CN106316735A - Method for producing aromatic hydrocarbons - Google Patents
Method for producing aromatic hydrocarbons Download PDFInfo
- Publication number
- CN106316735A CN106316735A CN201510345812.4A CN201510345812A CN106316735A CN 106316735 A CN106316735 A CN 106316735A CN 201510345812 A CN201510345812 A CN 201510345812A CN 106316735 A CN106316735 A CN 106316735A
- Authority
- CN
- China
- Prior art keywords
- optionally substituted
- aromatic hydrocarbons
- branched
- straight
- zro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 112
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005899 aromatization reaction Methods 0.000 claims description 9
- 239000010902 straw Substances 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 3
- 229910019788 NbF3 Inorganic materials 0.000 claims description 3
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 229910017050 AsF3 Inorganic materials 0.000 claims description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 claims description 2
- JCMGUODNZMETBM-UHFFFAOYSA-N arsenic trifluoride Chemical compound F[As](F)F JCMGUODNZMETBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 claims 1
- 150000005846 sugar alcohols Chemical class 0.000 claims 1
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 2
- JNBVLGDICHLLTN-DZUOILHNSA-N (2s)-2-acetamido-n-[(2s,3s)-4-[[[(2s)-2-acetamido-3-methylbutanoyl]amino]-(cyclohexylmethyl)amino]-3-hydroxy-1-phenylbutan-2-yl]-3-methylbutanamide Chemical compound C([C@H](NC(=O)[C@@H](NC(C)=O)C(C)C)[C@@H](O)CN(CC1CCCCC1)NC(=O)[C@@H](NC(C)=O)C(C)C)C1=CC=CC=C1 JNBVLGDICHLLTN-DZUOILHNSA-N 0.000 abstract 1
- 150000001555 benzenes Chemical class 0.000 abstract 1
- 125000002541 furyl group Chemical group 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 150000005172 methylbenzenes Chemical class 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 abstract 1
- 150000003738 xylenes Chemical class 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 28
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 26
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000002028 Biomass Substances 0.000 description 17
- 238000004445 quantitative analysis Methods 0.000 description 17
- 238000001819 mass spectrum Methods 0.000 description 16
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 12
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 12
- 238000004451 qualitative analysis Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000011973 solid acid Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229940040102 levulinic acid Drugs 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000508 aqueous-phase reforming Methods 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 210000000582 semen Anatomy 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing aromatic hydrocarbons. Raw materials are in contact with solid strong acid catalysts, under aromizing conditions, to prepare the aromatic hydrocarbon material flow, which contains benzenes, methyl benzenes and xylenes. The raw materials have a structural formula (I) shown in the description. In the formula (I), R1 is hydrogen, optional substituted linear or branched alkyl from C1 to C20, optional substituted linear or branched alkenyl from C2 to C20, optional substituted linear or branched alkynyl from C2 to C20, optional substituted cycloalkyl from C3 to C20 or optional substituted aryl from C6 to C20; R2 is optional substituted linear or branched carboxyl from C1 to C20, furyl or hydroxyl alkyl furyl. The hydroxyl alkyl furyl has a structural formula (II) shown in the description. In the formula (II), R3 is optional substituted linear or branched alkyl from C1 to C20, optional substituted linear or branched alkenyl from C2 to C20, optional substituted linear or branched alkynyl from C2 to C20. The method can be applied to the field of preparation of aromatic hydrocarbons through non-fossil resources.
Description
Technical field
The present invention relates to a kind of method producing aromatic hydrocarbons, particularly relate to one prepare benzene, toluene and
The method of dimethylbenzene light aromatics.
Background technology
Benzene, toluene and dimethylbenzene are the important basic organic chemical industry raw materials of social development, himself or
Can to derive multiple product chain through reproduction, product be widely used in polyester, chemical fibre, rubber,
The numerous areas such as medicine and fine chemistry industry, domestic consumption amount reaches up to ten million ton, to national economy
Development has material impact.Benzene is a kind of basic petrochemical material of multipurpose, can produce what it derived
Numerous products, including ethyl benzene/styrene, cumene/phenol etc..Xylol mainly for the manufacture of
P-phthalic acid, by p-phthalic acid (PTA) or diethyl terephthalate (DMT) intermediate,
For producing poly-cruel fiber such as polyethylene terephthalate (PET), resin and thin film.This three class
Aromatic hydrocarbons is typical light aromatics, is abbreviated as BTX.The production of BTX the most both at home and abroad relies primarily on
In non-renewable fossil resource, such as by a catalyst by oil through hydrogenation, reform,
The technical processs such as aromatic hydrocarbons conversion and separation obtain.But, fossil resource reserves finite sum is non-renewable
Property so that more see surging with the cost that oil is mainly refining raw material production aromatic hydrocarbons.It addition, fossil
The utilization of continually developing of resource produces a large amount of greenhouse gas emissions, caused series of environmental problems
It is on the rise, therefore develops and using value significant from Renewable resource route production aromatic hydrocarbons.
