C optionally replaced1‑8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1‑10Linear or branched alkyl group, the positive integer that n is 1~6.This method can be used for non-fossil sources aromatic hydrocarbons field.

Description

Aromatization method
Technical field
The present invention relates to a kind of aromatization method, in particular to a kind of aromatisation prepares benzene,toluene,xylene light aromatics Method.
Background technique
Aromatic hydrocarbon product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, domestic consumption It measures considerable, there is great influence to the national economic development, while being the important basic organic chemical industry raw material of social development.Benzene, first Benzene, dimethylbenzene are widely used three kinds of aromatic hydrocarbons bulk chemicals in aromatic hydrocarbons.Benzene is a kind of basic petrochemical material of multipurpose, can be with Produce numerous products, including ethyl benzene/styrene, cumene/phenol derived from it etc..Paraxylene is mainly for the manufacture of to benzene Dioctyl phthalate gathers cruel fiber as gathered for producing by terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) intermediate Ethylene glycol terephthalate (PET), resin and film.The production of aromatic hydrocarbons depends on non-renewable change both at home and abroad at present Stone resource, such as can be by the way that by petroleum, by adding, hydrogen, reformation, aromatic hydrocarbons converts and separation technical process obtains on a catalyst.But It is that fossil resource reserves are limited and non-renewable, so that being that the cost that main refining raw material produces aromatic hydrocarbons is more shown in height with petroleum Rise.In addition, fossil resource is continually developed using a large amount of greenhouse gas emissions are generated, caused a series of environmental problems is increasingly Seriously, thus development from the production of renewable resource route, aromatic hydrocarbons is significant and application value.
Levulic acid (4-Oxyvalerate, levulonic acid or valeric acid) is a kind of short chain non-volatile fatty acid.Acetyl Propionic acid low toxicity, has hygroscopicity, distills under normal pressure and hardly decompose, and carbonyl and carboxyl is contained in molecule, it is prone at salt, ester Change, add the series of chemical such as hydrogen, condensation, oxidation and halogenation, is the important centre for preparing a variety of chemical products with high added-value Body is widely used in the industrial circles such as fragrance, solvent, oil dope, medicine and plasticizer.Levulinate is short-chain Aliphatic ester, generally colourless liquid, boiling point is higher, and a kind of important organic chemicals, can be directly used as fragrance, food Additive, gasoline additive and biological liquid fuel etc. can be used for the row such as food, cosmetics, medicine, plastics and communications and transportation Industry.
Currently, people expand research to the utilization of levulic acid.Document US20140171688A1 is disclosed levulinic Acid is converted into the ketones solvents such as methyl ethyl ketone.After this method converts levulic acid and formic acid for hexose first, by alkali process Metal salt is formed, obtains can be used as the methyl ethyl ketone of solvent after electrolytic decarbodylation in electrolytic cell again later.Document US20060247444A1, which is disclosed, converts N- alkyl pyrrolidone for levulic acid.N- alkyl pyrrolidone may be used as molten Agent, surfactant, dispersing agent and emulsifier can be used for the maintenance of oil well and gas well, the synthesis of polymer and medicine aspect. That patent describes 2 step processes, and catalytic hydrogenation prepares 5- methyl-N- alkane under hydrogen after levulic acid and organic amine are mixed - 2 pyrrolidones of base.Document CN200910073688.5 discloses the method that levulic acid is prepared angelica lactone.Levulic acid The middle inorganic liquid acid or solid acid catalyst that its weight 1~10% is added, at a temperature of 100~150 DEG C, control vacuum degree is 20 ~150mmHg, levulic acid and alpha-angelica lactone in reaction system gas phase are separated by rectifying, and levulic acid is back to Reaction system, alpha-angelica lactone condensation, controls 60~90 DEG C of condensation temperature, separation and purification obtains product.On the whole, levulic acid Conversion be concentrated mainly on and be converted into the fine chemicals such as pure and mild ester, be rarely reported and convert benzene, toluene, diformazan for levulic acid The aromatic hydrocarbons such as benzene.
