CN106256812B - The composition that the method and this method for preparing aromatic hydrocarbons obtain - Google Patents
The composition that the method and this method for preparing aromatic hydrocarbons obtain Download PDFInfo
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Abstract
The present invention relates to the compositions that a kind of method for preparing aromatic hydrocarbons and this method obtain.Method includes the following steps: a) levulic acid contacts logistics of the generation containing methyltetrahydrofuran under hydroconversion condition with hydrogenation catalyst；B) logistics containing methyltetrahydrofuran, 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 preparing 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 new method for preparing 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 aromatic hydrocarbons is prepared, is wrapped
Include following steps:
A) levulic acid, which contacts under hydroconversion condition with hydrogenation catalyst, generates the logistics containing methyltetrahydrofuran；
B) logistics containing methyltetrahydrofuran contacts generation containing benzene, first under aromatization conditions with aromatized catalyst
The arene stream of benzene and 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, 2.0~10.0MPa of reaction pressure,
Air 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 the ZSM Series Molecules sieve is 10~150, MCM-22 type molecule
The silica alumina ratio of sieve 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 for preparing aromatic hydrocarbons
Composition made from method.
In above-mentioned technical proposal, it is preferable that by weight percentage, the content 5.0~15.0% of benzene in the composition,
The content of toluene is 20.0~38.0%, and the content of dimethylbenzene is 25.0~45.0%, 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 have
In the presence of machine acid or inorganic acid, (Effective Production of is produced by the biomass substrate such as cellulose, stalk
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),pp 18796–18805；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 methyltetrahydrofuran by further hydrogenation process.In aromatized catalyst
Under the action of, aromatization process occurs for methyltetrahydrofuran, and then realizes from methyltetrahydrofuran to benzene, toluene and dimethylbenzene etc.
The conversion of aromatic hydrocarbons.The formic acid of cellulose decomposition process by-product is decomposable to generate hydrogen, together with the hydrogen that aromatization process generates
As the hydrogen source of hydrogenation reaction, 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
The benzene and xylene production of renewable resource route, carbon utilisation rate is higher, and it is reachable that benzene, toluene and dimethylbenzene account for products weight
92.5%, hydrogen consumption is lower, and cost of material is low, achieves preferable technical effect.
Specific embodiment
[embodiment 1]
Raw material is 1 ton of bagasse, and dry fabric cellulose content is 52%.After these bagasse are sufficiently crushed, with 3.5 tons
1.5% aqueous hydrochloric acid solution is stirred, and is added 1.2 kilograms of ferric trichlorides, so that mixed solution is existed under microwave heating condition
1.0MPa, it keeps under the conditions of 180 DEG C completing within 10 minutes acid hemolysis process, 248 kilograms of acetyl can be obtained in liquid product after separation
Propionic acid, 95 kilograms of formic acid.95 kilograms of formic acid, which decompose, can be obtained 4.1 kilograms of hydrogen.
On 2%Ru/C catalyst, reaction pressure 1.2MPa, 130 DEG C of reaction temperature, hydrogen/levulic acid molar ratio is
20, levulic acid air speed 0.3h-1, levulic acid conversion ratio 98%, the molar selectivity of methyltetrahydrofuran is 97.3%.248
Kilogram levulic acid passes through hydrogenation reaction, generates 175.3 kilograms of methyltetrahydrofurans.Wherein, levulic acid adds hydrogen used in hydrogen
It is decomposed from formic acid gas part.
Methyltetrahydrofuran further converts on aromatized catalyst.Catalyst contains 80% MCM-22 type zeolite
(silica alumina ratio 32), 3% SiO2With 17% Al2O3, 450 DEG C of reaction temperature, reaction pressure 0.8MPa, air speed 0.5h-1, the conversion ratio of methyltetrahydrofuran is 100%, and hydrocarbon product total amount is 132.5 kilograms, and composition is as shown in table 1, aromatic hydrocarbons weight
117.0 kilograms of content, benzene, toluene and dimethylbenzene account for the 92.5% 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% | 15.5 | 7.2 | 32.7 | 2.4 | 8.7 | 18 | 9.2 | 5.6 | 0.7 |
| Yield/KG | 20.5 | 9.5 | 43.3 | 3.2 | 11.5 | 23.9 | 12.2 | 7.4 | 0.9 |
[embodiment 2]
Raw material is 1 ton of rice straw, and dry fabric cellulose content is 42.5%.After these straw are sufficiently crushed, it is added
2.8kg tin tetrachloride, the aqueous sulfuric acid with 5 ton 3.2% are stirred, make under agitation mixed solution 2.0MPa,
Keep completing for 30 minutes acid hemolysis process under the conditions of 205 DEG C, liquid product can be obtained after separation 169 kilograms of levulic acids and
70.3 kilogram formic acid.70.3 kilograms of formic acid decompose to obtain 3 kilograms of hydrogen.