The plant that nature is widely present is the Renewable resource of a quasi-representative, belongs to the one of biomass
Kind.The whole world annual yield of biomass is about 200,000,000,000 tons, rich reserves, wide material sources, inexpensively
It is easy to get.The aromatic hydrocarbon product being widely used from the preparation of reproducible biomass resource causes science
Boundary and the extensive concern of industrial quarters.
In recent years, biological legal system aromatic hydrocarbons is all studied by whole world Duo Jia research institution, achieves
Certain progress.In addition to fermentative routes, the route with certain development prospect has 4: biomass
Through synthesis gas aromatisation again；Fast pyrogenation aromatic hydrocarbons；Biomass sugar platform is through catalytic cracking aromatic hydrocarbons；
Biomass-based isobutanol aromatisation etc..Below the technology with certain economy is analyzed.
Anellotech company develops the Biomassto of the catalytic pyrolysis preparing aromatic hydrocarbons of lignocellulose
AromaticTMTechnique [Katherine Bourzac.From biomass to chemicals in one step.
MIT Technology Review, 2010-03-29.], and be devoted to push it against industrialized production.
This technique is with non-grain biomass such as straw, culled wood etc. as raw material, by catalysis quickly
Pyrolytic technique aromatic hydrocarbons, built up demonstration experimental provision in 2011.CFP technology is at 600 DEG C
Biomass material is ground to after drying powder, mixes feeding high temperature with powdery ZSM-5 catalyst and follow
In circulation fluidized bed reactor, being sufficiently mixed with the form of air whirl and heat, material powder is through urging
Heat-transformation solution is partially converted into aromatic hydrocarbons, simultaneously catalyst coking and deactivation, afterwards separating catalyst and purification
Product can get light aromatics (US20090227823).
Virent company develops BioFormingTMTechnology, based on sugar platform, uses liquid phase
The technology reformed is reformate to biomass compound deoxidation, further virtue on ZSM-5 catalyst
Structure turns to aromatic hydrocarbons.Its raw material includes the biomass such as Semen Maydis, Caulis Sacchari sinensis and lignocellulose.Main process
For using aqueous-phase reforming (APR) technology, carbohydrate admixture is turned through pallium-on-carbon-rhenium catalyst deoxidation
Turning to alcohol, aldehyde list oxygen compound, product carbochain after condensation hydrogenation is increased, further virtue
Structure prepares oil product and aromatic hydrocarbons (US20110257416A1).This process is from hydrogen producing, in theory
Can reduce and even not use external hydrogen source.
Above-mentioned technology path is respectively arranged with feature, emphasizes particularly on different fields, and there is also problem in various degree,
Such as problems such as the utilization rate of raw material, the price of raw material, the stability of aromatisation system.
Summary of the invention
It is desirable to provide a kind of method producing aromatic hydrocarbons.
For achieving the above object, the technical scheme that the present invention takes is as follows: a kind of production aromatic hydrocarbons
Method, under aromatization conditions, make raw material contact generation with strong solid acid catalyst containing benzene, first
Benzene and the arene stream of dimethylbenzene；Wherein, described raw material has a structure formula (I):
In formula (I), R1For hydrogen, optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20
Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkanes
Base or optionally substituted C6-20Aryl；R2For optionally substituted C1-20Straight or branched carboxyl, furan
Base or hydroxyl alkyl furyl；Wherein, described hydroxyl alkyl furyl has a structural formula (II):
In formula (II), R3For optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20Straight chain
Or branched-chain alkenyl, optionally substituted C2-20Straight or branched alkynyl.
In technique scheme, it is preferable that in formula (I), R1For optionally substituted C2-10Straight chain or
Alkyl group, optionally substituted C2-10Straight or branched thiazolinyl.
