CN106256811B - The composition that the method and this method for synthesizing aromatic hydrocarbons obtain - Google Patents
The composition that the method and this method for synthesizing aromatic hydrocarbons obtain Download PDFInfo
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Abstract
The present invention relates to the compositions that a kind of method for synthesizing aromatic hydrocarbons and this method obtain.Method includes the following steps: a) levulic acid contacts logistics of the generation containing gamma-valerolactone under hydroconversion condition with hydrogenation catalyst；B) logistics containing gamma-valerolactone, which contacts under aromatization conditions with aromatized catalyst, generates the arene stream containing benzene, toluene and dimethylbenzene.This method can be used for from the industrial production that cellulose-containing biomass material produces the aromatic hydrocarbons such as benzene, toluene and dimethylbenzene.
Description
Technical field
The present invention relates to the compositions that a kind of method for synthesizing aromatic hydrocarbons and this method obtain.
Background technique
The aromatic hydrocarbons such as benzene, toluene and dimethylbenzene (BTX) are important basic organic chemical industry raw material, are promoting national economy and society
The numerous areas that can develop has a wide range of applications.Currently, BTX production is using fossil resources as raw material, and main pass through is catalyzed weight
Whole and cracking of ethylene by-product is realized, is realized on a small quantity by coal chemical industry process.In the long term, traditional petrochemical material has non-renewable
Property, the utilization of fossil resources also exacerbates the discharge of greenhouse gases simultaneously, does not meet the development strategy of green low-carbon.
Biomass is mainly made of cellulose, hemicellulose and lignin etc., is that nature is obtained by photosynthesis
Renewable resource, from a wealth of sources, reserves are huge.There is the aromatic hydrocarbon product of significant application value by the production of reproducible biomass,
Can alleviate dependence of the existing route to fossil resources to a certain extent, at the same can rich high in aromatics production method, be reliable and stable
Ground supplies reproducible aromatic hydrocarbon product and provides new approaches, has important Development volue and prospect.China's biomass resource scale of construction
Huge, in liberal supply, as strategic new technology, the exploitation of biomass aromatic hydrocarbons technology is of great significance.
Studied currently, preparing aromatic hydrocarbons to biomass in the world, with Anellotech, Virent, Gevo and
Micromidas is that the company of representative has carried out in-depth study work, and is attempting to be commercialized.It is summed up, biomass
Aromatic hydrocarbons processed mainly has four routes, comprising: (1) biomass fast pyrogenation and biology pyrolysis oil refinement；(2) biomass polysaccharides liquid phase
It reforms and reforms oil refinement and produce aromatic hydrocarbons mixture；(3) biomass ferment isobutanol and isobutanol catalyzed conversion are directly made pair
Dimethylbenzene；(4) dimethyl furan and ethylene Diels-Alder addition produce paraxylene.
Anellotech company of the U.S. develops catalysis fast pyrolysis and prepares the technology of aromatic hydrocarbons, cellulose series biomass according to
Secondary thermal decomposition is oligosaccharide or even furan compound, and the hydrocarbon compounds such as aromatic hydrocarbons are then converted on ZSM-5 zeolite
(US2009001382,CN200980116001).Fast pyrolysis process can handle rich cellulose-containing timber, agricultural waste material
Equal raw materials, raw material have cost advantage.Wang Chang etc. has carried out pyrolysis in fact to timber biological matter using double grain fluidized bed reactors
It tests, works as CoMo-S/Al2O3When catalyst carries out hydropyrolysis as fluidizing agent, [biomass is urged up to 6.3% for the yield of BTXN
Change pyrolysis and produce light aromatics, be catalyzed journal, 2008,29,907-912].Patent CN201410183533 is proposed with biomass
It is total to the composite catalyst and preparation method thereof that catalytic pyrolysis prepares aromatic hydrocarbons with plastics, biomass is total to catalytic pyrolysis with plastics and can improve
Total liquid aromatic hydrocarbon (such as benzene,toluene,xylene, naphthalene etc.) carbon yield and mononuclear aromatics selectivity.But due to biomass material
Effective hydrogen-carbon ratio is very low, and a large amount of carbon species are discharged in the form of carbon dioxide in the conversion process, and overall carbon utilization efficiency is not
It is high.And since the ingredient of original biomass raw material is more complex, the zeolite molecular sieve as catalyst is difficult to realize reuse.
