CN101209415B - Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate - Google Patents
Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate Download PDFInfo
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- CN101209415B CN101209415B CN200610148173A CN200610148173A CN101209415B CN 101209415 B CN101209415 B CN 101209415B CN 200610148173 A CN200610148173 A CN 200610148173A CN 200610148173 A CN200610148173 A CN 200610148173A CN 101209415 B CN101209415 B CN 101209415B
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Abstract
The invention discloses a hydrogenation catalyst which is used for preparing linalyl acetate by using dehydroabietic linalyl acetate The catalyst uses calcium carbonate as a carrier, loaded active components of the catalyst comprises Pd, Pb and component A, wherein, the constituent A is a mixture of one or both of Bi and Zn, total content of Pd and Pb in the catalyst is 0.1 to 4.0 percent by weight, mass ratio of Pd to Pb is between 5 to 1 and 1 to 1, and content of the component A in the catalyst is 0.5 to 3.0 percent by weight. Compared with common Lindlar catalysts, the catalyst of the invention has the advantages that the catalyst does not need to use compounds of naphthyridine and quinoline, etc., as catalyst accelerators, does not use solvents in the hydrogenation process and has higher product selectivity under the precondition of high conversion rate; furthermore, the dosage of noble metal Pd is markedly reduced.
Description
Technical field
The present invention relates to a kind of catalyst that dehydroactic acid virtue camphor tree ester through hydrogenation prepares bergamio that is used for, catalyst is carrier with calcium carbonate, contains Pd and Pb in the active constituent of load.
Background technology
Acetate dehydrogenation virtue camphor tree ester is a kind of important fine-chemical intermediate for preparing spices, can be used for producing fine chemical products such as citral, irisone.Acetate dehydrogenation virtue camphor tree ester also can obtain bergamio by hydrogenation reaction, bergamio is one of lavender main body of oil, the fragrance elegance, approximate bergamot oil and lavender oil are the important source material of the high-grade perfume of preparation and multiple senior spices or essence.Bergamio adopts linalool and acetic anhydride to make through esterification more in the prior art, because linalool can be made by the products of separated isoprene of the C5 fraction of petroleum cracking system ethylene by-product, raw material sources are abundant and price is comparatively cheap, introduced two kinds of methods of using different catalyst linalool and acetic anhydride to be prepared bergamio by esterification respectively as Chinese patent ZL03129192.9 and ZL03129214.3.But, react simultaneously with multiple accessory substance generation such as neryl acetate, geranyl acetate because linalool is the relative higher reversible reaction of a kind of opposite direction rate constant with the esterification of acetic anhydride.The general difficult higher reaction conversion ratio that obtains, when conversion ratio is higher than 90%, selectivity will obviously descend, and generally can only reach about 60%.
In fact, preparing linalool by isoprene is to make dehydrolinalool earlier, obtains linalool through hydrogenation then.And dehydrolinalool and suitable acylating agent also can carry out esterification, and as obtaining acetate dehydrogenation virtue camphor tree ester with acetic anhydride, reaction equation is:
Acetate dehydrogenation virtue camphor tree ester can obtain bergamio equally through hydrogenation again, and reaction equation is:
According to experience in the past, though the esterification of dehydrolinalool and acetic anhydride also belongs to a kind of reversible reaction, side reactions such as isomery, cyclisation also may take place in the esterification process generate accessory substances such as ring-type pyrans and cyclic ester.But the reciprocal rate constant of this esterification is relatively low, and therefore, dehydrolinalool is carried out esterification and then obtains bergamio through hydrogenation with acetic anhydride earlier should be a kind of even more ideal process route.In one's early years really once the someone to propose with the dehydrolinalool be raw material, first esterification generates acetate dehydrogenation virtue camphor tree ester, obtains the method for bergamio then through hydrogenation, as U.S. Pat 2,797,235 are introduced.