Copper nitrate and nickel nitrate aqueous solution are immersed in 150 grams of ZrO2On, the quality of Ni metal used and Ni account for respectively
ZrO2The 15% of quality and 3%, 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 500 DEG C.In Cu-Ni/ZrO2On catalyst, reaction
Levulic acid is carried out under conditions of 210 DEG C of reaction temperature plus hydrogen, hydrogen/levulic acid molar ratio is 80, second by pressure 3.5MPa
Acyl propionic acid air speed 2h-1, levulic acid conversion ratio 100%, the molar selectivity of methyltetrahydrofuran is 98.8%, obtains methyl four
123.7 kilograms of hydrogen furans.Wherein, levulic acid adds hydrogen portion used in hydrogen to decompose from formic acid.
Methyltetrahydrofuran further converts on aromatized catalyst.Catalyst contains 40% ZSM-5 type zeolite (silicon
Al mole ratio be 25), 20% ZSM-11 type zeolite (silica alumina ratio 30), 40% Al2O3, 460 DEG C of reaction temperature, instead
Answer pressure 1.0MPa, air speed 3.0h-1, the conversion ratio of methyltetrahydrofuran is 100%, and hydrocarbon product total amount is 83.2 kilograms, group
At as shown in table 2,74.6 kilograms of aromatic hydrocarbons weight content, benzene, toluene and dimethylbenzene account for the 90.0% 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% | 10.3 | 8.9 | 35.3 | 2.7 | 8.2 | 17.2 | 8.4 | 7.2 | 1.8 |
| Yield/KG | 8.6 | 7.4 | 29.4 | 2.2 | 6.8 | 14.3 | 7.0 | 6.0 | 1.5 |
[embodiment 3]
Raw material is 1 ton of cellulose, and dry fabric cellulose content is 98.3%.By these celluloses and 3.5 ton 3.7% of sulfuric acid
Aqueous solution is stirred, and mixed solution is made to keep completing acidolysis in 30 minutes under the conditions of 3.0MPa, 205 DEG C under agitation
511 kilograms of levulic acids and 194 kilograms of formic acid can be obtained in process, liquid product after separation.194 kilograms of formic acid decompose to obtain
8.3 kilograms of hydrogen.
Copper nitrate and zinc nitrate aqueous solution are immersed on alumina-silica carriers, the matter of metallic copper used and zinc
Amount accounts for the 10% and 2% of carrier quality respectively, which is impregnated 24 hours at room temperature, and it is small to be put into oven drying 24
When.Obtained dried catalyst precursor is put into tube furnace the reductase 12 hour at 400 DEG C later.In Cu-Zn/SiO2Catalysis
In agent, reaction pressure 4.0MPa, 220 DEG C of reaction temperature, hydrogen/levulic acid molar ratio is 100, levulic acid air speed 0.3h-1,
Levulic acid conversion ratio 92%, the molar selectivity of methyltetrahydrofuran are 75.6%.511 kilograms of levulic acids are anti-by adding hydrogen
It answers, generates 286.4 kilograms of methyltetrahydrofurans.Wherein, levulic acid adds hydrogen portion used in hydrogen to decompose from formic acid.
Methyltetrahydrofuran further converts on aromatized catalyst.Catalyst contains 60% ZSM-5 type zeolite (silicon
Al mole ratio be 25), 10% zeolite beta (silica alumina ratio 60), 8% ZrO2With 22% Al2O3, reaction temperature 430
DEG C, reaction pressure 0.8MPa, air speed 1.0h-1, the conversion ratio of methyltetrahydrofuran is 100%, and hydrocarbon product total amount is 206.5 thousand
Gram, as shown in table 3,190.2 kilograms of aromatic hydrocarbons weight content, benzene, toluene and dimethylbenzene account for the 88.7% of products weight to composition.