Virent company of the U.S. is based on " aqueous-phase reforming technology " [Renewable alkanes by aqueous-phase
Reforming of biomass-derived oxygenates, Angew.Chem.Int.Ed.2004,43,1549-1551],
Having studied biological polyoses class is the technology path (US8053615) that raw material produces dimethylbenzene, and biological polyoses lead to again through aqueous-phase reforming
It crosses catalyzed conversion and generates the hydrocarbon mixture for being rich in aromatic hydrocarbons.Due to the limitation of aqueous-phase reforming process, biomass material can only be selected
With edible sucrose, fructose etc., cost of material is higher.GEVO company of the U.S. passes through biomass carbohydrate even micro- life of cellulose
Object fermentation technique produces large basic chemical industry raw material isobutanol, and isobutyl dehydration of alcohols obtains isobutene, then passes through two, three intermediaries
Oligomeric/oligomerization, dehydrocyclization i.e. obtain paraxylene (US2011/0087000).Compared with chemical conversion process, biomass
Fermentation process efficiency it is obviously relatively low, the yield of isobutanol product is very low, cause this technology path produce dimethylbenzene
The cost of product is apparently higher than other routes.Micromidas company of the U.S., which proposes, utilizes the new of biomass production paraxylene
Route (WO2013/040514) produces dimethyl furan, dimethyl furan using biomass such as rice chaff, branch, sawdust and waste paperboards
It mutters and is dehydrated paraxylene can be obtained again after Diels-Alder addition reaction occurs with ethylene.The Atom economy of the route compared with
It is good, but need to consume a large amount of ethylene and hydrogen.
Summary of the invention
The first technical problem to be solved by the present invention be the prior art that there are carbon utilisation rates is lower, hydrogen consumption is higher,
The high problem of cost of material provides a kind of method of new synthesis aromatic hydrocarbons.This method is used to contain from cellulose series biomass production
The aromatic hydrocarbons mixture of benzene, toluene and dimethylbenzene, while hydrogen can be generated, with carbon utilisation rate is higher, hydrogen consumption is lower, raw material
The characteristics of cost is relatively low.The second technical problem to be solved by the present invention is to provide a kind of one of solution technical problem method therefor
Obtained composition.
One of to solve above-mentioned technical problem, the technical solution adopted by the present invention is as follows: a method of synthesis aromatic hydrocarbons, packet
Include following steps:
A) levulic acid, which contacts under hydroconversion condition with hydrogenation catalyst, generates the logistics containing gamma-valerolactone；
B) logistics containing gamma-valerolactone contacts generation containing benzene, toluene under aromatization conditions with aromatized catalyst
With the arene stream of dimethylbenzene.
In above-mentioned technical proposal, it is preferable that levulic acid comes from cellulose.
In above-mentioned technical proposal, it is preferable that levulic acid is by cellulose-containing biomass material through acidolysis, supercritical water
Solution, catalyzing part oxidation or metal chloride catalyzed conversion and obtain.
In above-mentioned technical proposal, it is preferable that by weight percentage, in the biological material content of cellulose be 30~
99%, hemicellulose level is 0~50%, and content of lignin is 1~40%.
In above-mentioned technical proposal, it is preferable that the hydroconversion condition are as follows: 50~500 DEG C of reaction temperature, reaction pressure 0.1~
10.0MPa, air speed 0.1~10.0 hour-1；It is highly preferred that 100~300 DEG C of reaction temperature, 0.5~3.0MPa of reaction pressure, it is empty
Speed 0.5~3.0 hour-1。
In above-mentioned technical proposal, it is preferable that the hydrogenation catalyst includes following components by weight percentage: 0.1~
80% selected from least one of Ni, Ru, Zn, Cu or Pd metal；20~99.9% be selected from Al2O3、SiO2、ZrO2Or it is living
At least one of property charcoal.
In above-mentioned technical proposal, it is preferable that the aromatization conditions are as follows: 100~800 DEG C of reaction temperature, reaction pressure 0.1
~10.0MPa, air speed 0.1~10.0 hour-1；It is highly preferred that 300~600 DEG C of reaction temperature, 0.5~6.0MPa of reaction pressure,
Air speed 0.5~5.0 hour-1。
In above-mentioned technical proposal, it is preferable that the aromatized catalyst, based on parts by weight, including following component: a) 20
~80 parts be selected from least one of ZSM-5, ZSM-11, MCM-22, ZSM-23 or zeolite L molecular sieve；B) 20~80 parts
Binder.
In above-mentioned technical proposal, it is preferable that the silica alumina ratio of ZSM Series Molecules sieve is 10~150, MCM-22 type molecular sieve
Silica alumina ratio is 20~250, and L-type molecular sieve silica alumina ratio is 10~80.
In above-mentioned technical proposal, it is preferable that the cellulosic acid solution preocess also generates formic acid, the hydrogen that formic acid decomposes
Hydrogenation process for levulic acid.
To solve above-mentioned technical problem two, the technical solution adopted by the present invention is as follows: pass through the side of the synthesis aromatic hydrocarbons
Composition made from method.
In above-mentioned technical proposal, it is preferable that by weight percentage, the content 2.0~10.0% of benzene in the composition,
The content of toluene is 25.0~40.0%, and the content of dimethylbenzene is 25.0~50.0%, remaining is non-aromatics and heavy aromatics.It is described
Heavy aromatics refers to carbon nine and its above aromatic hydrocarbons.
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 pass through
Acidolysis, supercritical hydrolysis, catalyzing part oxidation or metal chloride are obtained by the biomass substrate such as cellulose, stalk through catalyzed conversion
Obtain (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；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), pp18796-18805；Conversion of
cellulose to glucose and levulinic acid via solid-supported acid catalysis
Tetrahedron Lett.2010,51(17)2356–2358；High yield production of levulinic acid
By catalytic partial oxidation of cellulose in aqueous media, Energy
Environ.Sci.,2012,5,9773-9777；Catalytic Conversion of Cellulose to Levulinic
Acid by Metal Chlorides；Molecules 2010,15(8),5258-5272).
In the present invention, formic acid be decomposed into hydrogen process be known in the art.Generally with activated carbon supported palladium
For catalyst, reaction condition is that normal pressure, 80 DEG C of reactions are (activated carbon modified to the Pd/ activated-carbon catalyst decomposed for formic acid
It influences, chemical industry progress, 2010 (1), 76-79).
The present invention provides a kind of new ways from lower-cost biomass material production aromatic hydrocarbons, can produce and stone brain
The oily comparable aromatic hydrocarbon product of raw material route cost.Different from the thermochemical process such as bioenzymatic conversion process and fast pyrogenation, this hair
The bright decomposition realized by liquid-phase chemistry to cellulose macromolecule, it is higher to the carbon utilisation rate of biomass material.Levulinic
Product of the acid as cellulose conversion can generate gamma-valerolactone by further hydrogenation process.Under the effect of the catalyst,
Aromatization process can occur for second gamma-valerolactone, and then realizes and turn from oxygenatedchemicals to aromatic hydrocarbons such as benzene, toluene and dimethylbenzene
Change.Levulic acid add hydrogen depth and aromatization process carbon utilisation rate it is closely related, the method can be by more carbon hydrogen elements
It is transformed into aromatic product.Moreover, the formic acid of cellulose decomposition process by-product is decomposable to generate hydrogen, generated with aromatization process
Hydrogen together as hydrogenation reaction hydrogen source, to realize lower hydrogen wastage in bulk or weight.
As can be seen that such technology path, can convert containing cellulose biolobic material to aromatic hydrocarbons mixture, and then realize
Benzene, toluene and the xylene production of renewable resource route, carbon utilisation rate is higher, and benzene, toluene and dimethylbenzene account for products weight can
Up to 85.6%, hydrogen consumption is lower, and cost of material is low, achieves preferable technical effect.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
Hydrogenation catalyst preparation: the aqueous solution of ethyl orthosilicate, ethyl alcohol and copper nitrate is mixed with the mass ratio of 1:3.5:10
Merging is stirred, and wherein the molar ratio of ethyl orthosilicate and copper nitrate is 1:1.37, and the solution is transferred into tetrafluoro later
Reactor plastic.Resulting mixture is slowly warming up to 100 DEG C in an oven and is kept for 48 hours, crushes and turns after obtaining dry glue
Muffle furnace is moved up into roast 2 hours at 500 DEG C.After mixture molding, then by incipient impregnation method, with palladium chloride solution
Dipping, makes Pd account for the amount 0.5% of catalyst to get Cu-Pd/SiO2Catalyst.
