CN106316735B - The method for producing aromatic hydrocarbons - Google Patents
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Abstract
The present invention relates to a kind of methods for producing aromatic hydrocarbons, under aromatization conditions, contact raw material with strong solid acid catalyst and generate the arene stream containing benzene, toluene and dimethylbenzene；Wherein, the raw material has structure formula (I):In formula (I), R1For hydrogen, optionally the C replaced1‑20Linear or branched alkyl group, the C optionally replaced2‑20Linear chain or branched chain alkenyl, the C optionally replaced2‑20Linear chain or branched chain alkynyl, the C optionally replaced3‑20Naphthenic base or the C optionally replaced6‑20Aryl；R2For the C optionally replaced1‑20Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furyl；Wherein, the hydroxyl alkyl furyl has structural formula (II):In formula (II), R3For the C optionally replaced1‑20Linear or branched alkyl group, the C optionally replaced2‑20Linear chain or branched chain alkenyl, the C optionally replaced2‑20Linear chain or branched chain alkynyl.This method can be used for non-fossil sources aromatic hydrocarbons field.
Description
Technical field
The present invention relates to a kind of methods for producing aromatic hydrocarbons, prepare benzene, toluene and dimethylbenzene lightweight virtue more particularly to a kind of
The method of hydrocarbon.
Background technique
Benzene, toluene and dimethylbenzene are the important basic organic chemical industry raw materials of social development, its own or pass through reproduction
Multiple product chain can be derived, product is widely used in the numerous areas such as polyester, chemical fibre, rubber, medicine and fine chemistry industry, state
Interior consumption figure reaches up to ten million tons, has great influence to the national economic development.Benzene is a kind of basic petrochemical material of multipurpose, can
To produce numerous products, including ethyl benzene/styrene, cumene/phenol etc. derived from it.Paraxylene is mainly for the manufacture of right
Phthalic acid gathers cruel fiber such as producing by terephthalic acid (TPA) (PTA) or diethyl terephthalate (DMT) intermediate
Polyethylene terephthalate (PET), resin and film.These three types of aromatic hydrocarbons are typical light aromatics, are abbreviated as BTX.Mesh
The production of preceding domestic and international BTX depends on non-renewable fossil resource, such as can be by a catalyst by petroleum by adding
The technical process such as hydrogen, reformation, aromatic hydrocarbons conversion and separation obtain.But fossil resource reserves are limited and non-renewable, so that with
Petroleum is that the cost that main refining raw material produces aromatic hydrocarbons is more shown in surging.In addition, continually developing for fossil resource is a large amount of using generating
Greenhouse gas emission, caused a series of environmental problems are on the rise, therefore develop from renewable resource route and produce aromatic hydrocarbons
Significant and application value.
The plant that nature is widely present is a kind of typical renewable resource, belongs to one kind of biomass.Global biology
The annual yield of matter is about 200,000,000,000 tons, and rich reserves are from a wealth of sources, cheap and easy to get.From reproducible biomass resource
It is prepared with the extensive concern that widely applied aromatic hydrocarbon product causes scientific circles and industry.
In recent years, biological legal system aromatic hydrocarbons is studied by global more research institutions, makes some progress.It removes
Outside fermentative routes, the route with certain development prospect has 4: biomass is through synthesis gas aromatisation again；Fast pyrogenation aromatic hydrocarbons；
Biomass sugar platform is through catalytic cracking aromatic hydrocarbons；Biomass-based isobutanol aromatisation etc..Below to certain economy
Technology is analyzed.
