CN103342627B - A kind of method of citral selective hydrogenation synthesis vernol and geraniol mixture in water-organic biphasic system - Google Patents
A kind of method of citral selective hydrogenation synthesis vernol and geraniol mixture in water-organic biphasic system Download PDFInfo
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- CN103342627B CN103342627B CN201310269530.1A CN201310269530A CN103342627B CN 103342627 B CN103342627 B CN 103342627B CN 201310269530 A CN201310269530 A CN 201310269530A CN 103342627 B CN103342627 B CN 103342627B
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Abstract
The present invention relates to a kind of method of selective hydrogenation synthesis vernol and geraniol mixture in citral water-organic biphasic system.Existing multiple citral process for selective hydrogenation, is difficult to the highly selective obtaining unsaturated alcohol.The invention is characterized in that the water soluble complex formed with the VIIIth race's water-soluble metal salt and water soluble ligand is for catalyzer, the water-soluble salt of group VIII metal and the mass ratio of water soluble ligand are 0.001 ~ 0.01:1; In water-organic biphasic system, carry out selective hydrogenation to citral, after reaction terminates, stratification, the aqueous phase containing catalyzer continues cover and uses lower batch reaction, and organic phase is the mixture of vernol and Geraniol.Present invention process is simple, and reaction conversion ratio is high, and selectivity is good; Activity and the stability of catalyzer are high, can repeatedly recycled, reduce cost, be applicable to suitability for industrialized production while decreasing pollution.
Description
Technical field
The present invention relates to α, the method for beta-unsaturated aldehyde selective hydrogenation synthesis unsaturated alcohol, specifically the method for a kind of citral selective hydrogenation synthesis vernol and geraniol mixture in water-organic biphasic system.
Background technology
Citral is a kind of typical α, and beta-unsaturated aldehyde, its selective hydrogenation product is the mixture of Geraniol and vernol.Geraniol and vernol, there is gentle fragrant and sweet smell, in Rose Essentielle, be widely used in the various bouquet type composition of allotment, be the raw material manufacturing VANILLYL ALCOHOL MIN 98, Vanillin, citral, hydroxycitronellal, jononeionone and vitamin A, have a wide range of applications in the industry such as essence, medicine.
Citral Hydrogenation is to have two C=C and C=O double bond in citral molecule for the difficult point of Geraniol simultaneously, and two both the C=O that are strong and end position of C=C in the middle of it have conjugation, hydrogen is only added to C=O double bond and is not added to C=C double bond (difficulty is larger).Therefore design the catalyst system of highly selective, make it be the key of the problems referred to above by the hydrogenation selectivity that kinetic approach improves C=O.
Current bibliographical information to prepare the research of Geraniol and vernol with citral selective hydrogenation main on a catalyst.
US4100180 describes under PtO/Zn/Fe catalyst, and unsaturated aldehyde hydrogenation obtains the discontinuous method of unsaturated alcohol, and when citral transformation efficiency reaches 70%, the overall selectivity of Geraniol and vernol is 85.5%.
CN101747152 then with the platinum of load on ferric oxide for catalyzer, by citral selective hydrogenation synthesis vernol and Geraniol, achieve Geraniol and vernol selective regulation.When citral transformation efficiency is 14.2%, the overall selectivity of Geraniol and vernol is 58.9%.
All there is citral low conversion rate in above-mentioned two kinds of methods, the problem that the overall selectivity of Geraniol and vernol is low.
CN02155367 proposes to carry out citral selective hydrogenation with the iron ruthenium catalyst of load on carbon, reacts and carries out in fixed bed or suspension bed.When citral transformation efficiency is 95.61%, the overall selectivity of vernol and Geraniol is 95.22%, and the selectivity of geraniol is 1.8%.
The people such as Chatterjee (AdvSynthCatal, 2008,350,624-632) for catalyzer with the molecular sieve carried Pt of MCM-41, carry out selective hydrogenation to citral, have investigated solvent, temperature, CO
2pressure, H
2pressure etc., on the impact of catalyst activity and selectivity, find to use supercritical CO
2for solvent, the transformation efficiency of citral is up to 99.8% under certain conditions, and the overall selectivity of Geraniol and vernol reaches 100%.Although selectivity is higher in aforesaid method, need with supercritical CO
2for solvent, operational condition is comparatively harsh; Use fixed-bed reactor in addition, require that catalyzer has long-term work-ing life.