Aromatized catalyst preparation: it weighs the ZSM-5 that 80 grams of silica alumina ratios are 50 and is mixed with 20 grams of boehmites, added
Enter 3.9 grams of sesbania powder, is uniformly mixed.50 grams of aqueous solution of nitric acid that addition mass percentage is 5.5% later, kneading and compacting,
Extrusion.It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 550 DEG C, obtains catalyst.
Raw material is 1 ton of straw straw, and dry fabric cellulose content is 42.5%.After these straw straw are sufficiently crushed, with 3.5 tons
2.5% aqueous sulfuric acid is thoroughly mixed, and is stirred to react 30 minutes under the conditions of 3.0MPa, 210 DEG C and is completed acidolysis
196.8 kilograms of levulic acids and 83.3 kilograms of formic acid can be obtained in journey after separation.83.3 kilograms of formic acid decompose available 3.6
Kilogram hydrogen.
In Cu-Pd/SiO2On catalyst, obtain 196.8 kilograms of levulic acids are carried out to add hydrogen, reaction pressure
3.0MPa, 190 DEG C of reaction temperature, hydrogen/levulic acid molar ratio is 30, levulic acid air speed 0.5h-1, levulic acid conversion ratio
100%, the molar selectivity of gamma-valerolactone is 95.2%, obtains 156.1 kilograms of gamma-valerolactone.
Logistics containing gamma-valerolactone is further converted on aromatized catalyst.420 DEG C of reaction temperature, reaction pressure
Power 1.5MPa, air speed 1.0h-1, the conversion ratio of gamma-valerolactone is 100%, and the quality for obtaining hydro carbons is 81.2kg, composition such as table 1
Shown, the quality of aromatic hydrocarbons is 74.7kg, and benzene, toluene and dimethylbenzene account for the 84.1% of products weight.
1 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 8.0 | 5.2 | 36.7 | 3.5 | 8.1 | 15.9 | 8.0 | 11.6 | 3.0 |
| Yield/KG | 6.5 | 4.2 | 29.8 | 2.8 | 6.6 | 12.9 | 6.5 | 9.4 | 2.4 |
[embodiment 2]
Hydrogenation catalyst preparation: copper nitrate and zinc nitrate aqueous solution are immersed on alumina-silica carriers, used
The quality of metallic copper and zinc accounts for the 10% and 2% of carrier quality respectively, which is impregnated 24 hours at room temperature, and is put into
Oven drying 24 hours.Obtained dried catalyst precursor is put into tube furnace the reductase 12 hour at 400 DEG C later.
Aromatized catalyst preparation: it weighs the ZSM-11 that 60 grams of silica alumina ratios are 150 and is mixed with 140 grams of kaolin, added
Enter 7.5 grams of sesbania powder, is uniformly mixed.5.5% 90 grams of aqueous solution of nitric acid, 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 catalyst.
Raw material is 1 ton of corn stalk, and dry fabric cellulose content is 36%.After these corn stalks are sufficiently crushed, with 3.5 tons
2.5% aqueous sulfuric acid is thoroughly mixed, and is stirred to react 25 minutes under the conditions of 0.5MPa, 230 DEG C and is completed acidolysis
187.2 kilograms of levulic acids and 76.5 kilograms of formic acid can be obtained in journey, liquid product after separation.76.5 kilograms of formic acid decomposition can
Obtain 3.1 kilograms of hydrogen.
In Cu-Zn/Al2O3-SiO2On catalyst, reaction pressure 3.0MPa, by acetyl under conditions of 180 DEG C of reaction temperature
Propionic acid carries out plus hydrogen, and hydrogen/levulic acid molar ratio is 10, levulic acid air speed 3h-1, levulic acid conversion ratio 100%, γ-
The molar selectivity of valerolactone is 97.8%, obtains 155.9 kilograms of gamma-valerolactones.
Logistics containing gamma-valerolactone is further converted on aromatized catalyst.450 DEG C of reaction temperature, reaction pressure
Power 1.5MPa, air speed 1.0h-1, the conversion ratio of gamma-valerolactone is 100%, and the quality for obtaining hydro carbons is 85.7kg, composition such as table 2
Shown, the quality of aromatic hydrocarbons is 74.7kg, and benzene, toluene and dimethylbenzene account for the 83.9% of products weight.
