CN102126904A - Method for isomerizing alpha-pinene - Google Patents
Method for isomerizing alpha-pinene Download PDFInfo
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- CN102126904A CN102126904A CN2011100223434A CN201110022343A CN102126904A CN 102126904 A CN102126904 A CN 102126904A CN 2011100223434 A CN2011100223434 A CN 2011100223434A CN 201110022343 A CN201110022343 A CN 201110022343A CN 102126904 A CN102126904 A CN 102126904A
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Abstract
The invention relates to a method for isomerizing alpha-pinene. The method comprises the following steps of: immobilizing active components such as halide, chloride and bromide on the surface of alumina, silicon oxide, SiO2-Al2O3 or silicon-aluminium molecular sieve by virtue of surface grafting reaction, and catalyzing isomerisation reaction of the alpha-pinene with solid acid, wherein halide can be aluminium, stibium, zinc, iron, titanium, tin and zirconium, and the reaction is performed for 10-240 minutes at the temperature of 5-80 DEG C in the manner of constant-pressure liquid-solid multiphase stirring reaction or fixed bed reaction. The new method for isomerizing the alpha-pinene, provided by the invention, has the advantages that the reaction condition is mild, the selectivity of main products (camphene, limonene and terpinolene) is high, and the catalyst produces no pollution to the equipment and environment, thus the catalysis process is environmentally friendly.
Description
Technical field
The present invention relates to the isomerized novel method of a kind of α-Pai Xi.Specifically, be the method that on immobilized halide catalyst, adopts liquid-solid heterogeneous stirring reaction mode or fixed bed reaction mode to carry out the α-Pai Xi isomerization reaction.
Background technology
α-Pai Xi is terebinthine main component, and turps is output maximum, essential oil that price is the most cheap in the world.α-Pai Xi is responsive especially to acid, and reaction, the especially isomerization products under the acid effect such as isomerization, oxidation, hydrogenation, addition, esterification and polymerization can take place, and is the important intermediate of preparation spices, medicine and fine chemicals, as by the amphene artificial camphor.The catalyzer that is used for the α-Pai Xi isomerization reaction has a lot, but the reaction product complexity.Therefore, under gentle relatively reaction conditions, improve the transformation efficiency and the high added value product selectivity of α-Pai Xi, just become investigator's main purpose.
U.S. Pat P 2,799, and 717 employing sulfuric acid are catalyzer, and catalysis is mixed with the α-Pai Xi isomerization reaction of menthadiene, and optimum raw material and sulfuric acid volume ratio are 100:35, at 35-65
oUnder the temperature of reaction of C, having obtained with α-terpinene, γ-Song Youxi and terpinolene is principal product and the mix products that does not contain limonene.But the employing liquid acid is a catalyzer, has environmental pollution and the numerous and diverse problem of product aftertreatment.Adopting solid acid is that catalyzer can address the above problem.Adopt the isomerization reaction of halloysite catalysis firpene as patent USP 2,385,711, raw material and catalyst volume are 155-165 than 25:1 in temperature of reaction
oIn the C scope, can obtain the amphene productive rate (this moment, the transformation efficiency of α-Pai Xi was 90%) about 60%.USP 3,780, and 125 propose at 150-170
oUnder the C, with the isomerization of 13X molecular sieve catalytic α-Pai Xi, the volume ratio of α-Pai Xi and catalyzer is 100:1, mainly obtains limonene and a spot of amphene and terpinolene.The transformation efficiency that the productive rate of principal product limonene reaches as high as 74%(α-Pai Xi this moment is 90%).USP 4,508, and 930 propose to load on the carrier as catalyzer with alkali metalsulphide, the catalysis terpenes, and the volume ratio of α-Pai Xi and catalyzer is 2:1, at 300-450
oUnder the C, mainly obtain limonene (highly selective can reach 90%, and this moment, the transformation efficiency of α-Pai Xi was 44%).USP 5,826, and 202 adopt hydrous titanium oxide to make catalyzer, and catalyst levels is the 0.05-1%(weight percentage of α-Pai Xi), earlier at 155-165
oUnder the C raw material α-Pai Xi being refluxed is reduced to about 3% up to α-Pai Xi content, makes reactive system be cooled to 150-155
oC continues reaction again, and the selectivity of amphene can reach more than 60%, also has a spot of tricyclene and terpinolene.This method has effectively suppressed the generation of polymkeric substance.Chinese patent CN 200810099188.4 is (ZrO2-Nd2O3/Al2O3) load SO on the Nano type complex carrier
4 2-, and this catalyzer is used for the α-Pai Xi isomerization reaction, 150
oC reacts the selectivity that 2 h can obtain 98% α-Pai Xi transformation efficiency and 65% above monocyclic terpene.