In the prior art, Lindlar catalyst (promptly be carrier with calcium carbonate, active constituent is Pd, or also further contains the loaded catalyst that helps catalyst component Pb) is can promote the acetylene bond selection hydrogenation in hydro carbons and other compound efficiently and to be widely used.But its shortcoming is that the selectivity of reaction is relatively low, in order to remedy this defective, introduces compounds such as pyridine, quinoline usually in reaction system or catalyst carrier.Though these organic matters can improve reaction selectivity effectively, make the reactant mixture variable color easily and bring peculiar smell, and compound such as pyridine, quinoline is difficult to be separated from hydrocarbon compound.Because the purposes of bergamio is mainly the manufacturing raw material of fragrance product, general Lindlar catalyst is used for acetate dehydrogenation virtue camphor tree ester through hydrogenation prepares bergamio, then the form and aspect of product and flavouring essence quality obviously can be seriously influenced.Above-mentioned U.S. Pat 2,797,235 its hydrogenation processes of the method for being introduced have promptly adopted a kind of hydrogenation catalyst of similar Lindlar catalyst, it not only will add quinoline as catalytic promoter, and hydrogenation reaction to add a large amount of cyclohexane gives be solvent, so the refining very difficulty of product is difficult to reach the requirement of making high-grade spices.
Summary of the invention
The invention provides a kind of catalyst that dehydroactic acid virtue camphor tree ester through hydrogenation prepares bergamio that is used for, it has higher activity, desirable conversion ratio and selectivity, need not to use compounds such as pyridine, quinoline as catalytic promoter, hydrogenation process is not used any solvent yet, can solve the technical problem that prior art exists effectively.
Below be the detailed technical scheme of the present invention:
A kind ofly be used for the catalyst that dehydroactic acid virtue camphor tree ester through hydrogenation prepares bergamio, this catalyst is carrier with calcium carbonate, contains Pd, Pb and component A in the active constituent of load, and A is Zn, or the mixture of Zn and Bi.The total content of Pd and Pb is 0.1～4.0wt% in the catalyst, and the mass ratio of Pd and Pb is (5～1): 1, and the content of component A is 0.5～3.0wt% in the catalyst.
The total content of active constituent Pd and Pb is preferably 0.5～1.5wt% in the above-mentioned catalyst; The mass ratio of Pd and Pb is preferably (3～1): 1; The content of component A is preferably 1.0～2.0wt% in the catalyst.
As the preparation of loaded catalyst, catalyst provided by the invention also can adopt the known infusion process in present technique field to prepare.Following preparation process is what the present invention recommended:
The starting material of each active component is selected certain density metal salt solution for use, can adopt palladium nitrate solution as Pd, and Pb can adopt lead nitrate solution, and the Bi among the component A can adopt bismuth nitrate solution, and Zn can adopt zinc nitrate solution.Earlier each starting material is mixed with maceration extract by required proportioning, then calcium carbonate carrier is placed the maceration extract dipping to obtain catalyst precarsor, the dipping liquid measure is 95～110% of a carrier hygroscopicity value; In addition roasting after the catalyst precarsor oven dry; Catalyst precarsor after the roasting reduces processing, and reducing agent generally can adopt formaldehyde, hydrazine hydrate or hydrogen etc., and then promptly gets the catalyst finished product after washing, oven dry.
Hydrogenation reaction is generally carried out in autoclave, and it is favourable imposing stirring during reaction, and acetate dehydrogenation virtue camphor tree ester through hydrogenation speed is directly proportional with hydrogen dividing potential drop and hydrogenation temperature.Following reaction condition is that the present invention recommends: the hydrogenation reaction temperature is 20～150 ℃, and Hydrogen Vapor Pressure is 1.0～10.0Mpa, and the hydrogenation reaction time is 30～240min, and catalyst consumption is 0.01～5.0wt% that catalyst accounts for reactant liquor.
The solid-liquid separating method of available routine was more easily separated catalyst after reaction finished from product, catalyst is reusable, reuse generally speaking and still show goodish activity more than 10 times, and decaying catalyst can be regenerated with the method that present technique field those skilled in the art know.