3 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 7.9 | 9.2 | 28.6 | 3.9 | 8.5 | 21.3 | 10.2 | 8.0 | 2.4 |
| Yield/KG | 16.3 | 19.0 | 59.1 | 8.1 | 17.6 | 44.0 | 21.1 | 16.5 | 5.0 |
[embodiment 4]
Raw material is municipal 1 ton of waste paper, and dry fabric cellulose content is 92.1%.After these municipal administration waste paper are sufficiently crushed, with
3.5 ton 3.5% of aqueous sulfuric acid is stirred, and is added 13 kilograms of sodium sulfites, is made mixed solution under agitation
3.0MPa, it keeps under the conditions of 205 DEG C completing within 30 minutes acid hemolysis process, 503.5 kilograms of second can be obtained in liquid product after separation
Acyl propionic acid and 197.6 kilograms of formic acid.197.6 kilograms of formic acid, which decompose, can be obtained 8.5 kilograms of hydrogen.
In Pd-Ni/SiO2On catalyst, reaction pressure 9.0MPa, 280 DEG C of reaction temperature, hydrogen/levulic acid molar ratio
It is 40, levulic acid air speed 0.4h-1, levulic acid conversion ratio 93.9%, the molar selectivity of methyltetrahydrofuran is 80.3%.
503.5 kilograms of levulic acids pass through hydrogenation reaction, generate 281.4 kilograms of methyltetrahydrofurans.Wherein, levulic acid adds used in hydrogen
Hydrogen portion from formic acid decompose.
Methyltetrahydrofuran further converts on aromatized catalyst.Catalyst contains 60% ZSM-5 (sial mole
Than for 38), 10% ZSM-23 type zeolite (silica alumina ratio 25) and 30% SiO2.450 DEG C of reaction temperature, reaction pressure
0.8MPa, air speed 0.5h-1, methyltetrahydrofuran conversion ratio is 100%, and hydrocarbon product total amount is 198.5 kilograms, composition such as table 4
Shown, 178.8 kilograms of aromatic hydrocarbons weight content, benzene, toluene and dimethylbenzene account for the 86.6% of aromatic product weight.
4 aromatization products of table composition
| Non-aromatics | Benzene | Toluene | Ethylbenzene | Paraxylene | Meta-xylene | Ortho-xylene | C9 aromatic | C10 +Aromatic hydrocarbons | |
| Composition/wt% | 9.9 | 8.5 | 37.3 | 3.5 | 6.2 | 14.9 | 7.6 | 8.5 | 3.6 |
| Yield/KG | 19.7 | 16.9 | 74.0 | 6.9 | 12.3 | 29.6 | 15.1 | 16.9 | 7.1 |
Claims (6)
1. a kind of method for preparing aromatic hydrocarbons, comprising the following steps:
A) levulic acid, which contacts under hydroconversion condition with hydrogenation catalyst, generates the logistics containing methyltetrahydrofuran；
B) logistics containing methyltetrahydrofuran contact under aromatization conditions with aromatized catalyst generation contain benzene, toluene and
The arene stream of dimethylbenzene；Wherein, the hydroconversion condition are as follows: 50~500 DEG C of reaction temperature, 2.0~10.0MPa of reaction pressure,
Air speed 0.1~10.0 hour-1；By weight percentage, include following components: 0.1~80% is selected from for the hydrogenation catalyst
At least one of Ni, Ru, Zn, Cu or Pd metal；20~99.9% be selected from Al2O3、SiO2、ZrO2Or in active carbon extremely
Few one 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
The hydrogenation process of levulic acid.
2. preparing the method for aromatic hydrocarbons according to claim l, 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. preparing 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. preparing 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. preparing 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. any method for preparing aromatic hydrocarbons according to claim 1~5, it is characterised in that by weight percentage, the side
The content 5.0~15.0% of benzene in the composition of method preparation, the content of toluene is 20.0~38.0%, and the content of dimethylbenzene is
25.0~45.0%, remaining is non-aromatics and heavy aromatics.
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Citations (2)
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| CN101092347A (en) * | 2007-06-05 | 2007-12-26 | 浙江大学 | Method for preparing levulinic acid from hexabasic sugar catalyzed and hydrolyzed by fire resistant and highly acidic resin |
| 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 |
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2015
- 2015-06-19 CN CN201510345984.1A patent/CN106256812B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092347A (en) * | 2007-06-05 | 2007-12-26 | 浙江大学 | Method for preparing levulinic acid from hexabasic sugar catalyzed and hydrolyzed by fire resistant and highly acidic resin |
| 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 |
Non-Patent Citations (1)
| Title |
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| "Cycloaddition of Biomass-Derived Furans for Catalytic Production of Renewable p-Xylene";C. Luke Williams et al.;《ACS Catal.》;20120418;第2卷;935-939 |
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