Summary of the invention
Goal of the invention: a kind of novel method of α-Pai Xi isomerization reaction is provided, adopts liquid-solid heterogeneous reaction mode or fixed bed reaction mode to carry out.The reaction conditions gentleness, running cost is low.And the catalyzer environment close friend who uses is to equipment and environmental nonpollution.
The technical scheme that adopts: a kind of α-Pai Xi isomerization method is provided, adopt immobilized muriate or bromide catalyzer as isomerization reaction, described isomerization reaction is carried out in normal pressure, liquid-solid heterogeneous stirred reactor or fixed-bed reactor, and temperature of reaction is 5-80
OC, reaction times 10-240 min, catalyst levels are the 3-25% of raw material α-Pai Xi weight, described catalyzer comprises support of the catalyst and active ingredient; Described active ingredient comprises that the immobilized separately or various active component of a kind of active ingredient of the muriate of aluminium, antimony, zinc, iron, titanium, tin, zirconium or bromide mixes immobilized.
According to α-Pai Xi isomerization method one optimal technical scheme provided by the invention be: the supported quantity of described active ingredient is the 3-20% of catalyst weight.
According to α-Pai Xi isomerization method one optimal technical scheme provided by the invention be: the carrier of described immobilized muriate or bromide catalysts is γ-Al
2O
3, SiO
2, SiO
2-Al
2O
3Or Si-Al molecular sieve.
According to α-Pai Xi isomerization method one optimal technical scheme provided by the invention be: described active ingredient muriate or bromide are by realizing that with the hydroxyl reaction of carrier surface grafting is immobilized.
According to α-Pai Xi isomerization method one optimal technical scheme provided by the invention be: described temperature of reaction is 30-50
OC
According to α-Pai Xi isomerization method one optimal technical scheme provided by the invention be: the described reaction times is 30-120 min.
Beneficial technical effects: α-Pai Xi isomerization novel method provided by the invention, related principal product is amphene, limonene and terpinolene, and a small amount of α-and γ-Song Youxi.Characteristics of the present invention are reaction conditions gentlenesses, weak point consuming time, the reactive behavior height is good to the selectivity of principal product.
Embodiment
Below in conjunction with specific embodiment purpose of the present invention, principle and effect are described further.
Inventive principle: the employing solid acid is a catalyzer, is specially active ingredient, and is immobilized at aluminum oxide, silicon oxide, SiO by the surface graft reaction as the halogenide (comprising muriate and bromide) of aluminium, antimony, zinc, iron, titanium, tin, zirconium etc.
2-Al
2O
3Or on the surface of Si-Al molecular sieve, the isomerization reaction of catalysis α-Pai Xi.Reaction adopts liquid-solid heterogeneous stirring reaction of normal pressure or fixed bed reaction mode to carry out temperature of reaction 5 ~ 80
oC, reaction times 10 ~ 240 min.