Anellotech company develops the Biomassto Aromatic of the catalytic pyrolysis aromatic hydrocarbons of lignocellulosicTMWork
Skill [Katherine Bourzac.From biomass to chemicals in one step.MIT Technology
Review, 2010-03-29.], and be dedicated to pushing it against industrialized production.The technique is with non-grain biomass such as plant straw
Stalk, culled wood etc. are raw material, by catalysis fast pyrolysis technology aromatic hydrocarbons, have built up demonstration experimental provision in 2011.CFP skill
Art will be ground to powder after biomass material drying at 600 DEG C, mixes with powdery ZSM-5 catalyst and is sent into high temperature circulation fluidisation
In bed reactor, it is sufficiently mixed and is heated in the form of air whirl, raw material powder is partially converted into aromatic hydrocarbons through catalytic pyrolysis, together
When catalyst coking and deactivation, light aromatics (US20090227823) can be obtained in separating catalyst and purified product later.
Virent company develops BioFormingTMTechnology, based on sugared platform, using the technology of aqueous-phase reforming to life
Materials compounds deoxidation is reformate, and further aromatization turns to aromatic hydrocarbons on ZSM-5 catalyst.Its raw material includes corn, sugarcane
With the biomass such as lignocellulosic.Main process is using aqueous-phase reforming (APR) technology, by carbohydrate admixture through pallium-on-carbon-rhenium
Catalyst deoxidation is converted into alcohol, aldehyde list oxygen compound, and product carbochain after condensation hydrogenation is increased, further aromatisation system
Standby oil product and aromatic hydrocarbons (US20110257416A1).The process can theoretically reduce even from hydrogen producing without using external hydrogen source.
Above-mentioned technology path respectively has feature, emphasizes particularly on different fields, there is also there is different degrees of problem, such as the utilization of raw material
The problems such as rate, the price of raw material, the stability of aromatisation system.
Summary of the invention
The present invention is intended to provide a kind of method for producing aromatic hydrocarbons.
For achieving the above object, the technical solution adopted by the present invention is as follows: a method of aromatic hydrocarbons is produced, in aromatization
Under the conditions of change, contacts raw material with strong solid acid catalyst and generate the arene stream containing benzene, toluene and dimethylbenzene；Wherein, described
Raw material has structure formula (I):
In formula (I), R1For hydrogen, optionally the C replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Linear chain or branched chain alkene
Base, the C optionally replaced2-20Linear chain or branched chain alkynyl, the C optionally replaced3-20Naphthenic base or the C optionally replaced6-20Aryl；R2
For the C optionally replaced1-20Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furyl；Wherein, the hydroxyl alkyl furyl
With structure formula (II):
In formula (II), R3For the C optionally replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Linear chain or branched chain alkene
Base, the C optionally replaced2-20Linear chain or branched chain alkynyl.
In above-mentioned technical proposal, it is preferable that in formula (I), R1For the C optionally replaced2-10Linear or branched alkyl group optionally takes
The C in generation2-10Linear chain or branched chain alkenyl.
In above-mentioned technical proposal, it is preferable that in formula (I), R2For the C optionally replaced2-10Linear chain or branched chain carboxyl.
In above-mentioned technical proposal, it is preferable that in formula (II), R3For the C optionally replaced2-10Linear or branched alkyl group optionally takes
The C in generation2-10Linear chain or branched chain alkenyl.
In above-mentioned technical proposal, it is preferable that the strong solid acid catalyst is selected from SO4 2-/ZrO2、S2O8 2-/ZrO2、
SO4 2-/TiO2、SO4 2-/ZrO2-Fe3O4、Pt/SO4 2-/TiO2、SO4 2-/TiO2-ZrO2、SO4 2-/TiO2-Al2O3、SO4 2-/
ZrO2-Fe2O3-Cr2O3、SbF5/SiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2-/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/
Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-
B2O3、NbF3/Al2O3-B2O3、AlCl3-CuCl2Or SO4 2-/ZrO2-Fe2O3-MnO2At least one of.
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.It is highly preferred that the aromatization conditions are as follows: reaction temperature
300~650 DEG C, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 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.