In technique scheme, it is preferable that in formula (I), R2For optionally substituted C2-10Straight chain or
Chain carboxyl.
In technique scheme, it is preferable that in formula (II), R3For optionally substituted C2-10Straight chain or
Branched alkyl, optionally substituted C2-10Straight or branched thiazolinyl.
In technique scheme, it is preferable that described 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-MnO2In at least one.
In technique scheme, it is preferable that described aromatization conditions is: reaction temperature 300～800 DEG C,
Hydrogen Vapor Pressure in terms of gauge pressure 0.1～5MPa, raw material weight air speed 0.3～10 hours-1.It is highly preferred that
Described aromatization conditions is: reaction temperature 300～650 DEG C, Hydrogen Vapor Pressure in terms of gauge pressure 0.5～4MPa,
Raw material weight air speed 0.3～5 hours-1。
In technique scheme, it is preferable that described raw material is from biological material.
In technique scheme, it is preferable that described raw material from xylitol, glucose, cellobiose,
At least one in hemicellulose or lignin.
In technique scheme, it is preferable that described raw material is from bagasse, glucose, timber, jade
At least one in rice straw or Caulis et Folium Oryzae straw.
As an embodiment of the invention, raw material of the present invention is biomass-based carbonyl class
Compound, such as furfural, 5 hydroxymethyl furfural, levulic acid.Such carbonyl complex can be by coming
Source is extensive, the biomass material of rich reserves obtains, and can prepare on a large scale.Such as, levulinic
Acid can in the presence of Zirconium oxide, metal chloride, organic acid or mineral acid, by cellulose,
The biomass substrates such as straw are produced.(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 18,796 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 in presence of an acid catalyst, by glucose,
The biomass such as cellulose prepare (Catalytic conversion of 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 Semen Maydis
Straw or corn cob are raw material, produce through acid catalysis and obtain.
In the present invention, the preparation method of strong solid acid catalyst is known in the art, permissible
Use precipitation-impregnation method.Specifically can be found in document " solid acid and fine chemistry industry " and " SO4 2-/MxOy
The progress of type solid super acid catalyst, applies chemical industry, 2014, vol43,1879-1883 ".
The inventive method has preferable conversion ratio to carbonyl complex, to benzene,toluene,xylene
Product has preferable selectivity, and during solving conventional biomass aromatic hydrocarbons, aromatics yield is low and anti-
The problem answering step length.Using the inventive method, feed stock conversion can reach 98%；Benzene,
Toluene, the selectivity of dimethylbenzene target product can reach 93%, achieve preferable technology effect
Really.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Weigh 60 grams of Caulis et Folium Oryzae straw, be placed in autoclave pressure and add 700 grams of water, adding water quality 7%
The sulfuric acid solution of 5mol/L, be warmed up at 210 DEG C reaction 30 minutes, cool down afterwards, will cooling
After reacting liquid filtering, obtain filter cake and filtrate, filtrate is the hydrolyzed solution of cellulose, reaction
After end, use mass spectrum that reaction result being identified, primary product is levulic acid, its generation amount
It it is 22.8 grams.
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2Catalyst, loads solid
Fixed bed reactor.Reaction substrate is levulic acidWeight space velocity 0.3 hour-1,
Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature 400 DEG C.After reaction terminates, use matter
Spectrum carries out qualitative analysis to reaction result, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate
Conversion ratio is 83%, and the selectivity of BTX is 87%.
[embodiment 2]
Weigh 5 grams to be dried except the water S of 12 hours at 120 DEG C2O8 2-/ZrO2Catalyst, loads solid
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 450 DEG C.After reaction terminates, use mass spectrum that reaction result is carried out fixed
Property analyze, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is 98%, BTX
Selectivity be 93%.
[embodiment 3]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/TiO2Catalyst, loads solid
Fixed bed reactor.Reaction substrate is levulic acid, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa,
Flow 20ml min-1, temperature 400 DEG C.After reaction terminates, use mass spectrum that reaction result is carried out fixed
Property analyze, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is 88%, BTX
Selectivity be 81%.
[embodiment 4]
Weigh 30 grams of timber, be placed in autoclave pressure and add 400 grams of water, adding water quality 7%
The sulfuric acid solution of 5mol/L, be warmed up at 200 DEG C reaction 30 minutes, cool down afterwards, will cooling
After reacting liquid filtering, obtain filter cake and filtrate, filtrate is the hydrolyzed solution of cellulose, reaction
After end, use mass spectrum that reaction result being identified, primary product is levulic acid, its generation amount
It it is 10.5 grams.