Essence of the present invention is to adopt suitable base metal (being component A) that general Lindlar catalyst is carried out modification, the inventor finds by a large amount of experiments, this improvement makes catalyst outside characteristic such as guarantee active height, hydrogenation technique mild condition that general Lindlar catalyst had, can be repeatedly used, also improved the performance of catalyst from many aspects, it shows as: need not to use compounds such as pyridine, quinoline as catalytic promoter; Hydrogenation process is not used solvent, has reduced reaction volume, thereby has reduced energy consumption and material consumption; Catalyst can avoid Pd to be poisoned by oxy radical impurity in hydrogenation process; Have higher selectivity of product under the prerequisite of high conversion, when conversion ratio was 99%, selectivity of product also can reach about 99%.Except that a small amount of unreacted raw material, do not have other impurity substantially in the hydrogenation products, can obtain highly purified purified product through simple rectifying.
It is that the consumption of precious metals pd significantly reduces that this improvement brings another benefit, and the Pd content of general Lindlar catalyst is generally about 5wt%, and catalyst provided by the invention just has extraordinary activity when Pd content is 1.0wt%.
The above is the advantage that the present invention is compared with prior art embodied.
Below will the invention will be further described by specific embodiment, conversion ratio and optionally being defined as in an embodiment:
The specific embodiment
[embodiment 1～12]
Preparation of catalysts:
The starting material of each active component is: Pd adopts palladium nitrate solution; Pb adopts lead nitrate solution; Bi among the component A adopts bismuth nitrate solution, and Zn adopts zinc nitrate solution.
Above-mentioned each starting material is mixed with maceration extract in required ratio with pure water; Place the maceration extract dipping to obtain catalyst precarsor a certain amount of calcium carbonate carrier, the dipping liquid measure is 95～110% of a carrier hygroscopicity value, floods respectively 1 hour at normal temperatures with under 70 ℃ of temperature; Catalyst precarsor oven dry back was 280 ℃ of roasting temperatures 5 hours; Catalyst precarsor after the roasting reduces processing with hydrazine hydrate, and is near neutral through washed several times with water pH value to the washing lotion again; Under 75 ℃ of temperature, dry at last, obtain the catalyst finished product.
Active component and content thereof in each embodiment catalyst see Table 1.
The performance evaluation of catalyst:
Pour 194g dehydroactic acid virtue camphor tree ester in being connected with the 500ml autoclave of cooling water, adding the catalyst that embodiment 1～12 obtains respectively, catalyst accounts for the 0.2wt% of reactant liquor.After the hydrogen exchange three times, feed hydrogen under reaction temperature, the control reaction temperature is 50 ℃, and Hydrogen Vapor Pressure is 2.5Mpa, imposes to stir to begin reaction.Reaction 60min and 120min be the assaying reaction result respectively.
The evaluation result of each embodiment catalyst sees Table 2.
Table 1.
| (Pd+Pb) content (wt%) | Pd/Pb (mass ratio) | Component A | A content (wt%) | |
| Embodiment 1 | 2.0 | 3/1 | Bi | 1.0 |
| Embodiment 2 | 4.0 | 3/1 | Bi | 0.5 |
| Embodiment 3 | 0.5 | 2/1 | Bi | 1.5 |
| Embodiment 4 | 2.0 | 3/1 | Zn | 1.0 |
| Embodiment 5 | 0.1 | 3/1 | Zn | 3.0 |
| Embodiment 6 | 2.0 | 2/1 | Zn | 1.0 |
| Embodiment 7 | 1.5 | 3/1 | Bi+Zn | 0.5 |
| Embodiment 8 | 1.5 | 2/1 | Bi+Zn | 2.0 |
| Embodiment 9 | 0.5 | 2.5/1 | Bi+Zn | 2.0 |
| Embodiment 10 | 4.0 | 1/1 | Bi+Zn | 1.0 |
| Embodiment 11 | 1.5 | 3/1 | Bi+Zn | 1.0 |
| Embodiment 12 | 2.0 | 5/1 | Bi+Zn | 1.0 |
Table 2.
