CN106316767B - Lactone compound aromatization method - Google Patents
Lactone compound aromatization method Download PDFInfo
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- CN106316767B CN106316767B CN201510346001.6A CN201510346001A CN106316767B CN 106316767 B CN106316767 B CN 106316767B CN 201510346001 A CN201510346001 A CN 201510346001A CN 106316767 B CN106316767 B CN 106316767B
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- -1 Lactone compound Chemical class 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 9
- 239000011973 solid acid Substances 0.000 claims abstract description 7
- 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
- 125000002541 furyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 120
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 8
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-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
- 239000010902 straw Substances 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 claims description 3
- 229910019788 NbF3 Inorganic materials 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 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
- 239000010905 bagasse Substances 0.000 claims description 3
- 239000012620 biological material Substances 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910017050 AsF3 Inorganic materials 0.000 claims description 2
- 229920002488 Hemicellulose Polymers 0.000 claims description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 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
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000811 xylitol Substances 0.000 claims description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 2
- 229960002675 xylitol Drugs 0.000 claims description 2
- 235000010447 xylitol Nutrition 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 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 35
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000001819 mass spectrum Methods 0.000 description 19
- 238000004587 chromatography analysis Methods 0.000 description 17
- 238000004451 qualitative analysis Methods 0.000 description 17
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- BGLUXFNVVSVEET-UHFFFAOYSA-N beta-angelica lactone Chemical group CC1OC(=O)C=C1 BGLUXFNVVSVEET-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical compound O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229940040102 levulinic acid Drugs 0.000 description 3
- 229940005605 valeric acid Drugs 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- IFYYFLINQYPWGJ-UHFFFAOYSA-N gamma-decalactone Chemical compound CCCCCCC1CCC(=O)O1 IFYYFLINQYPWGJ-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 2
- ZYDGQQTXLBNSGJ-UHFFFAOYSA-N oxonan-2-one Chemical compound O=C1CCCCCCCO1 ZYDGQQTXLBNSGJ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229960000380 propiolactone Drugs 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229910016287 MxOy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 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 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 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 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- IFYYFLINQYPWGJ-VIFPVBQESA-N gamma-Decalactone Natural products CCCCCC[C@H]1CCC(=O)O1 IFYYFLINQYPWGJ-VIFPVBQESA-N 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 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
- 230000009466 transformation Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of lactone compound aromatization methods.This method is included under aromatization conditions, and lactone compound is made to contact the step of generating the arene stream containing benzene, toluene and dimethylbenzene with strong solid acid catalyst, wherein the lactone compound has structure formula (I):In formula (I), R1For the C optionally replaced1‑20Linear or branched alkyl group, the C optionally replaced2‑20Linear chain or branched chain alkenyl, the C optionally replaced2‑20Linear chain or branched chain alkynyl, the C optionally replaced3‑20Naphthenic base or the C optionally replaced6‑20Aryl；R2For hydrogen, optionally the C replaced1‑20Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furyl；Wherein, the hydroxyl alkyl furyl has structural formula (II):In formula (II), R3For the C optionally replaced1‑20Linear or branched alkyl group, the C optionally replaced2‑20Linear chain or branched chain alkenyl, the C optionally replaced2‑20Linear chain or branched chain alkynyl.This method can be used for non-fossil sources aromatic hydrocarbons field.
Description
Technical field
The present invention relates to a kind of lactone compound aromatization method, in particular to a kind of lactone compound aromatisation system
The method of standby benzene,toluene,xylene light aromatics.
Background technique
BTX is the abbreviation of benzene, toluene and dimethylbenzene these three types aromatic hydrocarbon substance.BTX is the important substantially organic of social development
Industrial chemicals, its own or multiple product chain can be derived by reproduction, product be widely used in polyester, chemical fibre, rubber,
Numerous areas, the domestic consumption amount such as medicine and fine chemistry industry reach up to ten million tons, have great influence to the national economic development.
Benzene is a kind of basic petrochemical material of multipurpose, can produce numerous products derived from it, including ethyl benzene/styrene, isopropylbenzene/benzene
Phenol etc..Paraxylene passes through terephthalic acid (TPA) (PTA) or diethyl terephthalate mainly for the manufacture of terephthalic acid (TPA)
(DMT) intermediate gathers cruel fiber such as polyethylene terephthalate (PET), resin and film for producing.At present both at home and abroad
The production of aromatic hydrocarbons depends on non-renewable fossil resource, such as can by a catalyst by petroleum by plus hydrogen, reformation,
The technical process such as aromatic hydrocarbons conversion and separation obtain.But fossil resource reserves are limited and non-renewable, so that based on petroleum
Refine raw material production aromatic hydrocarbons cost more see it is surging.In addition, continually developing for fossil resource utilizes a large amount of greenhouse gases of generation
Discharge, caused a series of environmental problems are on the rise, therefore development has important meaning from renewable resource route production aromatic hydrocarbons
Justice and application value.