Summary of the invention
The purpose of the present invention is to provide a kind of methods of alcohol compound aromatisation production aromatic hydrocarbons.Such alcohol compound It can be obtained by the biomass material of rich reserves from a wealth of sources, it can be with large scale preparation.This method increase traditional aromatic hydrocarbons Production method can be used as the supplement of fossil resource production aromatic hydrocarbons, have at low cost, the high-efficient and easy industrialization amplification of aromatisation The characteristics of.
For achieving the above object, The technical solution adopted by the invention is as follows: a kind of aromatization method, in aromatisation item Under part, contacts raw material with molecular sieve catalyst and generate the arene stream containing benzene, toluene and dimethylbenzene；Wherein, the raw material tool There is structure formula (I):
In formula (I), R1For the C optionally replaced1-8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1-10Straight chain or branch Alkyl group, the positive integer that n is 1~6.
In above-mentioned technical proposal, it is preferable that in formula (I), R1For the C optionally replaced1-4Linear or branched alkyl group.
In above-mentioned technical proposal, it is preferable that in formula (I), R2For hydrogen, optionally the C replaced1-5Linear or branched alkyl group.
In above-mentioned technical proposal, it is preferable that in formula (I), n be 1~4 positive integer.
In above-mentioned technical proposal, it is preferable that the molecular sieve catalyst based on parts by weight, including following component: a) 20 ~80 parts of molecular sieve；B) 20~80 parts of binder.
In above-mentioned technical proposal, it is preferable that the molecular sieve be selected from ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, At least one of beta, MCM-22 or MCM-41 molecular sieve.It is highly preferred that the molecular sieve be selected from ZSM-5, Y, beta or At least one of MCM-41.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio SiO of ZSM type molecular sieve2/Al2O3=10~500；It is more excellent Selection of land, the silica alumina ratio SiO of ZSM type molecular sieve2/Al2O3=15~100.The silica alumina ratio SiO of Y molecular sieve2/Al2O3= 2~70；It is highly preferred that the silica alumina ratio SiO of Y molecular sieve2/Al2O3=3~50.The silica alumina ratio of beta molecular sieve SiO2/Al2O3=10~150；It is highly preferred that the silica alumina ratio SiO of beta molecular sieve2/Al2O3=15~65.MCM type molecule The silica alumina ratio SiO of sieve2/Al2O3=20~250；It is highly preferred that the silica alumina ratio SiO of MCM type molecular sieve2/Al2O3= 40~150.
In above-mentioned technical proposal, it is preferable that the aromatization conditions are as follows: 300~800 DEG C of reaction temperature, Hydrogen Vapor Pressure with Gauge pressure 0.1~5MPa of meter, raw material weight air speed 0.3~10 hour-1。
In above-mentioned technical proposal, it is preferable that the raw material comes from biological material.
In above-mentioned technical proposal, it is preferable that the raw material comes from xylitol, glucose, cellobiose, hemicellulose or wood At least one of quality.
In above-mentioned technical proposal, it is preferable that the raw material is in bagasse, glucose, timber, corn stalk or straw straw At least one.
Catalyst described in the method for the present invention the preparation method is as follows: molecular sieve, binder, extrusion aid, expanding agent are mixed It pinches, extruded moulding, 100~200 DEG C drying 1~24 hour after molding roasts 1~10 hour at 400~700 DEG C.Wherein, The extrusion aid is at least one of sesbania powder, polyethylene glycol or sodium carboxymethylcellulose, and the expanding agent is citric acid, grass At least one of acid or ethylenediamine tetra-acetic acid, the extrusion aid of addition and the total amount of expanding agent are no more than mixture weight 10%.Acid is added when molding to be mediated, the acid of addition includes at least one of inorganic acid or acetic acid, and inorganic acid includes nitre At least one of acid, sulfuric acid or phosphoric acid, the amount for the acid solution being added are the 50~90% of mixture weight.