As an embodiment of the invention, raw material of the present invention is biomass-based carbonyl complex, such as
Furfural, 5 hydroxymethyl furfural, levulic acid.Such carbonyl complex can be former by biomass from a wealth of sources, rich reserves
Material obtains, can be with large scale preparation.For example, levulic acid can be in Zirconium oxide, metal chloride, organic acid or inorganic acid
In the presence of, it is 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).And 5 hydroxymethyl furfural can be urged in acid
In the presence of agent, (Catalytic conversion of is prepared by biomass such as glucose, celluloses
carbohydrates into 5-hydroxymethylfurfural over cellulose-derived
Carbonaceous catalyst in ionic liquid, Bioresour Technol.2013Nov；148:501-507.；
Production of 5-Hydroxymethylfurfural from Glucose Using a Combination of
Lewis andAcid Catalysts in Water in a Biphasic Reactor with an
Alkylphenol Solvent, ACS Catal., 2012,2 (6), pp 930-934).Equally, furfural can also with corn stalk or
Corncob is raw material, produces to obtain by acid catalysis.
In the present invention, the preparation method of strong solid acid catalyst is can to use precipitation-impregnation to be known in the art
Method.For details, reference can be made to document " solid acid and fine chemistry industry " and " SO4 2-/MxOyThe progress of type solid super acid catalyst, is answered
With chemical industry, 2014, vol43,1879-1883 ".
The method of the present invention has preferable conversion ratio to carbonyl complex, has preferable choosing to benzene,toluene,xylene product
Selecting property, aromatics yield is low long with reaction step during solving the problems, such as previous biomass aromatic hydrocarbons.Using the method for the present invention,
Feed stock conversion can reach 98%；The selectivity of benzene,toluene,xylene target product can reach 93%, achieve
Preferable technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
60 grams of straw straw 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 210 DEG C and reacts 30 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 22.8 grams.
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2Catalyst is packed into fixed bed reactors.Reaction
Substrate is levulic acidWeight space velocity 0.3 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml
min-1, 400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography determines reaction result
Amount analysis.The selectivity that reaction substrate conversion ratio is 83%, BTX is 87%.
[embodiment 2]
5 grams are weighed through the S for removing water 12 hours dry at 120 DEG C2O8 2-/ZrO2Catalyst is packed into fixed bed reactors.Instead
Answer substrate for levulic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 450 DEG C of temperature.Instead
After answering, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate turns
The selectivity that rate is 98%, BTX is 93%.
[embodiment 3]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2Catalyst is packed into fixed bed reactors.Reaction
Substrate is levulic acid, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.Reaction
After, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate conversion
The selectivity that rate is 88%, BTX is 81%.
[embodiment 4]
30 grams of timber are weighed, is placed in autoclave pressure and is added 400 grams of water, add the sulfuric acid of the 5mol/L of water quality 7%
Solution is warming up at 200 DEG C and reacts 30 minutes, cools down later, reaction solution after cooling is filtered, filter cake and filtered fluid are obtained,
Filtered fluid is that the hydrolyzate of cellulose uses mass spectrum to carry out identifying primary product for levulinic to reaction result after reaction
Acid, yield are 10.5 grams.
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe3O4Catalyst is packed into fixed bed reaction
Device.Reaction substrate is levulic acid, weight space velocity 5.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature 500
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 82%, BTX is 78%.
[embodiment 5]
5 grams are weighed through the Pt/SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2Catalyst is packed into fixed bed reactors.
Reaction substrate is levulic acid, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 3.0MPa, flow 20ml min-1, 450 DEG C of temperature.
After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate
The selectivity that conversion ratio is 89%, BTX is 81%.
[embodiment 6]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-ZrO2Catalyst is packed into fixed bed reaction
Device.Reaction substrate is levulic acid, weight space velocity 0.8 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 40ml min-1, temperature 400
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 87%, BTX is 81%.
[embodiment 7]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-Al2O3Catalyst is packed into fixed bed reaction
Device.Reaction substrate is furfuralWeight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1,
400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantitatively divides reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 79%, BTX is 85%.