Biomass lactone compound typical case such as valerolactone can be obtained after hydrolyzing deoxidation by cellulose.Gamma-valerolactone
One of biomass platform chemicals are had been cited as, gasoline, additive and other chemicals can be converted by the means of catalysis.
For example, the noble metal catalyst effect of acid carrier load is lower to use H2Reduction, can obtain valeric acid.Valeric acid by cerium oxide and
Decarboxylation coupling reaction can occur for the mixture through catalytic of zirconium oxide, butyl ketone be generated, using the available gasoline of hydrogenating reduction
Component.Use Pd/NbO2Catalyst, at 325 DEG C, 3.5MPa adds hydrogen to 50% gamma-valerolactone aqueous solution, and the yield of valeric acid is
92% (J.C.Serrano-Ruiz, D.Wang, J.A.Dumesic, Catalytic upgrading of levulinic
acid to 5-nonanone,Green Chemistry 2010,12,574-577.)。
On the whole, the conversion of valerolactone, which is concentrated mainly on, is converted into the essences such as oil product, oil dope and pyrrolidones
Thin chemicals is rarely reported and is translated into the aromatic hydrocarbons such as benzene,toluene,xylene.
Summary of the invention
The present invention is intended to provide a kind of lactone compound aromatization method.This method has at low cost, aromatisation efficiency
Height, BTX selectively high feature.
For achieving the above object, The technical solution adopted by the invention is as follows: a kind of lactone compound aromatisation side
Method is included under aromatization conditions, and lactone compound is made to contact generation with strong solid acid catalyst containing benzene, toluene and dimethylbenzene
Arene stream the step of；Wherein, the lactone compound has structure formula (I):
In formula (I), R1For the C optionally replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Linear chain or branched chain alkenyl,
The C optionally replaced2-20Linear chain or branched chain alkynyl, the C optionally replaced3-20Naphthenic base or the C optionally replaced6-20Aryl；R2For
Hydrogen, the C optionally replaced1-20Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furyl；Wherein, the hydroxyl alkyl furyl
With structure formula (II):
In formula (II), R3For the C optionally replaced1-20Linear or branched alkyl group, the C optionally replaced2-20Linear chain or branched chain alkene
Base, the C optionally replaced2-20Linear chain or branched chain alkynyl.
In above-mentioned technical proposal, it is preferable that in formula (I), R1For the C optionally replaced2-10Linear or branched alkyl group optionally takes
The C in generation2-10Linear chain or branched chain alkenyl.
In above-mentioned technical proposal, it is preferable that in formula (I), R2For the C optionally replaced2-10Linear chain or branched chain carboxyl.
In above-mentioned technical proposal, it is preferable that in formula (II), R3For the C optionally replaced2-10Linear or branched alkyl group optionally takes
The C in generation2-10Linear chain or branched chain alkenyl.
In above-mentioned technical proposal, it is preferable that the strong solid acid catalyst is selected from SO4 2-/ZrO2、S2O8 2-/ZrO2、
SO4 2-/TiO2、SO4 2-/ZrO2-Fe3O4、Pt/SO4 2-/TiO2、SO4 2-/TiO2-ZrO2、SO4 2-/TiO2-Al2O3、SO4 2-/
TiO2-WO3、SO4 2-/ZrO2-Fe2O3-Cr2O3、SbF5/SiO2-Al2O3、SO4 2-/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/
Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-
B2O3、NbF3/Al2O3-B2O3、SO4 2-/ZrO2-Fe2O3-MnO2Or AlCl3-CuCl2At least one of.
In above-mentioned technical proposal, it is preferable that the aromatization conditions are as follows: 300~800 DEG C of reaction temperature, Hydrogen Vapor Pressure with
Gauge pressure 0.1~5MPa of meter, raw material weight air speed 0.1~10 hour-1.It is highly preferred that the aromatization conditions are as follows: reaction temperature
300~650 DEG C, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 hour-1。
In above-mentioned technical proposal, it is preferable that the lactone compound comes from biological material.
In above-mentioned technical proposal, it is preferable that the lactone compound comes from xylitol, glucose, fructose, fiber two
At least one of sugar, hemicellulose or lignin.
In above-mentioned technical proposal, it is preferable that the lactone compound from bagasse, glucose, timber, corn stalk or
At least one of straw straw.