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2-Fe3O4Catalyst,
Load fixed bed reactors.Reaction substrate is levulic acid, weight space velocity 5.0 hours-1, hydrogen pressure
Power 1.0MPa, flow 20ml min-1, temperature 500 DEG C.After reaction terminates, use mass spectrum to instead
Result should carry out qualitative analysis, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio
Being 82%, the selectivity of BTX is 78%.
[embodiment 5]
Weigh 5 grams to be dried except the water Pt/SO of 12 hours at 120 DEG C4 2-/TiO2Catalyst, loads
Fixed bed reactors.Reaction substrate is levulic acid, weight space velocity 2.0 hours-1, Hydrogen Vapor Pressure
3.0MPa, flow 20ml min-1, temperature 450 DEG C.After reaction terminates, use mass spectrum to reaction knot
Fruit carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is
The selectivity of 89%, BTX is 81%.
[embodiment 6]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/TiO2-ZrO2Catalyst, dress
Enter fixed bed reactors.Reaction substrate is levulic acid, weight space velocity 0.8 hour-1, Hydrogen Vapor Pressure
1.0MPa, flow 40ml min-1, temperature 400 DEG C.After reaction terminates, use mass spectrum to reaction knot
Fruit carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is
The selectivity of 87%, BTX is 81%.
[embodiment 7]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/TiO2-Al2O3Catalyst,
Load fixed bed reactors.Reaction substrate is furfuralWeight space velocity 1.0 hours-1,
Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature 400 DEG C.After reaction terminates, use matter
Spectrum carries out qualitative analysis to reaction result, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate
Conversion ratio is 79%, and the selectivity of BTX is 85%.
[embodiment 8]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalysis
Agent, loads fixed bed reactors.Reaction substrate is furfural, weight space velocity 2.0 hours-1, hydrogen pressure
Power 1.0MPa, flow 50ml min-1, temperature 450 DEG C.After reaction terminates, use mass spectrum to instead
Result should carry out qualitative analysis, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio
Being 91%, the selectivity of BTX is 87%.
[embodiment 9]
Weigh 5 grams to be dried except the water SbF of 12 hours at 120 DEG C5/SiO2-Al2O3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is furfural, weight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa,
Flow 20ml min-1, temperature 400 DEG C.After reaction terminates, use mass spectrum that reaction result is carried out fixed
Property analyze, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is 78%, BTX
Selectivity be 89%.
[embodiment 10]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/TiO2-WO3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is furfural, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa,
Flow 20ml min-1, temperature 500 DEG C.After reaction terminates, use mass spectrum that reaction result is carried out fixed
Property analyze, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is 86%, BTX
Selectivity be 82%.
[embodiment 11]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2-WO3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is levulic acid, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure
1.0MPa, flow 20ml min-1, temperature 380 DEG C.After reaction terminates, use mass spectrum to reaction knot
Fruit carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is
The selectivity of 92%, BTX is 90%.
[embodiment 12]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/TiO2-MoO3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 2.0 hours-1, hydrogen
Pressure 1.0MPa, flow 20ml min-1, temperature 380 DEG C.After reaction terminates, use mass spectrum pair
Reaction result carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate converts
Rate is 79%, and the selectivity of BTX is 83%.
[embodiment 13]
Weigh 5 grams to be dried except the water BiF of 12 hours at 120 DEG C3/Al2O3-B2O3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 1.0 hours-1, hydrogen
Pressure 1.0MPa, flow 20ml min-1, temperature 420 DEG C.After reaction terminates, use mass spectrum pair
Reaction result carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate converts
Rate is 86%, and the selectivity of BTX is 82%.
[embodiment 14]
Weigh 5 grams to be dried except the water NbF of 12 hours at 120 DEG C3/Al2O3-B2O3Catalyst, dress
Enter fixed bed reactors.Reaction substrate is 5 hydroxymethyl furfural, weight space velocity 2.0 hours-1, hydrogen
Pressure 1.0MPa, flow 20ml min-1, temperature 360 DEG C.After reaction terminates, use mass spectrum pair
Reaction result carries out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate converts
Rate is 87%, and the selectivity of BTX is 91%.