Embodiment 1
10 ml granular (diameter≤2 mm) high purity γ-Al
2O
3In the glass material fixed bed reaction pipe I of packing into, at high purity N
2(purity 〉=99.99%, in flow 20-100ml/min) atmosphere in 500
oC pre-treatment 2h afterwards, feeds CCl simultaneously with the flow of 0.8-2.00 ml/h
4(drying dewaters in advance), original position generates AlCl
3The mesoporous SiO of the 5ml40-60 purpose of packing in the fixed bed reaction pipe II
2, at high purity N
2In the air-flow (40 ml/min) 300
oBehind C pre-treatment 2 h, the reaction tubes I is linked to each other with the reaction tubes II, at N
2The air-flow carrier band is realized generated in-situ AlCl down
3With SiO
2AlCl is carried out in the reaction of surface hydroxyl
3Immobilized.Behind the 2-3h, stop to feed CCl
4, 300
oContinue to use N under the C
2Purge 1 h, at N
2It is standby to be cooled to room temperature under the protection.This catalyzer is designated as AlCl
3/ SiO
2
In the exsiccant reaction tubes, add magneton, 2ml α-Pai Xi, 0.2ml n-decane (internal standard substance) and 0.1 g AlCl
3/ SiO
2Catalyzer reacts 30 min, and product is analyzed with GC.Temperature of reaction is 30-60
OCThe α-Pai Xi isomerization reaction the results are shown in Table 1: AlCl
3/ SiO
2Catalysis α-Pai Xi isomerization reaction result (temperature of reaction difference).
Table 1
Embodiment 2
Press the AlCl of preparation among the embodiment 1
3/ SiO
2Catalyzer is 40
OCTemperature of reaction under, respectively α-Pai Xi is carried out the isomerization reaction of 60 min, 120 min.Other condition is with embodiment 1.The results are shown in Table 2:AlCl
3/ SiO
2Catalysis α-Pai Xi isomerization reaction result (reaction times difference).
Table 2
Embodiment 3
Press Preparation of catalysts method among the embodiment 1, carrier is changed to diplopore γ-Al
2O
3Carrier is in high-purity N
2In the air-flow 400
oBehind C pre-treatment 2 h, at N
2Be cooled to 300 in the air-flow
oC is with generated in-situ AlCl
3React 3 h, N
2Be warming up to 400 in the air-flow
oC purges 1 h, and it is standby to reduce to room temperature, and the catalyzer that obtains is designated as AlCl
3/ γ-Al
2O
3
Isomerization reaction with this catalyst α-Pai Xi: in the exsiccant reaction tubes, add magneton, 2 ml α-Pai Xis, 0.2 ml n-decane (internal standard substance) and 0.1 g AlCl
3/ γ-Al
2O
3Catalyzer.The 3:AlCl that the results are shown in Table in differential responses temperature and reaction times
3/ γ-Al
2O
3Catalysis α-Pai Xi isomerization reaction result.
Table 3
Above content be in conjunction with optimal technical scheme to further describing that the present invention did, can not assert that the concrete enforcement of invention only limits to these explanations.Concerning the general technical staff of the technical field of the invention, under the prerequisite that does not break away from design of the present invention, can also make simple deduction and replacement, all should be considered as protection scope of the present invention.
Claims (6)
1. a α-Pai Xi isomerization method is characterized in that, adopts immobilized muriate or the bromide catalyzer as isomerization reaction, and described isomerization reaction is carried out in normal pressure, liquid-solid heterogeneous stirred reactor or fixed-bed reactor, and temperature of reaction is 5-80
OC, reaction times 10-240 min, catalyst levels are the 3-25% of raw material α-Pai Xi weight, described catalyzer comprises support of the catalyst and active ingredient; Described active ingredient comprises that the immobilized separately or various active component of a kind of active ingredient of the muriate of aluminium, antimony, zinc, iron, titanium, tin, zirconium or bromide mixes immobilized.
2. α-Pai Xi isomerization method according to claim 1 is characterized in that, the supported quantity of described active ingredient is the 3-20% of catalyst weight.
3. α-Pai Xi isomerization method according to claim 1 is characterized in that, the carrier of described immobilized muriate or bromide catalysts is γ-Al
2O
3, SiO
2, SiO
2-Al
2O
3Or Si-Al molecular sieve.
4. α-Pai Xi isomerization reaction method according to claim 1 is characterized in that, described active ingredient muriate or bromide are by realizing that with the hydroxyl reaction of carrier surface grafting is immobilized.
5. α-Pai Xi isomerization reaction method according to claim 1 is characterized in that described temperature of reaction is 30-50
OC
6. α-Pai Xi isomerization reaction method according to claim 1 is characterized in that the described reaction times is 30-120 min.