In above-mentioned technical proposal, it is preferable that the lactone compound be selected from propiolactone, butyrolactone, gamma-valerolactone, when
Return at least one of lactone, δ-valerolactone, caprolactone or decalactone.
In the method for the present invention, the lactone compound comes from biological material.Such as valerolactone, it can be passed through by cellulose
It is obtained after hydrolysis deoxidation, reference can be made to document " Direct conversion of cellulose to levulinic acid
And gamma-valerolactone using solid acid catalysts, Catal.Sci.Technol., 2013,3,
927-931；Production of levulinic acid and gamma-valerolactone(GVL)from
Cellulose using GVL as a solvent in biphasic systems, Energy Environ.Sci.,
2012,5,8199-8203”。
In the present invention, the preparation method of strong solid acid catalyst is can to use precipitation-impregnation to be known in the art
Method.For details, reference can be made to document " solid acid and fine chemistry industry " and " SO4 2-/MxOyThe progress of type solid super acid catalyst, is answered
With chemical industry, 2014, vol43,1879-1883 ".
The method of the present invention has preferable conversion ratio to lactone compound, has preferable choosing to benzene,toluene,xylene product
Selecting property, aromatics yield is low long with reaction step during solving the problems, such as previous biomass aromatic hydrocarbons.Using the method for the present invention,
Feed stock conversion can reach 99%；The selectivity of benzene,toluene,xylene target product can reach 94%, achieve
Preferable technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
50 grams of bagasse are weighed, is placed in autoclave pressure and is added 500 grams of water, add the salt of the 5mol/L of water quality 5%
Acid solution is warming up to 1 hour of reaction at 180 DEG C, cools down later, reaction solution after cooling is filtered, filter cake and filtering are obtained
Liquid, filtered fluid are that the hydrolyzate of cellulose uses mass spectrum to carry out identifying primary product for acetyl to reaction result after reaction
Propionic acid, yield are 16 grams.Obtained levulic acid adds hydrogen to obtain in fixed bed on the RuSn/C of 2% content of metal
Gamma-valerolactone, conversion ratio 99%, product yield 98%.
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2Catalyst is packed into fixed bed reactors.Reaction
Substrate is gamma-valerolactoneWeight space velocity 0.3 hour-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml min-1, temperature
400 DEG C of degree.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.
The selectivity that reaction substrate conversion ratio is 99%, BTX is 83%.
[embodiment 2]
5 grams are weighed through the S for removing water 12 hours dry at 120 DEG C2O8 2-/ZrO2Catalyst is packed into fixed bed reactors.Instead
Answering substrate is third dodecalactoneWeight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa,
Flow 20ml min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography is to reaction
As a result quantitative analysis is carried out.The selectivity that reaction substrate conversion ratio is 93%, BTX is 93%.
[embodiment 3]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2Catalyst is packed into fixed bed reactors.Reaction
Substrate is third caprolactoneWeight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1,
400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantitatively divides reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 84%, BTX is 87%.
[embodiment 4]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe3O4Catalyst is packed into fixed bed reaction
Device.Reaction substrate is gamma decalactoneWeight space velocity 5.0 hours-1, Hydrogen Vapor Pressure
1.0MPa, flow 20ml min-1, 500 DEG C of temperature.After reaction, qualitative analysis, chromatography are carried out to reaction result using mass spectrum
Quantitative analysis is carried out to reaction result.The selectivity that reaction substrate conversion ratio is 86%, BTX is 81%.
[embodiment 5]
5 grams are weighed through the Pt/SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2Catalyst is packed into fixed bed reactors.
Reaction substrate is third heptalactoneWeight space velocity 2.0 hours -1, Hydrogen Vapor Pressure 3.0MPa, flow 20ml
min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography determines reaction result
Amount analysis.The selectivity that reaction substrate conversion ratio is 85%, BTX is 82%.
[embodiment 6]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-ZrO2Catalyst is packed into fixed bed reaction
Device.Reaction substrate is third caprylolactoneWeight space velocity 0.8 hour-1, Hydrogen Vapor Pressure
1.0MPa, flow 40ml min-1, 400 DEG C of temperature.After reaction, qualitative analysis, chromatography are carried out to reaction result using mass spectrum
Quantitative analysis is carried out to reaction result.The selectivity that reaction substrate conversion ratio is 84%, BTX is 87%.
[embodiment 7]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-Al2O3Catalyst is packed into fixed bed reaction
Device.Reaction substrate is gamma-butyrolactonWeight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantifies reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 81%, BTX is 85%.