[embodiment 15]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2-Fe2O3-MnO2Catalysis
Agent, loads 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 400 DEG C.After reaction terminates, use matter
Spectrum carries out qualitative analysis to reaction result, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate
Conversion ratio is 88%, and the selectivity of BTX is 85%.
[embodiment 16]
Weigh 5 grams to be dried except the water SO of 12 hours at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalysis
Agent, loads fixed bed reactors.Reaction substrate is levulic acid, weight space velocity 1.0 hours-1, hydrogen
Atmospheric pressure 1.0MPa, flow 20ml min-1, temperature 380 DEG C.After reaction terminates, use mass spectrum
Reaction result is carried out qualitative analysis, and chromatograph carries out quantitative analysis to reaction result.Reaction substrate turns
Rate is 94%, and the selectivity of BTX is 87%.
[embodiment 17]
Weigh 5 grams to be dried except the water AlCl of 12 hours at 120 DEG C3-CuCl2Catalyst, loads solid
Fixed bed reactor.Reaction substrate is furfural, weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa,
Flow 20ml min-1, temperature 400 DEG C.After reaction terminates, use mass spectrum that reaction result is carried out fixed
Property analyze, chromatograph carries out quantitative analysis to reaction result.Reaction substrate conversion ratio is 81%, BTX
Selectivity be 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 (10)
1. the method producing aromatic hydrocarbons, under aromatization conditions, makes raw material be catalyzed with solid strong acid
Agent contact generates containing benzene, toluene and the arene stream of dimethylbenzene；Wherein, described raw material has structure
Formula (I):
In formula (I), R1For hydrogen, optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20
Straight or branched thiazolinyl, optionally substituted C2-20Straight or branched alkynyl, optionally substituted C3-20Cycloalkanes
Base or optionally substituted C6-20Aryl；R2For optionally substituted C1-20Straight or branched carboxyl, furan
Base or hydroxyl alkyl furyl；Wherein, described hydroxyl alkyl furyl has a structural formula (II):
In formula (II), R3For optionally substituted C1-20Straight or branched alkyl, optionally substituted C2-20Straight chain
Or branched-chain alkenyl, optionally substituted C2-20Straight or branched alkynyl.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that in formula (I), R1
For optionally substituted C2-10Straight or branched alkyl, optionally substituted C2-10Straight or branched thiazolinyl.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that in formula (I), R2
For optionally substituted C2-10Straight or branched carboxyl.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that in formula (II), R3
For optionally substituted C2-10Straight or branched alkyl, optionally substituted C2-10Straight or branched thiazolinyl.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that described solid strong acid is urged
Agent 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-CuCl2In at least one.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that described aromatization conditions
For: reaction temperature 300～800 DEG C, Hydrogen Vapor Pressure in terms of gauge pressure 0.1～5MPa, raw material weight is empty
Speed 0.3～10 hour-1。
The method producing aromatic hydrocarbons the most according to claim 6, it is characterised in that described aromatization conditions
For: reaction temperature 300～650 DEG C, Hydrogen Vapor Pressure in terms of gauge pressure 0.5～4MPa, raw material weight is empty
Speed 0.3～5 hour-1。
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that described raw material comes spontaneous
Material.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that described raw material is from wood
At least one in sugar alcohol, glucose, cellobiose, hemicellulose or lignin.
