CN106220464A - A kind of method being catalyzed α pinene dimerization reaction - Google Patents
A kind of method being catalyzed α pinene dimerization reaction Download PDFInfo
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- CN106220464A CN106220464A CN201610524540.9A CN201610524540A CN106220464A CN 106220464 A CN106220464 A CN 106220464A CN 201610524540 A CN201610524540 A CN 201610524540A CN 106220464 A CN106220464 A CN 106220464A
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- australene
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- 238000006471 dimerization reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 title claims abstract description 12
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 title claims abstract description 6
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 18
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 150000001768 cations Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000011572 manganese Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- MKBBSFGKFMQPPC-UHFFFAOYSA-N 2-propyl-1h-imidazole Chemical class CCCC1=NC=CN1 MKBBSFGKFMQPPC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 8
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000011565 manganese chloride Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000003292 diminished effect Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- -1 glyoxaline cation Chemical class 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002608 ionic liquid Substances 0.000 abstract description 2
- 150000007517 lewis acids Chemical class 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract 1
- 238000013019 agitation Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 235000007586 terpenes Nutrition 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000003505 terpenes Chemical class 0.000 description 4
- 229930006722 beta-pinene Natural products 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000005893 bromination reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 150000002773 monoterpene derivatives Chemical class 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000006280 diesel fuel additive Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane of uncertain configuration Natural products CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000002215 pyrolysis infrared spectroscopy Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/50—Diels-Alder conversion
- C07C2/52—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2527/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Inorganic Chemistry (AREA)
Abstract
The invention discloses one to haveThe Inorganic whisker heteropolyacid salt catalyst Mn of Lewis bisgallic acid0.5[MIMPS]2PW12O40The method of catalysis α pinene dimerization reaction.It is characterized in that respectively with the form of covalent bond and ionic bond by suitableAcid site and metal Lewis acid site introduce in the class ionic liquid cation structure of catalyst, and method for preparing catalyst is simple, and structure is clear and definite, and active component does not runs off, and show good catalysis activity and stability in α pinene dimerization reaction.This method for catalytic dimerization have simple and easy to do, catalyst is easily separated and reuse, advantages of environment protection, for α pinene high added value deep processing substitute fossil resource open a feasible new way.
Description
Technical field
The present invention relates to a kind of method being catalyzed australene dimerization reaction, be particularly to use to haveThe inorganic-organic hybrid heteropolyacid salt Mn of bisgallic acid0.5[MIMPS]2PW12O40For catalyst, it is catalyzed australene
The method of alkene dimerization reaction.
Background technology
Oleum Terebinthinae is one of the abundantest renewable natural resources, and China's Oleum Terebinthinae annual production 100000 tons occupies generation
First of boundary, develop and its deep process technology replacement non-renewable resources are had huge environmental benefit and economic worth.Australene is
The main component of Oleum Terebinthinae, content is up to more than 80%, it is possible to provide C10 skeleton and many rings and bridged ring, cyclic olefinic bond etc., has
Active chemical reactivity, is the important source material of many high added value fine chemical products.Traditionally, australene is in acid catalysis
Under the conditions of there is polyreaction, be mainly used in terpene resin and produce, thus when catalysis process is studied, be mainly concentrated in energy
Increase the australene degree of polymerization and improve (Shiwei Liu, Congxia Xie, Shitao Yu, et in terpene resin quality
al.Polymerization ofα-pinene using Lewis acidic ionic liquid as catalyst[J]
.Catalysis Communications, 2009,10,986-988), not deep to its mechanism of polymerization understanding, seldom there is pinane
Alkene oligomerization is studied.Until it is renewable to occur that prepared by the biomass material replacement fossil resources such as cyclic terpene alkene high-performance in recent years
The report of fuel, the especially important monoterpene raw material with the pure Hydrocarbon such as pinene and limonene as representative, its oligomeric hydrogenation
Product is considered as the reason developing novel Aero-Space high energy density fuel (High Energy Density Fuel, HEDF)
Think succedaneum (Tracy NI, Chen D, Crunkleton DW and Price GL.Hydrogenated monoterpenes
as diesel fuel additives[J].Fuel,2009,88,2238-2240；Peralta-Yahya PPOuellet M,
Chan R,Mukhopadhyay A,Keasling JD and Lee TS.Identification and microbial
production of a terpene-based advanced biofuel[J].Nature Comm,2011,2,483).Cause
This research australene dimerization reaction not only has theory significance, the most important environmental benefit and commercial application value.
Harvey etc. use ion exchange resin Amberlyst-15, perfluorinated sulfonic resin Nafion and acid montmorillonite
MMT-K-10 catalysis nopinene isomery and dimerization reaction, find that acid more weak Amberlyst-15 is difficult to catalysis and obtains dimerization
Thing, and with acid stronger Nafion and MMT-K-10 can obtain higher yields dimer (B.G.Harvey,
M.E.Wright,R.L.Quintana.High-Density Renewable Fuels Based on the Selective
Dimerization of Pinenes[J].Energy Fuels.2010,24,267-273；Heather A.Meylemans,
Roxanne L.Quintana,Benjamin G.Harvey.Efficient conversion of pure and mixed
terpene feedstocks to high density fuels[J].Fuel,2012,97,560-568).Zou Jijun etc. are also
Finding, the acidity of Al-MCM-41 mesopore molecular sieve is to affect direct factor, the total acid content of nopinene dimerization reaction catalytic effect
The most, acid strength is the highest, catalytic effect the best (Jijun Zou, Na Chang, Xiangwen Zhang, et
al.Isomerization and dimerization of pinene using Al-incorporated MCM-
41mesoporous materials[J].ChemCatChem,2012,4,1289-1297).Use in above-mentioned technology easily divides
In a lot of acid catalyzed reactions, certain progress is achieved from the solid acid catalyst of recoverable.But meanwhile, resinae is urged
The chemical stability of formed material, and the problem such as the preparation repeatability of montmorillonite and meso-porous molecular sieve material, acid sites distribution also
It is directly to limit its key issue putting into actual application in acid catalyzed reaction technique.Additionally, main the grinding of above-mentioned background technology
Study carefully object and be all the dimerization reaction of nopinene, therefore, develop a kind of prepare simple, structure clearly, the catalyst of stability and high efficiency uses
In the dimerization reaction of biomass Oleum Terebinthinae main component australene, thus provide raw material for novel biomass base HEDF, be Colophonium
Field of deep and the current demand in energy greenization field.
Summary of the invention
It is an object of the present invention to provide and a kind of prepare simple, structure and determine haveThe nothing of bisgallic acid
Machine-organic composite heteropolyacid salt Mn0.5[MIMPS]2PW12O40Catalyst, is applied to australene dimerization reaction and prepares the side of dimer
Method, thus provide raw material for biomass high-energy-density aviation fuel.
Technical scheme is as follows:
Having described in technical solution of the present inventionThe inorganic-organic hybrid heteropolyacid salt of bisgallic acid
Mn0.5[MIMPS]2PW12O40Catalyst australene dimerization reaction is carried out in batch (-type) normal pressure reactor, and raw material is australene
Alkene, uses toluene as solvent:
Equipped with condensing reflux pipe, thermometer 100mL there-necked flask in add 0.60g haveDouble
Acid inorganic-organic hybrid heteropolyacid salt Mn0.5[MIMPS]2PW12O40Catalyst, 10mL toluene, at N2Protection under, machinery
Stir and be warming up to 80 DEG C, being slowly added dropwise 10mL australene (10-12d/min), after dropping, reacting 16h.After reaction terminates
Standing, catalyst sedimentation to reactor bottom, the method for available decant separates and direct reuse, and upper strata reactant mixture is clear
Liquid, can be directly as the raw material of follow-up Turpentine biomass high-density propellant after solvent toluene is distilled off.
Having described in technique schemeThe inorganic-organic hybrid heteropolyacid salt of bisgallic acid
Mn0.5[MIMPS]2PW12O40Catalyst, its preparation method is:
(1) organic intermediate synthesis:
The 250mL reaction bulb be furnished with mechanical agitation, thermometer, constant pressure funnel and reflux condensing tube adds
0.3mol1,3-propane sultone and 150mL ethyl acetate, be warming up to 50 DEG C by mixed liquor, be slowly added dropwise (6～7d/min) with
The N-Methylimidazole. of the amount of the materials such as PS, after dropping, insulation reaction 2h, filtration under diminished pressure, filter cake second
Acetoacetic ester washs 3 times, is dried 2h, obtains intermediate 1-methyl-3-(3-sulfonic group) propyl imidazole salt white powder at 110 DEG C
End.
(2) haveThe inorganic-organic hybrid heteropolyacid salt Mn of bisgallic acid0.5[MIMPS]2PW12O40's
Synthesis
Intermediate 1-methyl-3-(3-sulfonic group) the propyl imidazole salt that step (1) obtained, phosphotungstic acid are by the amount ratio of material
2:1 joins in there-necked flask (100mL), adds 20mL deionized water and makes it dissolve, after room temperature (25 DEG C) mechanical agitation 12h,
Adding the manganese chloride of the amount of 1/4 times of phosphotungstic acid material, liter high-temperature is to 50 DEG C simultaneously, and after continuing stirring 12h, decompression distillation removes
Water, 110 DEG C of dry 6h, gained pale solid is catalyst Mn0.5[MIMPS]2PW12O40。
Having prepared by the present inventionThe inorganic-organic hybrid heteropolyacid salt Mn of bisgallic acid0.5
[MIMPS]2PW12O40, use mentality of designing and the preparation method of similar acidic functionalized ionic liquid, have preparation method simple,
The feature that structure is clear and definite；In catalyst structureAcid site and Lewis acid site are respectively with covalent bond and ionic bond
Form introduces, and active component stably not easily runs off.This catalyst shows good catalysis activity in australene dimerization reaction
And stability, Catalytic processes is simple, it is easy to separates and reuses, and provides an effective way for australene high value added utilization
Footpath.
Accompanying drawing explanation
Fig. 1 is embodiment 1 prepared catalyst Mn0.5[MIMPS]2PW12O40Prepare reaction equation.
Fig. 2 is the FT-IR that embodiment 1, comparative example 2 prepared catalyst and raw material thereof and embodiment 3 reclaim catalyst
Spectrogram；Wherein (a) MIMPS (b) H3PW12O40(c)H[MIMPS]2PW12O40(d)Mn0.5[MIMPS]2PW12O40E () reclaims Mn0.5
[MIMPS]2PW12O40。
Fig. 3 is the XRD spectra of embodiment 1 prepared catalyst and raw material thereof；Wherein (a) H3PW12O40(b)Mn0.5
[MIMPS]2PW12O40(c)MnCl2、MIMPS、H3PW12O40Three's mechanical impurity.
Fig. 4 is the TG-DTG spectrogram of embodiment 1 prepared catalyst.
Fig. 5 is the Py-IR spectrogram of embodiment 1 prepared catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the inventive method is further illustrated, but be not limitation of the invention.
Embodiment 1
0.3mol is added in the 250mL reaction bulb be furnished with mechanical agitation, thermometer, Dropping funnel and reflux condensing tube
PS and 150mL ethyl acetate, be warming up to 50 DEG C by mixed liquor, is slowly added dropwise (6～7d/min) and 1,3-third
The N-Methylimidazole. of the amount of the materials such as alkane sultone, after dropping, insulation reaction 2h, filtration under diminished pressure, filter cake ethyl acetate
Wash 3 times, at 110 DEG C, be dried 2h, obtain intermediate 1-methyl-3-(3-sulfonic group) propyl imidazole salt white powder.
2.50mmol phosphotungstic acid is added, in 5.00mmol in the there-necked flask (100mL) being furnished with mechanical agitation, thermometer
Mesosome 1-methyl-3-(3-sulfonic group) propyl imidazole salt, adds 20mL deionized water and makes it dissolve, room temperature (25 DEG C) stirring 12h
After, adding 1.25mmol manganese chloride, liter high-temperature is to 50 DEG C simultaneously, continues stirring 12h, and decompression distillation removes water, and 110 DEG C are dried
6h, obtains Mn0.5[MIMPS]2PW12O40Pale solid.Its fusing point > 300 DEG C, insoluble in toluene, insoluble in australene.Such as Fig. 2
Shown in (d), IR (KBr, v/cm-1) characterization result is: 1574,1463,1181,1086,976,885,811,742；Such as Fig. 2 (b)
Shown XRD figure spectrum, because cationic components replaces the Hydrogen Proton in phosphotungstic acid, cause its diffraction maximum to weaken, it was demonstrated that Mn0.5
[MIMPS]2PW12O40The formation of structure；TG-DTG collection of illustrative plates as shown in Figure 3,160 DEG C of mass losses are knot contained in catalyst
Brilliant water, 450 DEG C of mass losses are that intermediate cation is decomposed and caused, 621 DEG C, 712 DEG C of mass losses be phosphotungstic acid root anion
Decompose；Use pyridine-IR (KBr, v/cm-1) characterize acid site type, as shown in Figure 5: peak instruction near 1540In
The heart, near 1450 peak instruction Lewis center, it was demonstrated that this catalyst hasBisgallic acid.
Table 1The bisgallic acid inorganic-organic hybrid heteropolyacid salt catalytic performance to australene dimerization reaction
Embodiment 2
Equipped with reflux condensing tube, thermometer 100mL there-necked flask in add 0.60g catalyst Mn0.5[MIMPS]2PW12O40, 10mL toluene, at N2Protection under, mechanical agitation is also warming up to 80 DEG C, is slowly added dropwise 10mL australene (10-12d/
Min), reaction 16h.Reaction terminates cooling and stands, and catalyst sedimentation to reactor bottom, it is clear that decant separates upper strata reactant mixture
Liquid, with its composition of gas chromatographic analysis, catalytic reaction the results are shown in Table 1.
Embodiment 3-10
The solid catalyst separated with upper strata organic reaction mixture in embodiment 2, in same reaction unit, without place
Reason is directly circulated use: add 10mL toluene, at N2Protection under, mechanical agitation is also warming up to 80 DEG C, is slowly added dropwise
10mL (10-12d/min) australene, reacts 16h, and reaction terminates cooling and stands, and catalyst sedimentation to reactor bottom, decant divides
Go out upper strata reactant mixture clear liquid, with its composition of gas chromatographic analysis, so carry out catalyst and recycle experiment eight times, gained
Catalyst recycles and the results are shown in Table 2.
Table 2Bisgallic acid type inorganic-organic hybrid heteropolyacid salt catalyst Mn0.5[MIMPS]2PW12O40Weight
Multiple serviceability
Comparative example 1
0.3mol is added in the 250mL reaction bulb be furnished with mechanical agitation, thermometer, Dropping funnel and reflux condensing tube
PS and 150mL ethyl acetate, be warming up to 50 DEG C by mixed liquor, is slowly added dropwise (6～7d/min) and 1,3-third
Alkane sultone equimolar N-Methylimidazole., after dropping, insulation reaction 2h, filtration under diminished pressure, filter cake ethyl acetate washs 3
Secondary, at 110 DEG C, it is dried 2h, obtains intermediate 1-methyl-3-(3-sulfonic group) propyl imidazole salt white powder.
2.50mmol phosphotungstic acid is added, in 2.50mmol in the there-necked flask (100mL) being furnished with mechanical agitation, thermometer
Mesosome 1-methyl-3-(3-sulfonic group) propyl imidazole salt, adds 20mL deionized water and makes it dissolve, room temperature (25 DEG C) stirring 12h
After, taking 2.50mmol manganese chloride and add in there-necked flask, liter high-temperature is to 50 DEG C simultaneously, continues stirring 12h, and decompression distillation removes
Water, 110 DEG C of dry 6h, gained pale solid is comparative catalyst Mn [MIMPS] PW12O40.Its fusing point > 300 DEG C, do not dissolve in
Toluene, insoluble in australene.
Comparative example 2
0.3mol1 is added in the 250mL reaction bulb be furnished with mechanical agitation, thermometer, Dropping funnel and reflux condensing tube,
3-propane sultone and 150mL ethyl acetate, be warming up to 50 DEG C by mixed liquor, is slowly added dropwise (6～7d/min) and 1,3-propane
The N-Methylimidazole. of the amount of the materials such as sultone, after dropping, insulation reaction 2h, filtration under diminished pressure, filter cake ethyl acetate is washed
Wash 3 times, at 110 DEG C, be dried 2h, obtain intermediate 1-methyl-3-(3-sulfonic group) propyl imidazole salt white powder.
2.50mmol phosphotungstic acid is added, in 5.00mmol in the there-necked flask (100mL) being furnished with mechanical agitation, thermometer
Mesosome 1-methyl-3-(3-sulfonic group) propyl imidazole salt, adds 20mL deionized water and makes it dissolve, room temperature (25 DEG C) stirring 24h,
Decompression distillation is except water, and 110 DEG C of dry 6h, gained white solid is comparative catalyst H [MIMPS]2PW12O40, its fusing point 135.6-
137.5 DEG C, insoluble in toluene, insoluble in australene.As shown in Fig. 2 (c), IR (KBr, v/cm-1) characterization result is: 1576,
1467,1180,1076,981,888,793,734。
Comparative example 3
N-Methylimidazole. is added in the there-necked flask (100mL) being furnished with mechanical agitation, thermometer, reflux condensing tube
0.10mo1 and 1-bromination of n-butane 0.12mol, under mechanical agitation, 70 DEG C of insulation reaction 36h, decompression distillation is except unreacted 1-
Bromination of n-butane, obtaining light yellow transparent liquid is intermediate 1-butyl-3-methylimidazolium bromide salt.
2.50mmol phosphotungstic acid is added, in 5.00mol in the there-necked flask (100mL) being furnished with mechanical agitation, thermometer
Mesosome 1-butyl-3-methylimidazolium bromide salt, adds 20mL deionized water and makes it dissolve, and after room temperature (25 DEG C) stirring 12h, takes
In 1.25mmol manganese chloride addition there-necked flask, liter high-temperature is to 50 DEG C simultaneously, continues stirring 12h, and decompression is distilled and removed water, and 110
DEG C dry 6h, gained pale solid is comparative catalyst Mn0.5[BMIM]2PW12O40, its fusing point > and 300 DEG C, insoluble in toluene,
Insoluble in australene.
Comparative example 4
Equipped with condensing reflux pipe, thermometer 100mL there-necked flask in add the catalysis of preparation in 0.60g comparative example 1
Agent Mn [MIMPS] PW12O40, 10mL toluene, at N2Protection under, mechanical agitation is also warming up to 80 DEG C, is slowly added dropwise 10mL australene
Alkene (10-12d/min), reacts 16h.Reaction terminates cooling and stands, and catalyst sedimentation to reactor bottom, it is anti-that decant separates upper strata
Answering mixture clear liquid, with its composition of gas chromatographic analysis, catalytic reaction the results are shown in Table 1.
Comparative example 5
Equipped with condensing reflux pipe, thermometer 100mL there-necked flask in add the catalysis of preparation in 0.60g comparative example 2
Agent H [MIMPS]2PW12O40, 10mL toluene, at N2Protection under, mechanical agitation is also warming up to 80 DEG C, is slowly added dropwise 10mL australene
Alkene (10-12d/min), reacts 16h.Reaction terminates cooling and stands, and catalyst sedimentation to reactor bottom, it is anti-that decant separates upper strata
Answering mixture clear liquid, with its composition of gas chromatographic analysis, catalytic reaction the results are shown in Table 1.
Comparative example 6
Equipped with condensing reflux pipe, thermometer 100mL there-necked flask in add the catalysis of preparation in 0.60g comparative example 3
Agent Mn0.5[BMIM]2PW12O40, 10mL toluene, at N2Protection under, mechanical agitation is also warming up to 80 DEG C, be slowly added dropwise 10mL α-
Pinene (10-12d/min), reacts 16h.Reaction terminates cooling and stands, and catalyst sedimentation to reactor bottom, decant separates upper strata
Reactant mixture clear liquid, with its composition of gas chromatographic analysis, catalytic reaction the results are shown in Table 1.
Claims (1)
1. the method for an inorganic-organic hybrid heteropolyacid salt catalysis australene dimerization reaction, it is characterised in that: use manganese metal
The glyoxaline cation of ion and sulfonic functional, collectively as the anti-lotus cation of phosphotungstic acid root, is prepared and is hadThe inorganic-organic hybrid heteropolyacid salt Mn of bisgallic acid0.5[MIMPS]2PW12O40As catalyst, catalysis α-
Pinene dimerization reaction；
Wherein said inorganic-organic hybrid heteropolyacid salt Mn0.5[MIMPS]2PW12O40Preparation method be: will wait material amount
PS and N-Methylimidazole. be 50 DEG C of reaction 2h in ethyl acetate solvent, and the solid filtration under diminished pressure obtained also uses second
Acetoacetic ester washs three times, is dried 2h, obtains intermediate 1-methyl-3-(3-sulfonic group) propyl imidazole salt at 110 DEG C；By intermediate 1-
Methyl-3-(3-sulfonic group) propyl imidazole salt, phosphotungstic acid press the amount of material than 2:1 in aqueous room temperature reaction 12h after, then add
Entering the manganese chloride of the amount of 1/4 times of phosphotungstic acid material, be warming up to 50 DEG C of reaction 12h, distillation is except water and is dried, and obtains for australene
The inorganic-organic hybrid heteropolyacid salt catalyst Mn of dimerization reaction0.5[MIMPS]2PW12O40；
Wherein said dimerization reaction method is: use 100mL there-necked flask to have as reactor, additionThe inorganic-organic hybrid heteropolyacid salt Mn of bisgallic acid0.5[MIMPS]2PW12O40Catalyst 0.60g, toluene
10mL, at N2Protection under, dropping australene 10mL in 80 DEG C react 16h, reaction terminate after, the method for catalyst decant is divided
From also direct reuse.
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