[embodiment 8]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalyst is packed into fixed bed
Reactor.Reaction substrate is 6-caprolactoneWeight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 50ml
min-1, 450 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography determines reaction result
Amount analysis.The selectivity that reaction substrate conversion ratio is 93%, BTX is 85%.
[embodiment 9]
5 grams are weighed through the SbF for removing water 12 hours dry at 120 DEG C5/SiO2-Al2O3Catalyst is packed into fixed bed reaction
Device.Reaction substrate is δ-valerolactoneWeight space velocity 3.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantifies reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 83%, BTX is 89%.
[embodiment 10]
60 grams of corn stalks are weighed, is placed in autoclave pressure and is added 700 grams of water, add the sulphur of the 5mol/L of water quality 7%
Acid solution is warming up at 180 DEG C and reacts 45 minutes, cools down later, reaction solution after cooling is filtered, filter cake and filtering are obtained
Liquid, filtered fluid are that the hydrolyzate of cellulose uses mass spectrum to carry out identifying primary product for acetyl to reaction result after reaction
Propionic acid, yield are 18 grams.Obtained levulic acid is in fixed bed in the Cu/SiO of 20% content of metal2Upper plus hydrogen obtains
To gamma-valerolactone, conversion ratio 99%, product yield 98%.
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-WO3Catalyst is packed into fixed bed reactors.
Reaction substrate is gamma-valerolactoneWeight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 500 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantifies reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 86%, BTX is 86%.
[embodiment 11]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-WO3Catalyst is packed into fixed bed reactors.
Reaction substrate is angelica lactone, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 380 DEG C of temperature.
After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate
The selectivity that conversion ratio is 92%, BTX is 88%.
[embodiment 12]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/TiO2-MoO3Catalyst is packed into fixed bed reactors.
Reaction substrate is gamma-valerolactoneWeight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 380 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography quantifies reaction result
Analysis.The selectivity that reaction substrate conversion ratio is 82%, BTX is 83%.
[embodiment 13]
5 grams are weighed through the BiF for removing water 12 hours dry at 120 DEG C3/Al2O3-B2O3Catalyst is packed into fixed bed reactors.
Reaction substrate is beta-propiolactoneWeight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature
420 DEG C of degree.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.
The selectivity that reaction substrate conversion ratio is 86%, BTX is 86%.
[embodiment 14]
5 grams are weighed through the NbF for removing water 12 hours dry at 120 DEG C3/Al2O3-B2O3Catalyst is packed into fixed bed reactors.
Reaction substrate is third caprolactoneWeight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml
min-1, 360 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography determines reaction result
Amount analysis.The selectivity that reaction substrate conversion ratio is 88%, BTX is 94%.
[embodiment 15]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-MnO2Catalyst is packed into fixed bed
Reactor.Reaction substrate is gamma-butyrolactonWeight space velocity 2.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml
min-1, 400 DEG C of temperature.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography determines reaction result
Amount analysis.The selectivity that reaction substrate conversion ratio is 89%, BTX is 85%.
[embodiment 16]
5 grams are weighed through the SO for removing water 12 hours dry at 120 DEG C4 2-/ZrO2-Fe2O3-Cr2O3Catalyst is packed into fixed bed
Reactor.Reaction substrate is angelica lactone, weight space velocity 1.0 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, temperature
380℃.After reaction, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Instead
Answering the selectivity that the substrate transformation rate is 92%, BTX is 84%.
[embodiment 17]
5 grams are weighed through the AlCl for removing water 12 hours dry at 120 DEG C3-CuCl2Catalyst is packed into fixed bed reactors.Instead
Answer substrate for gamma-valerolactone, weight space velocity 2.5 hours-1, Hydrogen Vapor Pressure 1.0MPa, flow 20ml min-1, 400 DEG C of temperature.Instead
After answering, qualitative analysis is carried out to reaction result using mass spectrum, chromatography carries out quantitative analysis to reaction result.Reaction substrate turns
The selectivity that rate is 83%, BTX is 82%.