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| CN 201110022343 CN102126904B (en) | 2011-01-20 | 2011-01-20 | Method for isomerizing alpha-pinene |
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|---|---|---|---|
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| CN102126904A true CN102126904A (en) | 2011-07-20 |
| CN102126904B CN102126904B (en) | 2013-07-17 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903461A (en) * | 2016-04-25 | 2016-08-31 | 福建青松股份有限公司 | Catalyst for synthesizing camphene and preparation method thereof |
| CN107892640A (en) * | 2017-05-31 | 2018-04-10 | 怀集县长林化工有限责任公司 | A kind of α firpenes isomery prepares the preparation method of amphene |
| CN109651064A (en) * | 2018-12-21 | 2019-04-19 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of terpinolene |
| CN109721451A (en) * | 2018-12-21 | 2019-05-07 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of limonene |
| CN110548498A (en) * | 2019-09-05 | 2019-12-10 | 广东石油化工学院 | Alpha-pinene isomerization catalyst and preparation method thereof |
| WO2021164852A1 (en) | 2020-02-18 | 2021-08-26 | Symrise Ag | Process for preparing limonene and composition containing limonene |
| WO2021164850A1 (en) | 2020-02-18 | 2021-08-26 | Symrise Ag | Method for producing limonene and composition containing limonene |
Citations (2)
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|---|---|---|---|---|
| US4000207A (en) * | 1975-05-12 | 1976-12-28 | Scm Corporation | Isomerization of alpha-pinene to beta-pinene with neutralized alumina-supported mixed metal catalyst |
| CN101347740A (en) * | 2008-08-28 | 2009-01-21 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
-
2011
- 2011-01-20 CN CN 201110022343 patent/CN102126904B/en not_active Expired - Fee Related
Patent Citations (2)
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|---|---|---|---|---|
| US4000207A (en) * | 1975-05-12 | 1976-12-28 | Scm Corporation | Isomerization of alpha-pinene to beta-pinene with neutralized alumina-supported mixed metal catalyst |
| CN101347740A (en) * | 2008-08-28 | 2009-01-21 | 复旦大学 | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use |
Non-Patent Citations (4)
| Title |
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| 《林产化学与工业》 19931231 吴晓刚等 固体超强酸催化alpha-蒎烯异构反应研究 1-6 第13卷, 第2期 * |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105903461A (en) * | 2016-04-25 | 2016-08-31 | 福建青松股份有限公司 | Catalyst for synthesizing camphene and preparation method thereof |
| CN105903461B (en) * | 2016-04-25 | 2018-06-29 | 福建青松股份有限公司 | It is a kind of to be used to synthesize catalyst of amphene and preparation method thereof |
| CN107892640A (en) * | 2017-05-31 | 2018-04-10 | 怀集县长林化工有限责任公司 | A kind of α firpenes isomery prepares the preparation method of amphene |
| CN107892640B (en) * | 2017-05-31 | 2020-10-27 | 怀集县长林化工有限责任公司 | Preparation method for preparing camphene by alpha-pinene isomerization |
| CN109651064A (en) * | 2018-12-21 | 2019-04-19 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of terpinolene |
| CN109721451A (en) * | 2018-12-21 | 2019-05-07 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of limonene |
| CN110548498A (en) * | 2019-09-05 | 2019-12-10 | 广东石油化工学院 | Alpha-pinene isomerization catalyst and preparation method thereof |
| CN110548498B (en) * | 2019-09-05 | 2022-04-26 | 广东石油化工学院 | Alpha-pinene isomerization catalyst and preparation method thereof |
| WO2021164852A1 (en) | 2020-02-18 | 2021-08-26 | Symrise Ag | Process for preparing limonene and composition containing limonene |
| WO2021164850A1 (en) | 2020-02-18 | 2021-08-26 | Symrise Ag | Method for producing limonene and composition containing limonene |
| CN115210180A (en) * | 2020-02-18 | 2022-10-18 | 西姆莱斯股份公司 | Process for preparing limonene and compositions containing limonene |
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|---|---|
| CN102126904B (en) | 2013-07-17 |
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