As an embodiment of the invention, raw material of the present invention is biomass based compound.Such compound It can be obtained by biomass material from a wealth of sources, rich reserves, it can be with large scale preparation.For example, levulic acid can be in zirconium In the presence of oxide, metal chloride, organic acid or inorganic acid, produced by the biomass substrate such as cellulose, stalk (Efficient Conversion of Cellulose to Levulinic Acid by Hydrothermal Treatment Using Zirconium Dioxide as a Recyclable Solid Acid Catalyst, Ind.Eng.Chem.Res.,2014,53(49),pp 18796–18805；Production of levulinic acid from cellulose by hydrothermal decomposition combined with aqueous phase Dehydration with a solid acid catalyst, Energy Environ.Sci., 2012,5,7559-7574； Effective Production of Levulinic Acid from Biomass through Pretreatment Using Phosphoric Acid, Hydrochloric Acid, or Ionic Liquid, Ind.Eng.Chem.Res., 2014,53(29),pp 11611–11621)。
The method of the present invention has preferable selectivity to benzene,toluene,xylene product, solves previous biomass aromatic hydrocarbons mistake The problem that aromatics yield is low in journey and reaction step is long.Using the method for the present invention, feed stock conversion can reach 99%, benzene, Toluene, dimethylbenzene target product selectivity reach as high as 94%, achieve preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
60 grams of corn stalks are weighed, is placed in autoclave pressure and is added 700 grams of water, add the sulphur of the 5mol/L of water quality 7% Acid solution is warming up at 180 DEG C and reacts 45 minutes, cools down later, reaction solution after cooling is filtered, filter cake and filtering are obtained Liquid, filtered fluid are that the hydrolyzate of cellulose uses mass spectrum to carry out identifying primary product for acetyl to reaction result after reaction Propionic acid, yield are 18 grams.
It weighs the ZSM-5 that 35 grams of silica alumina ratios are 25 to be mixed with 35 grams of gama-alumina auxiliary agents, is added 2.7 grams of sesbania powder, It is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is urged Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C1.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.After reaction, In, the selectivity that reaction substrate conversion ratio is 95%, BTX is 87%.
[embodiment 2]
It weighs the ZSM-5 that 35 grams of silica alumina ratios are 50 to be mixed with 35 grams of boehmites, is added 2.7 grams of sesbania powder, mix It closes uniform.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C2.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl propionic acid, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.After reaction, In, the selectivity that reaction substrate conversion ratio is 96%, BTX is 86%.
[embodiment 3]
It weighs the ZSM-5 that 35 grams of silica alumina ratios are 150 to be mixed with 35 grams of boehmites, is added 2.7 grams of sesbania powder, mix It closes uniform.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C3.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl propionic acid, weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 4.0MPa, flow 50ml min-1, 550 DEG C of temperature.After reaction, instead Answering the selectivity that the substrate transformation rate is 99%, BTX is 89%.
[embodiment 4]
It weighs the ZSM-5 that 80 grams of silica alumina ratios are 500 to be mixed with 20 grams of boehmites, is added 3.9 grams of sesbania powder, mix It closes uniform.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is urged Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C4.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl propionic acid, weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 30ml min-1, 380 DEG C of temperature.After reaction, instead Answering the selectivity that the substrate transformation rate is 96%, BTX is 83%.
[embodiment 5]
It weighs the ZSM-38 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of silica solution, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C5.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 0.3 hour-1, Hydrogen Vapor Pressure 3.0MPa, flow 50ml min-1, 450 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 99%, BTX is 94%.
[embodiment 6]
It weighs the ZSM-11 that 80 grams of silica alumina ratios are 150 to be mixed with 20 grams of kaolin, sodium carboxymethylcellulose 3.9 is added Gram, it is uniformly mixed.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later. It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst C6.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 4.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 480 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 96%, BTX is 86%.
[embodiment 7]
It weighs the ZSM-11 that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of kaolin, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of phosphate aqueous solutions that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C6.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl ethyl propionate, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 92%, BTX is 83%.
[embodiment 8]
It weighs the ZSM-23 that 50 grams of silica alumina ratios are 100 to be mixed with 50 grams of aluminium oxide, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C6.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl ethyl propionate, weight space velocity 4.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 450 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 99%, BTX is 81%.
[embodiment 9]
It weighs the ZSM-5 that 35 grams of silica alumina ratios are 100 to be mixed with 35 grams of gama-alumina auxiliary agents, sesbania powder 2.7 is added Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.? It is 8 hours dry at 120 DEG C to catalyst precarsor, it is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst C9.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, reaction substrate acetyl Butyl propionate, weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 350 DEG C of temperature.After reaction, The selectivity that reaction substrate conversion ratio is 89%, BTX is 83%.
[embodiment 10]
It weighs the Y that 35 grams of silica alumina ratios are 6 to be mixed with 35 grams of gama-alumina auxiliary agents, sodium carboxymethylcellulose 2.7 is added Gram, it is uniformly mixed.48 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.? It is 8 hours dry at 120 DEG C to catalyst precarsor, it is roasted 2 hours by 500 DEG C, obtains molecular sieve catalyst C10.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 430 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 81%, BTX is 87%.
[embodiment 11]
It weighs the Y that 60 grams of silica alumina ratios are 8 to be mixed with 40 grams of gama-alumina auxiliary agents, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of phosphate aqueous solutions that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C11.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 2.0MPa, flow 50ml min-1, 450 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 93%, BTX is 78%.
[embodiment 12]
It weighs the Y that 70 grams of silica alumina ratios are 8 to be mixed with 30 grams of boehmites, is added 3.9 grams of sesbania powder, mixing is equal It is even.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.Obtain catalyst Precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C12.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 94%, BTX is 79%.
[embodiment 13]
It weighs the Y that 80 grams of silica alumina ratios are 8 to be mixed with 20 grams of boehmites, is added 3.9 grams of sesbania powder, mixing is equal It is even.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.Obtain catalyst Precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C13.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 470 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 86%, BTX is 87%.
[embodiment 14]
It weighs the beta that 50 grams of silica alumina ratios are 30 to be mixed with 50 grams of boehmites, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C15.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl methyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 430 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 91%, BTX is 82%.
[embodiment 15]
It weighs the beta that 60 grams of silica alumina ratios are 50 to be mixed with 40 grams of boehmites, is added 3.9 grams of sesbania powder, mixing Uniformly.68.6 grams of aqueous solution of nitric acid that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added later.It is catalyzed Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C15.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 88%, BTX is 77%.
[embodiment 16]
It weighs the beta that 70 grams of silica alumina ratios are 100 to be mixed with 30 grams of boehmites, is added 3.9 grams of sesbania powder, mix It closes uniform.68.6 grams of aqueous solution of nitric acid that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added later.It is urged Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C16.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 84%, BTX is 88%.
[embodiment 17]
It weighs the MCM-41 that 50 grams of silica alumina ratios are 20 to be mixed with 50 grams of boehmites, is added 3.9 grams of sesbania powder, mix It closes uniform.68.6 grams of aqueous solution of nitric acid that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added later.It is urged Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C17.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl butyl propionate, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, 400 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 81%, BTX is 82%.
[embodiment 18]
It weighs the MCM-22 that 50 grams of silica alumina ratios are 50 to be mixed with 50 grams of boehmites, is added 3.9 grams of sesbania powder, mix It closes uniform.68.6 grams of aqueous solution of nitric acid that quality of acetic acid percentage composition is 5.5%, kneading and compacting, extrusion are added later.It is urged Agent precursor is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C18.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl butyl propionate, weight space velocity 0.3 hour-1, Hydrogen Vapor Pressure 0.3MPa, flow 50ml min-1, 480 DEG C of temperature.Reaction terminates Afterwards, the selectivity that reaction substrate conversion ratio is 83%, BTX is 89%.
[comparative example 1]
Comparative example 1 is used to illustrate the synthesis of catalyst, the preparation of catalyst and its levulinic of 5A type main active component The performance of sour aromatisation.Specific reactant ratio and experimental method are as follows:
The 5A molecular sieve and 35 grams of gama-alumina auxiliary agent mixing that 35 grams of silica alumina ratios are 2 are weighed, 2.7 grams of sesbania powder is added, mixes It closes uniform.48 grams of aqueous solution of nitric acid that nitric acid mass fraction is 5.5%, kneading and compacting, extrusion are added later.Before obtaining catalyst Body is 8 hours dry at 120 DEG C, roasts 2 hours by 500 DEG C, obtains molecular sieve catalyst C5A.
Catalyst activity evaluation is evaluated on a fixed bed, and reaction condition catalyst quality is 3 grams, and reaction substrate is second Acyl propionic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50mlmin-1, 400 DEG C of temperature.After reaction, it counts It calculates reaction result and shows that the selectivity that reaction substrate conversion ratio is 35%, BTX is 17%.
Table 1

Claims (9)

1. a kind of aromatization method makes raw material contact generation with molecular sieve catalyst containing benzene, toluene and two under aromatization conditions The arene stream of toluene；Wherein, the raw material has structure formula (I):
In formula (I), R1For the C optionally replaced1-8Linear or branched alkyl group, R2For hydrogen, optionally the C replaced1-10Linear chain or branched chain alkane Base, the positive integer that n is 1~6；
The molecular sieve catalyst based on parts by weight, including following component:
A) 20~80 parts of molecular sieve；
B) 20~80 parts of binder；
The molecular sieve is in ZSM-5, ZSM-11, ZSM-23, ZSM-38, Y, beta, MCM-22 or MCM-41 molecular sieve It is at least one；
The silica alumina ratio SiO of ZSM type molecular sieve2/Al2O3=10~500；The silica alumina ratio SiO of Y molecular sieve2/Al2O3=2 ~70；The silica alumina ratio SiO of beta molecular sieve2/Al2O3=10~150；The silica alumina ratio SiO of MCM type molecular sieve2/ Al2O3=20~250.
2. aromatization method according to claim 1, it is characterised in that in formula (I), R1For the C optionally replaced1-4Straight chain or branch Alkyl group.
3. aromatization method according to claim 1, it is characterised in that in formula (I), R2For hydrogen, optionally the C replaced1-5Straight chain or Branched alkyl.
4. aromatization method according to claim 1, it is characterised in that in formula (I), n be 1~4 positive integer.
5. aromatization method according to claim 1, it is characterised in that the molecular sieve is selected from ZSM-5, Y, beta or MCM- At least one of 41；
The silica alumina ratio SiO of ZSM type molecular sieve2/Al2O3=15~100；The silica alumina ratio SiO of Y molecular sieve2/Al2O3=3 ~50；The silica alumina ratio SiO of beta molecular sieve2/Al2O3=15~65；The silica alumina ratio SiO of MCM type molecular sieve2/Al2O3 =40~150.
6. aromatization method according to claim 1, it is characterised in that the aromatization conditions are as follows: reaction temperature 300~800 DEG C, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, raw material weight air speed 0.3~10 hour-1。
7. aromatization method according to claim 1, it is characterised in that the raw material comes from biological material.
8. aromatization method according to claim 1, it is characterised in that the raw material comes from xylitol, glucose, fiber two At least one of sugar, hemicellulose or lignin.
9. aromatization method according to claim 1, it is characterised in that the raw material comes from bagasse, glucose, timber, jade Rice at least one of straw or straw straw.
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