[embodiment 13～15]
Get the catalyst that embodiment 8 obtains, change hydrogenation conditions and carry out the evaluation of catalyst performance.The reaction condition that changes sees Table 3, and all the other appreciation conditions are with embodiment 1～12, and evaluation result sees Table 4.
Table 3.
| Reaction temperature (℃) | Hydrogen Vapor Pressure (Mpa) | Reaction time (min) | Catalyst accounts for reactant liquor (wt%) | |
| Embodiment 13 | 30 | 1.5 | 100 | 1.0 |
| Embodiment 14 | 20 | 3.0 | 240 | 0.2 |
| Embodiment 15 | 50 | 2.5 | 110 | 0.2 |
| Embodiment 16 | 80 | 2.5 | 60 | 5.0 |
| Embodiment 17 | 50 | 3.5 | 120 | 0.01 |
| Embodiment 18 | 150 | 10 | 30 | 0.1 |
Table 4.
| Conversion ratio (%) | Selectivity (%) | |
| Embodiment 13 | 87.0 | 99.7 |
| Embodiment 14 | 96.0 | 99.3 |
| Embodiment 15 | 99.4 | 99.0 |
| Embodiment 16 | 99.8 | 95.6 |
| Embodiment 17 | 87.0 | 99.8 |
| Embodiment 18 | 99.2 | 77.3 |
Claims (4)
1. one kind is used for the catalyst that dehydroactic acid virtue camphor tree ester through hydrogenation prepares bergamio, this catalyst is carrier with calcium carbonate, contain Pd, Pb and component A in the active constituent of load, A is Zn, or the mixture of Zn and Bi, the total content of Pd and Pb is 0.1～4.0wt% in the catalyst, and the mass ratio of Pd and Pb is (5～1): 1, and the content of component A is 0.5～3.0wt% in the catalyst.
2. catalyst according to claim 1, the total content that it is characterized in that described active constituent Pd and Pb is 0.5～1.5wt%.
3. catalyst according to claim 1 is characterized in that the mass ratio of described active constituent Pd and Pb is (3～1): 1.
4. catalyst according to claim 1, the content that it is characterized in that described component A is 1.0～2.0wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101869845B (en) * | 2010-06-21 | 2012-06-13 | 浙江新和成股份有限公司 | Catalyst for selective hydrogenation of dehydroisophytol for synthesizing isophytol |
| CN102397788A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Method for preparing linalool from dehydrolinalool through selective hydrogenation |
| CN102397789A (en) * | 2010-09-17 | 2012-04-04 | 中国石油化工股份有限公司 | Fixed bed catalyst for preparing linalool by selective hydrogenation of dehydrolinalool |
| IN2015DN02648A (en) * | 2012-10-08 | 2015-09-18 | Dsm Ip Assets Bv |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273944A (en) * | 1978-11-08 | 1981-06-16 | Shin-Etsu Chemical Co., Ltd. | Method for selective preparation of cis isomers of ethylenically unsaturated compounds |
| CN1565740A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Catalyzer for preparing linalyl acetate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4273944A (en) * | 1978-11-08 | 1981-06-16 | Shin-Etsu Chemical Co., Ltd. | Method for selective preparation of cis isomers of ethylenically unsaturated compounds |
| CN1565740A (en) * | 2003-06-12 | 2005-01-19 | 中国石化上海石油化工股份有限公司 | Catalyzer for preparing linalyl acetate |
Non-Patent Citations (5)
| Title |
|---|
| JP特开平9-176089A 1997.07.08 |
| 翁羽飞等.Pb、Bi改性Pd催化剂合成芳樟醇.精细化工20 8.2003,20(8),481-482,508. |
| 翁羽飞等.Pb、Bi改性Pd催化剂合成芳樟醇.精细化工20 8.2003,20(8),481-482,508. * |
| 翁羽飞等.选择性加氢合成芳樟醇催化剂的研究进展.上海化工 18.2002,(18),25-27. |
| 翁羽飞等.选择性加氢合成芳樟醇催化剂的研究进展.上海化工 18.2002,(18),25-27. * |
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