Summary of the invention
For the deficiency that above-mentioned prior art exists, the invention provides the method for a kind of citral selective hydrogenation synthesis vernol and geraniol mixture in water-organic biphasic system, its step is as follows:
1) the water soluble complex catalyzer that the water-soluble salt of 1 part of citral, 1 ~ 10 part of water, 0.02 ~ 0.2 part of group VIII metal and water soluble ligand are formed is joined in autoclave, nitrogen replacement 3 times, hydrogen exchange 3 times, then at hydrogen pressure 0.5 ~ 15.0MPa, temperature of reaction 30 ~ 150 DEG C, under the condition of mixing speed 200 ~ 1000rpm, compressive reaction 2 ~ 20 hours, until citral transformation efficiency is greater than 98%;
2) after reaction terminates, stratification, the aqueous phase containing catalyzer continues cover and uses lower batch reaction, and organic phase is the mixture of vernol and Geraniol;
The water-soluble salt of described group VIII metal and the mass ratio of water soluble ligand are 0.001 ~ 0.01:1, and described number is parts by weight.
Further, the water-soluble salt of described group VIII metal is one or more in ruthenium acetate, ruthenium chloride, nitric acid ruthenium, rhodium sulfate, rhodium chloride, rhodium nitrate, acid chloride, Palladous chloride, Palladous nitrate.
Further, described water soluble ligand is preferably water-soluble phosphine ligand or water-soluble imine ligand.
Described water-soluble phosphine ligand be preferably in triphenylphosphine sodium sulfonate, triphenylphosphine potassium sulfonate, three-(to phenoxy group-Soxylat A 25-7)-phosphines, three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphines, three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphines one or more.
Further, described water-soluble imine ligand is preferably 5-[1-(2,6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium.
Selectivity, the transformation efficiency of water-soluble group VIII metal complex catalyst system catalyzing citral selective hydrogenation synthesis unsaturated alcohol used in the present invention are better than traditional supported solid catalyst, and at supercritical CO
2in quite.Present invention process is simple, convenient post-treatment, and aqueous phase can recycled, reduces cost, be applicable to suitability for industrialized production while decreasing pollution.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
10g ruthenium acetate and three-(to phenoxy group-Soxylat A 25-7)-phosphine complex catalyst (ruthenium acetate and three-(to phenoxy group-Soxylat A 25-7)-phosphine mass ratio is 0.008:1), 500g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then 500g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 100 DEG C, pressurized with hydrogen stirs to 0.5MPa, 500rpm, react 2 hours, the transformation efficiency of sampling analysis citral is greater than 98%.With water cooling, extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.85%, and vernol/Geraniol overall selectivity is 99.10%.
Embodiment 2
20g rhodium nitrate and triphenylphosphine sodium sulfonate complex catalyst (rhodium nitrate and triphenylphosphine sodium sulfonate mass ratio are 0.001:1), 1000g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then 100g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 150 DEG C, pressurized with hydrogen stirs to 1.5MPa, 1000rpm, react 20 hours, the transformation efficiency of sampling analysis citral is greater than 98%.With water cooling, extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.68%, and vernol/Geraniol overall selectivity is 99.22%.
Embodiment 3
25g Palladous chloride and three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphine complex catalyst (Palladous chloride and three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphine mass ratio is 0.01:1), 800g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then 200g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 30 DEG C, pressurized with hydrogen is to 1.4MPa, 800rpm stirs, react 12 hours, the transformation efficiency of sampling analysis citral is greater than 98%.Extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.23%, and vernol/Geraniol overall selectivity is 99.52%.
Embodiment 4
15g rhodium sulfate and three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphine complex catalyst (rhodium sulfate and three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphine mass ratio is 0.006:1), 600g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then 400g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 60 DEG C, pressurized with hydrogen is to 1.0MPa, 200rpm stirs, react 18 hours, the transformation efficiency of sampling analysis citral is greater than 98%.With water cooling, extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.39%, and vernol/Geraniol overall selectivity is 99.63%.
Embodiment 5
By 25g Palladous nitrate and 5-[1-(2, 6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium complex catalyst (Palladous nitrate and 5-[1-(2, 6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium mass ratio is 0.003:1), 700g water joins in the 2L autoclave with magnetic agitation and temperature controller, then 300g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 80 DEG C, pressurized with hydrogen is to 1.2MPa, 700rpm stirs, react 13 hours, the transformation efficiency of sampling analysis citral is greater than 98%.With water cooling, extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.71%, and vernol/Geraniol overall selectivity is 99.36%.
Embodiment 6
25g rhodium chloride and triphenylphosphine potassium sulfonate complex catalyst (rhodium chloride and triphenylphosphine potassium sulfonate mass ratio are 0.006:1), 500g water are joined in the 2L autoclave with magnetic agitation and temperature controller, then 500g citral is added, with nitrogen replacement three times, after use hydrogen exchange three times, be heated to 100 DEG C, pressurized with hydrogen stirs to 1.0MPa, 700rpm, react 6 hours, the transformation efficiency of sampling analysis citral is greater than 98%.With water cooling, extrude reaction solution, stratification, aqueous phase is that catalyzer can continue cover and uses lower batch reaction, and organic phase is the mixture of Geraniol and vernol.Through gas chromatographic analysis, the transformation efficiency of citral is 98.91%, and vernol/Geraniol overall selectivity is 99.31%.