Table 1
| Embodiment | Substrate | Catalyst | Conversion ratio/% | BTX selectivity/% |
| 1 | Gamma-valerolactone | SO4 2-/ZrO2 | 99 | 83 |
| 2 | Third dodecalactone | S2O8 2-/ZrO2 | 93 | 93 |
| 3 | Third caprolactone | SO4 2-/TiO2 | 84 | 87 |
| 4 | Gamma decalactone | SO4 2-/ZrO2-Fe3O4 | 86 | 81 |
| 5 | Third heptalactone | Pt/SO4 2-/TiO2 | 85 | 82 |
| 6 | Third caprylolactone | SO4 2-/TiO2-ZrO2 | 84 | 87 |
| 7 | Gamma-butyrolacton | SO4 2-/TiO2-Al2O3 | 81 | 85 |
| 8 | 6-caprolactone | SO4 2-/ZrO2-Fe2O3-Cr2O3 | 93 | 85 |
| 9 | δ-valerolactone | SbF5/SiO2-Al2O3 | 83 | 89 |
| 10 | Gamma-valerolactone | SO4 2-/TiO2-WO3 | 86 | 86 |
| 11 | Angelica lactone | SO4 2-/ZrO2-WO3 | 92 | 88 |
| 12 | Gamma-valerolactone | SO4 2-/TiO2-MoO3 | 82 | 83 |
| 13 | Beta-propiolactone | BiF3/Al2O3-B2O3 | 86 | 86 |
| 14 | Third caprolactone | NbF3/Al2O3-B2O3 | 88 | 94 |
| 15 | Gamma-butyrolacton | SO4 2-/ZrO2-Fe2O3-MnO2 | 89 | 85 |
| 16 | Angelica lactone | SO4 2-/ZrO2-Fe2O3-Cr2O3 | 92 | 84 |
| 17 | Gamma-valerolactone | AlCl3-CuCl2 | 83 | 82 |
Claims (9)
1. a kind of lactone compound aromatization method, is included under aromatization conditions, makes lactone compound and solid strong acid
The step of catalyst contact generates the arene stream containing benzene, toluene and dimethylbenzene；Wherein, the lactone compound has structure
Formula (I):
In formula (I), R1For C1-20Linear or branched alkyl group, C2-20Linear chain or branched chain alkenyl, C2-20Linear chain or branched chain alkynyl, C3-20Ring
Alkyl or C6-20Aryl；R2For hydrogen, C1-20Linear chain or branched chain carboxyl, furyl or hydroxyl alkyl furyl；Wherein, the hydroxyl
Alkyl furyl has structural formula (II):
In formula (II), R3For C1-20Linear or branched alkyl group, C2-20Linear chain or branched chain alkenyl, C2-20Linear chain or branched chain alkynyl；
The strong solid acid catalyst is selected from SO4 2-/ZrO2、S2O8 2-/ZrO2、SO4 2-/TiO2、SO4 2-/ZrO2-Fe3O4、Pt/
SO4 2-/TiO2、SO4 2-/TiO2-ZrO2、SO4 2-/TiO2-Al2O3、SO4 2-/TiO2-WO3、SO4 2-/ZrO2-Fe2O3-Cr2O3、
SbF5/SiO2-Al2O3、SO4 2-/ZrO2-WO3、SO4 2-/TiO2-MoO3、PF3/Al2O3-B2O3、AsF3/Al2O3-B2O3、SbF3/
Al2O3-B2O3、BiF3/Al2O3-B2O3、TaF3/Al2O3-B2O3、VF3/Al2O3-B2O3、NbF3/Al2O3-B2O3、SO4 2-/ZrO2-
Fe2O3-MnO2Or AlCl3-CuCl2At least one of.
2. lactone compound aromatization method according to claim 1, it is characterised in that in formula (I), R1For C2-10Straight chain or
Branched alkyl, C2-10Linear chain or branched chain alkenyl.
3. lactone compound aromatization method according to claim 1, it is characterised in that in formula (I), R2For C2-10Straight chain or
Branch carboxyl.
4. lactone compound aromatization method according to claim 1, it is characterised in that in formula (II), R3For C2-10Straight chain
Or branched alkyl, C2-10Linear chain or branched chain alkenyl.
5. lactone compound aromatization method according to claim 1, it is characterised in that the aromatization conditions are as follows: reaction
300~800 DEG C of temperature, Hydrogen Vapor Pressure 0.1~5MPa in terms of gauge pressure, raw material weight air speed 0.3~10 hour-1。
6. lactone compound aromatization method according to claim 5, it is characterised in that the aromatization conditions are as follows: reaction
300~650 DEG C of temperature, Hydrogen Vapor Pressure 0.5~4MPa in terms of gauge pressure, raw material weight air speed 0.3~5 hour-1。
7. lactone compound aromatization method according to claim 1, it is characterised in that the raw material comes from biological material
Material.
8. lactone compound aromatization method according to claim 1, it is characterised in that the raw material comes from xylitol, Portugal
At least one of grape sugar, cellobiose, hemicellulose or lignin.
9. lactone compound aromatization method according to claim 1, it is characterised in that the raw material comes from bagasse, Portugal
At least one of grape sugar, timber, corn stalk or straw straw.
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