[embodiment 8]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalyst is packed into fixed bed
Reactor.Reaction substrate is furfural, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 450
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 91%, BTX is 87%.
[embodiment 9]
5 grams are weighed through the SbF for removing water 12 hours dry at 120 DEG C5/SiO2-Al2O3Catalyst is packed into fixed bed reaction
Device.Reaction substrate is furfural, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.Instead
After answering, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate turns
The selectivity that rate is 78%, BTX is 89%.
[embodiment 10]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-WO3Catalyst is packed into fixed bed reactors.
Reaction substrate is furfural, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 500 DEG C of temperature.Reaction
After, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate conversion
The selectivity that rate is 86%, BTX is 82%.
[embodiment 11]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-WO3Catalyst is packed into fixed bed reactors.
Reaction substrate is levulic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 380 DEG C of temperature.
After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate
The selectivity that conversion ratio is 92%, BTX is 90%.
[embodiment 12]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-MoO3Catalyst is packed into fixed bed reactors.
Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature 380
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 79%, BTX is 83%.
[embodiment 13]
5 grams are weighed through the BiF for removing water 12 hours dry at 120 DEG C3/Al2O3-B2O3Catalyst is packed into fixed bed reactors.
Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature 420
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 86%, BTX is 82%.
[embodiment 14]
5 grams are weighed through the NbF for removing water 12 hours dry at 120 DEG C3/Al2O3-B2O3Catalyst is packed into fixed bed reactors.
Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature 360
℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction
The selectivity that the substrate transformation rate is 87%, BTX is 91%.
[embodiment 15]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-MnO2Catalyst is packed into fixed bed
Reactor.Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1,
400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantitatively divides reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 88%, BTX is 85%.
[embodiment 16]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalyst is packed into fixed bed
Reactor.Reaction substrate is levulic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature
380℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Instead
Answering the selectivity that the substrate transformation rate is 94%, BTX is 87%.
[embodiment 17]
5 grams are weighed through the AlCl for removing water 12 hours dry at 120 DEG C3-CuCl2Catalyst is packed into fixed bed reactors.Instead
Answer substrate for furfural, weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.Reaction knot
Shu Hou carries out qualitative analysis to reaction result using mass spectrum, and chromatography carries out quantitative analysis to reaction result.Reaction substrate conversion ratio
Selectivity for 81%, BTX is 79%.
Table 1
| Embodiment | Substrate | Catalyst | Conversion ratio/% | BTX selectivity/% |
| 1 | Levulic acid | SO4 2-/ZrO2 | 83 | 87 |
| 2 | Levulic acid | S2O8 2-/ZrO2 | 98 | 93 |
| 3 | Levulic acid | SO4 2-/TiO2 | 88 | 81 |
| 4 | Levulic acid | SO4 2-/ZrO2-Fe3O4 | 82 | 78 |
| 5 | Levulic acid | Pt/SO4 2-/TiO2 | 89 | 81 |
| 6 | Levulic acid | SO4 2-/TiO2-ZrO2 | 87 | 81 |
| 7 | Furfural | SO4 2-/TiO2-Al2O3 | 79 | 85 |
| 8 | Furfural | SO4 2-/ZrO2-Fe2O3-Cr2O3 | 91 | 87 |
| 9 | Furfural | SbF5/SiO2-Al2O3 | 78 | 89 |