The method producing aromatic hydrocarbons the most according to claim 1, it is characterised in that described raw material from
At least one in bagasse, glucose, timber, corn stalk or Caulis et Folium Oryzae straw.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 |
| KR1020187001728A KR102454225B1 (en) | 2015-06-19 | 2016-06-17 | Process for the preparation of aromatic hydrocarbons, paraxylene and terephthalic acid |
| PCT/CN2016/000315 WO2016201955A1 (en) | 2015-06-19 | 2016-06-17 | Methods for manufacturing 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 |
| JP2017565948A JP6877367B2 (en) | 2015-06-19 | 2016-06-17 | Method for producing aromatic hydrocarbons, p-xylene and terephthalic acid |
| ES16810696T ES2880326T3 (en) | 2015-06-19 | 2016-06-17 | Methods for making aromatic hydrocarbon, 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 |
| BR112017027347-0A BR112017027347B1 (en) | 2015-06-19 | 2016-06-17 | Processes for the production of aromatic hydrocarbon, paraxylene and terephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510345812.4A CN106316735B (en) | 2015-06-19 | 2015-06-19 | The method for producing aromatic hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106316735A true CN106316735A (en) | 2017-01-11 |
| CN106316735B CN106316735B (en) | 2019-06-11 |
Family
ID=57728743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510345812.4A Active CN106316735B (en) | 2015-06-19 | 2015-06-19 | The method for producing aromatic hydrocarbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106316735B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108187730A (en) * | 2018-01-26 | 2018-06-22 | 昆山普瑞凯纳米技术有限公司 | A kind of support type composition metal-acid bifunctional catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202548A (en) * | 2009-03-02 | 2010-09-16 | Kagoshima Univ | Apparatus for producing levulinic acid, apparatus for separating levulinic acid, and apparatus for producing hydrocarbon from levulinic acid |
-
2015
- 2015-06-19 CN CN201510345812.4A patent/CN106316735B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202548A (en) * | 2009-03-02 | 2010-09-16 | Kagoshima Univ | Apparatus for producing levulinic acid, apparatus for separating levulinic acid, and apparatus for producing hydrocarbon from levulinic acid |
Non-Patent Citations (2)
| Title |
|---|
| KAIGE WANG,ET AL.: "Catalytic conversion of carbohydrate-derived oxygenates over HZSM-5 in a tandem oxygenates over HZSM-5 in a tandem", 《GREEN CHEM.》 * |
| YAN ZHAO，ET AL.: "Production of aromatic hydrocarbons through catalytic pyrolysis of 5-Hydroxymethylfurfural from biomass", 《BIORESOURCE TECHNOLOGY》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106316735B (en) | 2019-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jamil et al. | Greener and sustainable production of bioethylene from bioethanol: Current status, opportunities and perspectives | |
| Guo et al. | Catalytic transformation of lignocellulosic biomass into arenes, 5‐hydroxymethylfurfural, and furfural | |
| Han et al. | Catalytic conversion of lignocellulosic biomass into hydrocarbons: A mini review | |
| Zhang et al. | Catalytic pyrolysis of biomass and polymer wastes | |
| Bohre et al. | Upgrading furfurals to drop-in biofuels: An overview | |
| Li et al. | Synthesis of high‐quality diesel with furfural and 2‐methylfuran from hemicellulose | |
| Sen et al. | A sulfuric acid management strategy for the production of liquid hydrocarbon fuels via catalytic conversion of biomass-derived levulinic acid | |
| Schandel et al. | Thermal cracking of sugars for the production of glycolaldehyde and other small oxygenates | |
| Arora et al. | pH‐Controlled Efficient Conversion of Hemicellulose to Furfural Using Choline‐Based Deep Eutectic Solvents as Catalysts | |
| Wang et al. | A review on catalytic depolymerization of lignin towards high-value chemicals: Solvent and catalyst | |
| Zhang et al. | Al2O3‐TiO2 modified sulfonated carbon with hierarchically ordered pores for glucose conversion to 5‐HMF | |
| CN106573852A (en) | Process for the manufacture of furfural and furfural derivatives | |
| CN106256809B (en) | The composition that the method and this method of biomass production aromatic hydrocarbons obtain | |
| EP2995672B1 (en) | Method for modifying biomass pyrolysis oil | |
| Ansaloni et al. | Wet air oxidation of industrial lignin case study: influence of the dissolution pretreatment and perovskite-type oxides | |
| Fridrich et al. | Selective coupling of bioderived aliphatic alcohols with acetone using hydrotalcite derived mg–al porous metal oxide and raney nickel | |
| CN106565396A (en) | Method for producing aromatic hydrocarbon by cycloaddition | |
| CN109054875A (en) | A kind of biomass efficient method for transformation | |
| CN105154129B (en) | Method for preparing liquid fuel by catalytic conversion of biomass platform compound and ABE fermentation product acetoin | |
| Zhang et al. | Valorization of waste lignin: Efficient and steady production of liquid fuels | |
| Ma et al. | A process insight into production of ethyl levulinate via a stepwise fractionation | |
| Zhu et al. | Continuous production of 5‐Hydroxymethylfurfural from monosaccharide over zirconium phosphates | |
| CN106316766A (en) | Aromatization method | |
| Ma et al. | Calcium oxide derived from eggshells supported on titanium oxide green catalysts for lignin hydrogenolysis under supercritical alcohol solvents | |
| CN106316735A (en) | Method for producing aromatic hydrocarbons |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |