CN103785468A - Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole - Google Patents
Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole Download PDFInfo
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- WEEGYLXZBRQIMU-UHFFFAOYSA-N Eucalyptol Chemical compound C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000007787 solid Substances 0.000 title claims abstract description 65
- 239000011964 heteropoly acid Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 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 abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 230000035484 reaction time Effects 0.000 claims abstract description 16
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- 238000010438 heat treatment Methods 0.000 claims abstract description 7
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- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 41
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 41
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 14
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- 238000001291 vacuum drying Methods 0.000 claims description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 12
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- RFFOTVCVTJUTAD-UHFFFAOYSA-N cineole Natural products C1CC2(C)CCC1(C(C)C)O2 RFFOTVCVTJUTAD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
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- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 238000001354 calcination Methods 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
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- 238000004458 analytical method Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 5
- -1 monoterpenes compound Chemical class 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 241000723346 Cinnamomum camphora Species 0.000 description 3
- 244000166124 Eucalyptus globulus Species 0.000 description 3
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 3
- 235000019134 Eucalyptus tereticornis Nutrition 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 description 2
- IBVJWOMJGCHRRW-UHFFFAOYSA-N 3,7,7-Trimethylbicyclo[4.1.0]hept-2-ene Chemical compound C1CC(C)=CC2C(C)(C)C12 IBVJWOMJGCHRRW-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 2
- 150000002268 gamma-terpinene derivatives Chemical class 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGLDWXZKYODSOB-UHFFFAOYSA-N α-phellandrene Chemical compound CC(C)C1CC=C(C)C=C1 OGLDWXZKYODSOB-UHFFFAOYSA-N 0.000 description 2
- KQAZVFVOEIRWHN-UHFFFAOYSA-N α-thujene Chemical compound CC1=CCC2(C(C)C)C1C2 KQAZVFVOEIRWHN-UHFFFAOYSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- IBVJWOMJGCHRRW-DTWKUNHWSA-N 2-Carene Natural products C1CC(C)=C[C@H]2C(C)(C)[C@@H]12 IBVJWOMJGCHRRW-DTWKUNHWSA-N 0.000 description 1
- 244000080208 Canella winterana Species 0.000 description 1
- 235000008499 Canella winterana Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 240000005125 Myrtus communis Species 0.000 description 1
- 235000013418 Myrtus communis Nutrition 0.000 description 1
- 241001593968 Vitis palmata Species 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- NDVASEGYNIMXJL-UHFFFAOYSA-N beta-sabinene Natural products C=C1CCC2(C(C)C)C1C2 NDVASEGYNIMXJL-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000000287 crude extract Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- WTARULDDTDQWMU-UHFFFAOYSA-N β-pinene Chemical compound C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses relates to 1,8-cineole and provides a preparation method for a solid heteropolyacid catalyst for synthesizing the 1,8-cineole. The solid heteropolyacid catalyst has the pollution-free, corrosion-free and reproducible effects and is high in catalysis activity and high in selectivity. The preparation method for the solid heteropolyacid catalyst comprises the steps of calcining a catalyst carrier; adding calcined catalyst carrier particles into a heteropolyacid aqueous solution, then adding ethyl alcohol, performing stirring and suction filtration to obtain a solid filter cake, and then drying and calcining the solid filter cake to obtain the solid heteropolyacid catalyst. A method for synthesizing the 1,8-cineole by catalyzing alpha-terpilenol by the solid heteropolyacid catalyst comprises the steps of adding the alpha-terpilenol and a solvent into a three-neck round-bottom flask, heating the flask to a pointed reaction temperature, adding the phosphotungstic acid/silicon dioxide catalyst to perform reaction, stopping heating-stirring when the pointed reaction time is achieved, cooling to the room temperature, and performing suction filtration and separation to obtain a reaction product.
Description
Technical field
The present invention relates to 1, 8-Cineole, especially relate to a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole.
Background technology
1, 8-Cineole, formal name used at school is 1,3,3-trimethyl-2-oxabicyclo [2,2,2] octane, is a kind of monoterpenes compound, has refrigerant, fragrant pungent, the camphoraceous smell of class.Natural 1,8-Cineole is mainly present in myrtle blue gum and canella camphor tree, it is a kind of important fine chemical product, be widely used in food, daily use chemicals, medicine and catalyst and the industrial circle (Li Shiyu such as prepared, Wang Jingkang. Cineole application and preparation summary [J]. fine chemistry industry, 1995,12 (5): 12).
At present, all adopt natural extraction method to prepare 1 both at home and abroad, 8-Cineole product, its key step is: first adopt steam distillation from the branches and leaves of blue gum or camphor tree, to obtain crude extract eucalyptus oil, then obtain the 1, 8-Cineole industrial products (Zhang Guangqiu of certain purity by process for purification such as rectifying, extraction and crystallizations, Wang Jiong, Yuan Yonghua. Cineole process for refining Primary Study [J]. Yunnan Institute for nationalities's journal (natural science edition), 2012,2:010).Because natural plants blue gum or Camphor resources are limited in recent years, cause 1, 8-Cineole product yield to be difficult to meet the need of market; In addition, because impurity component in eucalyptus oil is more, mainly contain: citrene, australene, nopinene, laurene, α-phellandrene, γ-terpinenes, to P-cymene, linalool, terpinene-4 alcohol, terpinol etc. (Li Shiyu. the purifying [J] of Cineole. fine chemistry industry, 2006,23 (1): 35-37), and most impurity components and 1, boiling point and the dissolution properties of 8-Cineole are more approaching, so adopt the process for purification such as traditional rectifying, extraction and crystallization to be difficult to obtain highly purified 1, 8-Cineole industrial products.
In recent years, some external researchers are devoted to study on the synthesis and the exploitation of 1, 8-Cineole.People (the Greider CE such as Greider CE, Cleveland.Process for the production of cineole:U.S.Patent[P] .1935) carry out the Primary Study of the synthetic Cineole of terpinol isocatalysis, prove theoretically the feasibility of the synthetic 1, 8-Cineole of catalytic reaction; People (the Mitchell P W D.Improved method for the preparation of1 such as Mitchell P W D, 4-cineole:U.S.Patent4,831,163[P] .1989-5-16) take terpineol or terpinol as raw material, under the effect of liquid organic acid or inorganic acid, catalyze and synthesize 1, 8-Cineole;
the people such as L (
l, Boido E, Carrau F, et al.Terpene compounds as possible precursors of1,8-cineole in red grapes and wines[J] .Journal of agricultural and food chemistry, 2005,53 (5): 1633-1636) also proving again of research, under liquid acid catalysis, citrene and alpha-terpineol all can be converted into 1, 8-Cineole, and it is as follows to have proposed possible reaction mechanism:
But the catalyst that above-mentioned research institute adopts is mainly the liquid acid such as inorganic acid or organic acid, the 1, 8-Cineole output that reaction obtains is very low, and liquid acid catalyst consumption is large, be difficult to recycle, and there is the problem such as contaminated environment and severe corrosion equipment in liquid acid catalyst.
the people such as E J (
lana E J, da Silva Rocha K A, Kozhevnikov I V, et al.Synthesis of1,8-cineole and1,4-cineole by isomerization of α-terpineol catalyzed by heteropolyacid[J] .Journal of Molecular Catalysis A:Chemical, 2006,259 (1): 99-102) will there is the heteropoly acid of Keggin structure first: phosphotungstic acid (H
3pW
12o
40) and the solid acid that makes of load phosphotungstic acid as catalyst, catalysis alpha-terpineol iso-synthesis 1, 8-Cineole in homogeneous phase and heterogeneous catalysis system respectively, the carbonium ion reaction mechanism that has proposed synthetic 1, 8-Cineole is as follows:
The solid acid catalyst of load phosphotungstic acid overcome the shortcoming of aforesaid liquid acid catalyzed reaction, and in heterogeneous catalysis system, obtained 70% alpha-terpineol conversion ratio and approached 35% 1, 8-Cineole selective.In view of this, catalyze and synthesize conversion ratio that 1, 8-Cineole is higher and selective for realizing alpha-terpineol, need to research and develop novel solid acid catalyst, and prepare the key that efficient reproducible solid heteropoly acid catalyst is synthetic 1, 8-Cineole technology.
Summary of the invention
The object of the invention is to for current liquid acid catalyst catalysis alpha-terpineol synthetic 1, the problem that 8-Cineole exists, provide pollution-free, corrosion-free, reproducible and there is higher catalytic activity and compared with the preparation method of the solid heteropoly acid catalyst of a kind of synthetic 1, 8-Cineole of high selectivity.
Another order of the present invention is to provide the method that adopts the synthetic 1, 8-Cineole of described solid heteropoly acid catalyst alpha-terpineol.
The preparation method of the solid heteropoly acid catalyst of described synthetic 1, 8-Cineole, comprises the following steps:
1) catalyst carrier roasting;
2) catalyst carrier particle after roasting is added in the heteropoly acid aqueous solution, then add ethanol, stir, suction filtration obtains solid filter cake;
3) by step 2) solid filter cake that obtains is dry, and roasting, obtains solid heteropoly acid catalyst, and described solid heteropoly acid catalyst is phosphotungstic acid/silica solid heteropolyacid catalyst.
In step 1), described catalyst carrier can be selected from the one in silica, molecular sieve, silica gel, active carbon etc.; The method of described roasting can be: under normal temperature, be warming up to 180 ℃, heating-up time 2h, is warming up to 350 ℃ again after constant temperature 1h, then the time of heating up be 2h, then be warming up to 550 ℃ the 3rd time after constant temperature 1h, the time of heating up for the 3rd time is 2h, then constant temperature 6h.
In step 2) in, described heteropoly acid can adopt the one in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid etc.; The mass ratio of described heteropoly acid and catalyst carrier can be (1～3): 5; The concentration of the described heteropoly acid aqueous solution can be 0.016～0.048g/ml; The volume ratio of described ethanol and the heteropoly acid aqueous solution can be 2: 1; The time of described stirring can be 12h.
In step 3), described dry condition can be: temperature is 50 ℃, and the time is 24～48h, and dry method is the one in vacuum drying, constant temperature forced air drying, supercritical fluid drying etc.; Vacuum drying vacuum can be 0.08MPa; The condition of described roasting can be: be placed in Muffle furnace roasting, the temperature of roasting is 200 ℃, and the time of roasting is 4h.
Adopt the method for the synthetic 1, 8-Cineole of described solid heteropoly acid catalyst alpha-terpineol as follows:
1) in three neck round-bottomed flasks, add alpha-terpineol and solvent, mix, heating, then add phosphotungstic acid/silica solid heteropolyacid catalyst to start reaction; Described solvent is selected from the one in cyclohexane, isopropyl alcohol, n-butanol, ethyl acetate; The mass ratio of described alpha-terpineol and solvent is 1: 33.7, and reaction temperature is 50～70 ℃, and the mass ratio of phosphotungstic acid/silica solid heteropolyacid catalyst and reaction raw materials liquid is 0.006: 1～0.0125: 1, and the reaction time is 2～7h.
2) reach to specify after the reaction time and stop adding thermal agitation, question response solution temperature drops to after room temperature, and suction filtration separates and obtains product, adopts gas chromatography-mass spectrometry chromatogram instrument analytical reactions product composition.
Main outstanding advantages of the present invention is as follows:
1) adopt straightforward procedure to prepare phosphotungstic acid/silica solid heteropolyacid catalyst of high catalytic activity and high selectivity.This catalyst stability is good, and environmentally safe is corrosion-free to equipment, is soluble in polar solvent, is easy to reclaim renewable repeated use.
2) reactions steps of the synthetic 1, 8-Cineole of phosphotungstic acid/silica solid heteropolyacid catalyst catalysis alpha-terpineol is simple, processing ease, and reaction temperature is moderate, and energy consumption is low, the selective height of the conversion ratio of alpha-terpineol and 1, 8-Cineole.
3) effect of the present invention can be by phosphotungstic acid/silica solid heteropolyacid catalyst catalysis alpha-terpineol of preparation synthetic 1, selective and the conversion ratio check of 8-Cineole reaction, the selective and conversion ratio of this reaction is mainly subject to the catalytic activity and selective and reaction temperature, reaction time, the control of raw material proportioning of phosphotungstic acid/silica solid heteropolyacid catalyst.Adopt the synthetic 1, 8-Cineole of phosphotungstic acid/silica solid heteropolyacid catalyst catalysis alpha-terpineol of preparing of the present invention, the highest 1, 8-Cineole that obtains 97.93% alpha-terpineol conversion ratio and 37.35% is selective.
Accompanying drawing explanation
The GC-MS spectrogram example of Fig. 1 product of the present invention.
The specific embodiment
The preparation method who presses phosphotungstic acid/silica solid heteropolyacid catalyst in summary of the invention, prepares solid acid heteropolyacid catalyst, and carries out the reaction of the synthetic 1, 8-Cineole of catalysis alpha-terpineol.Following examples further illustrate flesh and blood of the present invention in connection with accompanying drawing, but content of the present invention is not limited to this example.
Embodiment 1:
First obtain dry silica supports by calcination procedure roasting in Muffle furnace, calcination procedure is: slowly 2h to 180 ℃ of intensification (constant temperature 1h) under normal temperature; 2h to 350 ℃ (constant temperature 1h) more slowly heats up; 2h to 550 ℃ (constant temperature 6h) more slowly heats up.Press phosphotungstic acid and silica supports mass ratio 1: 5, add the phosphotungstic acid aqueous solution of 0.0016g/ml concentration, fixed rotating speed stirs after 12h, adds ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, and after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 69.18%, 1, 8-Cineole be selectively 34.79%.
Embodiment 2:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 5, add the phosphotungstic acid aqueous solution of 0.0048g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 97.60%, 1, 8-Cineole be selectively 29.35%.
Embodiment 3:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 2: 5, add the phosphotungstic acid aqueous solution of 0.0032g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 24h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 97.26%, 1, 8-Cineole be selectively 33.01%.
Embodiment 4:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 95.03%, 1, 8-Cineole be selectively 37.35%.
Embodiment 5:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 2h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 39%, 1, 8-Cineole be selectively 35.54%.
Embodiment 6:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 3h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 75.71%, 1, 8-Cineole be selectively 35.09%.
Embodiment 7:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,60 ℃ of reaction temperatures, reaction time 7h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 97.69%, 1, 8-Cineole be selectively 33.92%.
Embodiment 8:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,50 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 14.26%, 1, 8-Cineole be selectively 34.57%.
Embodiment 9:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0065: 1,70 ℃ of reaction temperatures, reaction time 5h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 97.93%, 1, 8-Cineole be selectively 16.08%.
Embodiment 10:
First (see embodiment 1 by calcination procedure, following examples are all identical) in Muffle furnace roasting obtain dry silica supports, press phosphotungstic acid and silica supports mass ratio 3: 10, add the phosphotungstic acid aqueous solution of 0.0024g/ml concentration, fixed rotating speed stirs after 12h, add ethanol at 2: 1 by the volume ratio of ethanol and phosphotungstic acid aqueous solution, after fixed rotating speed stirs, suction filtration obtains solid filter cake.By filter cake vacuum drying 48h under 50 ℃ of baking temperatures and 0.08MPa vacuum, then at 200 ℃ roasting 4h, obtain phosphotungstic acid/silica solid heteropolyacid catalyst.Catalyze and synthesize 1,8-Cineole reaction is pressed raw material alpha-terpineol and solvent cyclohexane mass ratio 1: 33.7, catalyst and reaction solution mass ratio 0.0125: 1,70 ℃ of reaction temperatures, reaction time 3h, product is through gas chromatography-mass spectrometry chromatogram analysis, and the conversion ratio that calculates alpha-terpineol is 78.11%, 1, 8-Cineole be selectively 33.06%.
The analysis condition of gas chromatography-mass spectrometry chromatogram: chromatographic column Rtx-5 capillary column 30m × 250 μ m × 0.25 μ m; 60 ℃ of (2min)～90 ℃ of temperature programming, 3 ℃/min; 90 ℃～260 ℃, 20 ℃/min; 210 ℃ of sample introduction temperature; Carrier gas He, 3ml/min; Sample size 1
μl, split ratio (volume ratio) 60: 1; 210 ℃ of interface temperature; Ionization mode is electronics bombardment; Ionizing energy 70eV; Multiplier voltage 0.77kV; Sweep limits 20～650amu, adopts full scan working method.By retrieval NIST98 spectrogram storehouse, and combined standard mass spectral database and related documents determine product composition, and instantiation is as shown in Fig. 1 and table 1.
The composition example of table 1 product of the present invention
| Retention time (min) | Component title |
| 8.674 | α-thujene |
| 9.066 | Isosorbide-5-Nitrae-Cineole |
| 9.126 | 2-carene |
| 9.588 | 1,2-bis-(1-methyl ethylene)-cyclobutane |
| 9.678 | 1, 8-Cineole |
| 10.769 | γ-terpinenes |
| 11.986 | Terpinolene |
| 14.44 | Alpha-terpineol |
The present invention adopts a kind of heteropoly acid with higher catalytic activity: phosphotungstic acid synthesizes the major catalyst of 1, 8-Cineole as catalysis alpha-terpineol, its good stability, and environmentally safe, is a kind of coming green catalyst.But due to little (the < 10m of the specific area of phosphotungstic acid
2/ g), be soluble in polar solvent, be difficult to reclaim, bring larger difficulty to product postprocessing.Therefore, the present invention adopts mesoporous silica particles to prepare solid heteropoly acid catalyst as the carrier of phosphotungstic acid, not only improve the specific area of phosphotungstic acid, and can improve the catalytic performance of phosphotungstic acid in heterogeneous catalytic reaction, also there is reusable, the advantage such as etching apparatus not simultaneously.
Claims (10)
1. the preparation method of the solid heteropoly acid catalyst of synthetic 1, a 8 ?Cineole, is characterized in that comprising the following steps:
1) catalyst carrier roasting;
2) catalyst carrier particle after roasting is added in the heteropoly acid aqueous solution, then add ethanol, stir, suction filtration obtains solid filter cake;
3) by step 2) solid filter cake that obtains is dry, and roasting, obtains solid heteropoly acid catalyst, and described solid heteropoly acid catalyst is phosphotungstic acid/silica solid heteropolyacid catalyst.
2. a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole as claimed in claim 1, is characterized in that in step 1), described catalyst carrier is selected from the one in silica, molecular sieve, silica gel, active carbon.
3. one synthesizes 1 as claimed in claim 1, the preparation method of the solid heteropoly acid catalyst of 8-Cineole, it is characterized in that in step 1), the method of described roasting is: under normal temperature, be warming up to 180 ℃, heating-up time 2h, is warming up to 350 ℃ again after constant temperature 1h, the time of heating up is again 2h, after constant temperature 1h, be warming up to 550 ℃ the 3rd time again, the time of heating up for the 3rd time is 2h, then constant temperature 6h.
4. a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole as claimed in claim 1, is characterized in that in step 2) in, described heteropoly acid adopts the one in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid; The mass ratio of described heteropoly acid and catalyst carrier can be (1～3): 5.
5. a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole as claimed in claim 1, is characterized in that in step 2) in, the concentration of the described heteropoly acid aqueous solution is 0.016～0.048g/ml.
6. a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole as claimed in claim 1, is characterized in that in step 2) in, the volume ratio of described ethanol and the heteropoly acid aqueous solution is 2: 1; The time of described stirring can be 12h.
7. one synthesizes 1 as claimed in claim 1, the preparation method of the solid heteropoly acid catalyst of 8-Cineole, it is characterized in that in step 3), described dry condition is: temperature is 50 ℃, time is 24～48h, and dry method is the one in vacuum drying, constant temperature forced air drying, supercritical fluid drying; Vacuum drying vacuum can be 0.08MPa.
8. a kind of preparation method of solid heteropoly acid catalyst of synthetic 1, 8-Cineole as claimed in claim 1, is characterized in that in step 3), the condition of described roasting is: be placed in Muffle furnace roasting, the temperature of roasting is 200 ℃, and the time of roasting is 4h.
9. adopt the method for the synthetic 1, 8-Cineole of solid heteropoly acid catalyst alpha-terpineol as claimed in claim 1, it is characterized in that comprising the following steps:
1) in three neck round-bottomed flasks, add alpha-terpineol and solvent, mix, heating, then add phosphotungstic acid/silica solid heteropolyacid catalyst to start reaction;
2) reach to specify after the reaction time and stop adding thermal agitation, question response solution temperature drops to after room temperature, and suction filtration separates and obtains product, adopts gas chromatography-mass spectrometry chromatogram instrument analytical reactions product composition.
10. method as claimed in claim 9, is characterized in that described solvent is selected from the one in cyclohexane, isopropyl alcohol, n-butanol, ethyl acetate; The mass ratio of described alpha-terpineol and solvent is 1: 33.7, and reaction temperature is 50～70 ℃, and the mass ratio of phosphotungstic acid/silica solid heteropolyacid catalyst and reaction raw materials liquid is 0.006: 1～0.0125: 1, and the reaction time is 2～7h.
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| CN106366090A (en) * | 2016-08-26 | 2017-02-01 | 云南森美达生物科技有限公司 | Method of synthesizing 1,8-cineole from alpha-terpilenol |
| CN106674244A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Preparation method of cineole |
| CN106732779A (en) * | 2017-01-13 | 2017-05-31 | 厦门大学 | A kind of carried heteropoly acid catalyst and preparation method and application |
| CN107008499A (en) * | 2017-04-13 | 2017-08-04 | 上海科技大学 | Terpenoid can be converted into the combination catalyst and method of aromatic hydrocarbon |
| CN107537573A (en) * | 2017-09-23 | 2018-01-05 | 江苏正大清江制药有限公司 | The method of the Cineole of high selectivity 1,8 |
| CN108558902A (en) * | 2018-05-25 | 2018-09-21 | 云南悦馨香料科技有限公司 | The method that terpinol synthesizes 1,8- Cineoles |
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| CN109810118A (en) * | 2019-01-07 | 2019-05-28 | 厦门大学 | A kind of method of alpha-terpineol synthesis 1,8- Cineole |
| CN110639615A (en) * | 2019-09-05 | 2020-01-03 | 广西民族师范学院 | Preparation method and application of immobilized phosphotungstic acid catalyst |
| CN111111780A (en) * | 2020-01-13 | 2020-05-08 | 广西民族师范学院 | Preparation method and application of terpineol isomerization catalyst |
| CN111606918A (en) * | 2020-05-19 | 2020-09-01 | 成都市明典世家生物科技有限公司 | Method for preparing high-purity 1, 8-cineole from crude cinnamomum camphora oil |
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| CN110639615A (en) * | 2019-09-05 | 2020-01-03 | 广西民族师范学院 | Preparation method and application of immobilized phosphotungstic acid catalyst |
| CN111111780A (en) * | 2020-01-13 | 2020-05-08 | 广西民族师范学院 | Preparation method and application of terpineol isomerization catalyst |
| CN111606918A (en) * | 2020-05-19 | 2020-09-01 | 成都市明典世家生物科技有限公司 | Method for preparing high-purity 1, 8-cineole from crude cinnamomum camphora oil |
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