2 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 12.9 | 4.7 | 34.8 | 3.9 | 7.7 | 15.0 | 7.0 | 8.2 | 5.8 |
| Yield/KG | 11.1 | 4.0 | 29.8 | 3.3 | 6.6 | 12.9 | 6.0 | 7.0 | 5.0 |
[embodiment 3]
Hydrogenation catalyst preparation: ruthenium trichloride aqueous solution is immersed on 150 grams of active carbons, the quality of metal Ru used
The 0.5% of quality of activated carbon is accounted for, which is impregnated 48 hours at room temperature, and be put into oven drying 24 hours.Later will
Obtained dried catalyst precursor is put into tube furnace the reductase 12 hour at 400 DEG C.
Aromatized catalyst preparation: it weighs the zeolite L that 300 grams of silica alumina ratios are 50 and is mixed with 300 grams of boehmites
It closes, is added 23 grams of sesbania powder, be uniformly mixed.270 grams of aqueous solution of nitric acid that nitric acid mass percentage is 5.5% are added later,
Kneading and compacting, extrusion.It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 550 DEG C, obtains catalyst.
Raw material is 1 ton of corrugated paper, and dry fabric cellulose content is 79%.These corrugated papers and 5.5 ton 3% of hydrochloric acid are water-soluble
Liquid is thoroughly mixed, and is stirred to react under the conditions of 0.5MPa, 210 DEG C and is completed within 25 minutes acid hemolysis process, and liquid product passes through
395.0 kilograms of levulic acids and 161.4 kilograms of formic acid can be obtained after separation.161.4 kilograms of formic acid, which decompose, can be obtained 6.5 kilograms of hydrogen
Gas.
On Ru/ activated-carbon catalyst, reaction pressure 0.5MPa, under conditions of 178 DEG C of reaction temperature by levulic acid into
Row plus hydrogen, hydrogen/levulic acid molar ratio are 10, levulic acid air speed 2h-1, levulic acid conversion ratio 100%, gamma-valerolactone
Molar selectivity be 98.8%.
Logistics containing gamma-valerolactone is further converted on aromatized catalyst.500 DEG C of reaction temperature, reaction pressure
Power 0.6MPa, air speed 5h-1, the conversion ratio of gamma-valerolactone is 100%, and the quality for obtaining hydro carbons is 209.4kg, is formed such as 3 institute of table
Show, the quality of aromatic hydrocarbons is 202.1kg, and benzene, toluene and dimethylbenzene account for the 82.7% of products weight.
3 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 3.5 | 3.7 | 28.9 | 3.1 | 10.6 | 22.5 | 11 | 9.5 | 7.2 |
| Yield/KG | 7.3 | 7.7 | 60.5 | 6.5 | 22.2 | 47.1 | 23.0 | 19.9 | 15.1 |
[embodiment 4]
Hydrogenation catalyst preparation: copper nitrate and nickel nitrate aqueous solution are immersed in 150 grams of ZrO2On, Ni metal used and
The quality of Ni accounts for ZrO respectively2The 15% of quality and 3%, which is impregnated 48 hours at room temperature, and be put into oven drying
24 hours.Obtained dried catalyst precursor is put into tube furnace the reductase 12 hour at 500 DEG C later.
Aromatized catalyst preparation: the ZSM-5 type zeolite and 30 grams of boehmites progress that 30 grams of silica alumina ratios are 50 are weighed
Mixing is added 23 grams of sesbania powder, is uniformly mixed.Be added mass percentage be 5.5% 37 grams of aqueous solution of nitric acid, kneading at
Type, extrusion.It is 8 hours dry at 120 DEG C to obtain catalyst precarsor, is roasted 2 hours by 550 DEG C, obtains catalyst.
Raw material is 1 ton of bagasse, and dry fabric cellulose content is 40%.After these bagasse are sufficiently crushed, with 3.5 tons
3% aqueous hydrochloric acid solution is thoroughly mixed, and is stirred to react 25 minutes under the conditions of 1.5MPa, 230 DEG C and is completed acid hemolysis process,
205 kilograms of levulic acids and 83.8 kilograms of formic acid can be obtained in liquid product after separation.83.8 kilograms of formic acid decompose available
3.4 kilograms of hydrogen.