| 10 | Furfural | SO4 2-/TiO2-WO3 | 86 | 82 |
| 11 | Levulic acid | SO4 2-/ZrO2-WO3 | 92 | 90 |
| 12 | 5 hydroxymethyl furfural | SO4 2-/TiO2-MoO3 | 79 | 83 |
| 13 | 5 hydroxymethyl furfural | BiF3/Al2O3-B2O3 | 86 | 82 |
| 14 | 5 hydroxymethyl furfural | NbF3/Al2O3-B2O3 | 87 | 91 |
| 15 | 5 hydroxymethyl furfural | SO4 2-/ZrO2-Fe2O3-MnO2 | 88 | 85 |
| 16 | Levulic acid | SO4 2-/ZrO2-Fe2O3-Cr2O3 | 94 | 87 |
| 17 | Furfural | AlCl3-CuCl2 | 81 | 79 |
Claims (5)
1. a kind of method for producing aromatic hydrocarbons makes raw material contact generation with strong solid acid catalyst containing benzene, first under aromatization conditions
The arene stream of benzene and dimethylbenzene；Wherein, the raw material has structure formula (I):
In formula (I), R1For hydrogen or methyl；R2For the C optionally replaced2-10Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furan
It mutters base；Wherein, the hydroxyl alkyl furyl has structural formula (II):
In formula (II), R3For methyl；
The strong solid acid catalyst is selected from SO4 2-/ZrO2、S2O8 2-/ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2-Fe3O4、Pt/
SO4 2-/TiO2、SO4 2-/TiO2-ZrO2、SO4 2-/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2-/ZrO2-Fe2O3-Cr2O3、
SbF5/SiO2-Al2O3、SO4 2-/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/
Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3、NbF3/Al2O3-B2O3、SO4 2-/ZrO2-
Fe2O3-MnO2Or AlCl3-CuCl2At least one of；
The aromatization conditions are as follows: 300~800 DEG C of reaction temperature, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, raw material weight is empty
Speed 0.3~10 hour-1。
2. producing the method for aromatic hydrocarbons according to claim 1, it is characterised in that the aromatization conditions are as follows: reaction temperature 300
~650 DEG C, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 hour-1。
3. producing the method for aromatic hydrocarbons according to claim 1, it is characterised in that the raw material comes from biological material.
4. producing the method for aromatic hydrocarbons according to claim 1, it is characterised in that the raw material comes from xylitol, glucose, fibre
Tie up at least one of disaccharides, hemicellulose or lignin.
5. producing the method for aromatic hydrocarbons according to claim 1, it is characterised in that the raw material comes from bagasse, glucose, wood
At least one of material, corn stalk or straw straw.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
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| CN201510345812.4A CN106316735B (en) | 2015-06-19 | 2015-06-19 | The method for producing aromatic hydrocarbons |
| US15/738,063 US10358606B2 (en) | 2015-06-19 | 2016-06-17 | Process for producing aromatics, p-xylene and terephthalic acid |
| JP2017565948A JP6877367B2 (en) | 2015-06-19 | 2016-06-17 | Method for producing aromatic hydrocarbons, p-xylene and terephthalic acid |
| BR112017027347-0A BR112017027347B1 (en) | 2015-06-19 | 2016-06-17 | Processes for the production of aromatic hydrocarbon, paraxylene and terephthalic acid |
| EP16810696.1A EP3312153B1 (en) | 2015-06-19 | 2016-06-17 | Methods for manufacturing aromatic hydrocarbon, paraxylene and terephthalic acid |
| KR1020187001728A KR102454225B1 (en) | 2015-06-19 | 2016-06-17 | Process for the preparation of aromatic hydrocarbons, paraxylene and terephthalic acid |
| DK16810696.1T DK3312153T3 (en) | 2015-06-19 | 2016-06-17 | PROCEDURES FOR THE PRODUCTION OF AROMATIC CARBOHYDRATE, PARAXYLENE AND TEREPHTHALIC ACID |
| ES16810696T ES2880326T3 (en) | 2015-06-19 | 2016-06-17 | Methods for making aromatic hydrocarbon, paraxylene, and terephthalic acid |
| PCT/CN2016/000315 WO2016201955A1 (en) | 2015-06-19 | 2016-06-17 | Methods for manufacturing aromatic hydrocarbon, paraxylene and terephthalic acid |
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