In Cu-Ni/ZrO2On catalyst, reaction pressure 3.5MPa, under conditions of 190 DEG C of reaction temperature by levulic acid into
Row plus hydrogen, hydrogen/levulic acid molar ratio are 20, levulic acid air speed 2h-1, levulic acid conversion ratio 100%, gamma-valerolactone
Molar selectivity be 99%, obtain 170.9 kilograms of gamma-valerolactone.
Logistics containing gamma-valerolactone is further converted on aromatized catalyst.480 DEG C of reaction temperature, reaction pressure
Power 0.5MPa, air speed 0.5h-1, the conversion ratio of gamma-valerolactone is 100%, and the quality for obtaining hydro carbons is 88.9kg, composition such as table 4
Shown, the quality of aromatic hydrocarbons is 77.0kg, and benzene, toluene and dimethylbenzene account for the 85.6% of products weight.
4 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 13.4 | 7.8 | 25.6 | 2.9 | 9.5 | 19.2 | 9.1 | 8.4 | 4.1 |
| Yield/KG | 11.9 | 6.9 | 22.8 | 2.6 | 8.4 | 17.1 | 8.1 | 7.5 | 3.6 |
Claims (6)
1. a kind of method for synthesizing aromatic hydrocarbons, comprising the following steps:
A) levulic acid, which contacts under hydroconversion condition with hydrogenation catalyst, generates the logistics containing gamma-valerolactone；
B) logistics containing gamma-valerolactone contacts generation containing benzene, toluene and two under aromatization conditions with aromatized catalyst
The arene stream of toluene；Wherein, the hydroconversion condition are as follows: 50~500 DEG C of reaction temperature, 0.1~10.0MPa of reaction pressure, empty
Speed 0.1~10.0 hour-1；The hydrogenation catalyst by weight percentage, include following components: 0.1~80% selected from Ni,
At least one of Ru, Zn, Cu or Pd metal；20~99.9% be selected from Al2O3、SiO2、ZrO2Or at least one in active carbon
Kind；Levulic acid comes from cellulose；The cellulosic acid solution preocess also generates formic acid, and the hydrogen that formic acid decomposes is used for acetyl
The hydrogenation process of propionic acid.
2. synthesizing the method for aromatic hydrocarbons according to claim 1, it is characterised in that levulic acid is former by cellulose-containing biomass
Material is obtained through acidolysis, supercritical hydrolysis, catalyzing part oxidation or metal chloride catalyzed conversion.
3. synthesizing the method for aromatic hydrocarbons according to claim 2, it is characterised in that by weight percentage, the biological material
Middle content of cellulose is 30~99%, and hemicellulose level is 0~50%, and content of lignin is 1~40%.
4. synthesizing the method for aromatic hydrocarbons according to claim 1, it is characterised in that the aromatization conditions are as follows: reaction temperature 100
~800 DEG C, 0.1~10.0MPa of reaction pressure, air speed 0.1~10.0 hour-1；
The aromatized catalyst, based on parts by weight, including following component: a) 20~80 parts selected from ZSM-5, ZSM-11,
At least one of MCM-22, ZSM-23 or zeolite L molecular sieve；B) 20~80 parts of binder.
5. synthesizing the method for aromatic hydrocarbons according to claim 4, it is characterised in that the silica alumina ratio of the ZSM Series Molecules sieve is 10
The silica alumina ratio of~150, MCM-22 type molecular sieve is 20~250, and L-type molecular sieve silica alumina ratio is 10~80.
6. the method for any synthesis aromatic hydrocarbons according to claim 1~5, it is characterised in that by weight percentage, the side
The content 2.0~10.0% of benzene in the composition of method preparation, the content of toluene is 25.0~40.0%, and the content of dimethylbenzene is
25.0~50.0%, remaining is non-aromatics and heavy aromatics.
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| CN102746092A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons |
| CN104230615A (en) * | 2014-08-25 | 2014-12-24 | 南京林业大学 | Method for preparing aromatic hydrocarbon and cyclopentenone from biomass derivative gamma-valerolactone by catalytic conversion |
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| CN102746092A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons |
| CN104230615A (en) * | 2014-08-25 | 2014-12-24 | 南京林业大学 | Method for preparing aromatic hydrocarbon and cyclopentenone from biomass derivative gamma-valerolactone by catalytic conversion |
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