Applied mechanically by aqueous phase containing catalyzer, its experimental result is as following table:
| Batch | Transformation efficiency/% | Selectivity/% |
| New throwing 1 | 98.91 | 99.31 |
| Apply mechanically 2 | 98.80 | 99.28 |
| Apply mechanically 3 | 99.08 | 99.11 |
| Apply mechanically 4 | 99.07 | 99.08 |
| Apply mechanically 5 | 99.38 | 98.88 |
| Apply mechanically 6 | 99.50 | 98.87 |
| Apply mechanically 7 | 99.12 | 99.07 |
| Apply mechanically 8 | 98.98 | 99.17 |
| Apply mechanically 9 | 98.95 | 99.20 |
| Apply mechanically 10 | 98.81 | 99.11 |
| Apply mechanically 11 | 99.10 | 99.20 |
| Apply mechanically 12 | 99.07 | 99.05 |
| Apply mechanically 13 | 99.13 | 98.95 |
| Apply mechanically 14 | 99.03 | 99.10 |
| Apply mechanically 15 | 99.12 | 99.09 |
| Apply mechanically 16 | 99.24 | 98.92 |
| Apply mechanically 17 | 99.12 | 98.93 |
| Apply mechanically 18 | 98.82 | 99.05 |
| Apply mechanically 19 | 98.69 | 99.16 |
| Apply mechanically 20 | 99.01 | 99.07 |
Note: catalyzer or part are added in "+" expression
The above is all preferred embodiments of the present invention.Every above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all fall within the scope of protection of the present invention.
Claims (1)
1. a method for citral selective hydrogenation synthesis vernol and geraniol mixture in water-organic biphasic system, its step is as follows:
1) the water soluble complex catalyzer that the water-soluble salt of 1 part of citral, 1 ~ 10 part of water, 0.02 ~ 0.2 part of group VIII metal and water soluble ligand are formed is joined in autoclave, first with nitrogen replacement repeatedly, afterwards with hydrogen exchange repeatedly, then at hydrogen pressure 0.5 ~ 15.0MPa, temperature of reaction 30 ~ 150 DEG C, under the condition of mixing speed 200 ~ 1000rpm, compressive reaction 2 ~ 20 hours, until citral transformation efficiency is greater than 98%;
2) after reaction terminates, stratification, the aqueous phase of containing water-soluble complex compound catalyst continues cover and uses lower batch reaction, and organic phase is the mixture of vernol and Geraniol;
The water-soluble salt of described group VIII metal and the mass ratio of water soluble ligand are 0.001 ~ 0.01:1, and described number is parts by weight;
The water-soluble salt of described group VIII metal is one or more in ruthenium acetate, ruthenium chloride, nitric acid ruthenium, rhodium sulfate, rhodium chloride, rhodium nitrate, acid chloride, Palladous chloride, Palladous nitrate;
Described water soluble ligand is water-soluble phosphine ligand or water-soluble imine ligand, described water-soluble phosphine ligand is one or more in triphenylphosphine sodium sulfonate, triphenylphosphine potassium sulfonate, three-(to phenoxy group-Soxylat A 25-7)-phosphines, three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphines, three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphines, described water-soluble imine ligand is 5-[1-(2,6-di-isopropyl phenyl imido)-ethyl]-2-furane sulfonic acid triethyl ammonium.
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| CN105622363B (en) * | 2014-11-04 | 2017-12-08 | 南京工业大学 | Technology for preparing vanillyl alcohol ether by one-step method |
| CN105175231B (en) * | 2015-09-22 | 2018-03-16 | 山东新和成药业有限公司 | A kind of method that propargyl ethanol selective hydrogenation prepares allyl alcohol |
| CN107089900B (en) * | 2017-04-28 | 2020-06-26 | 山东新和成药业有限公司 | Preparation method of β -phenethyl alcohol |
| CN109503327B (en) * | 2018-12-12 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing nerol and geraniol by hydrogenating citral |
| CN109647524B (en) * | 2018-12-25 | 2021-10-19 | 万华化学集团股份有限公司 | Catalyst and application thereof in production of citronellal and/or citronellol from citral |
| CN110963888B (en) * | 2019-11-26 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing nerol and geraniol from citral |
| CN111018666B (en) * | 2019-12-12 | 2022-11-04 | 万华化学集团股份有限公司 | Improved process for preparing nerol leaf alcohol and catalytic system therefor |
| CN112979422B (en) * | 2019-12-12 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing nerol/geraniol |
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|---|---|---|---|---|
| US4100180A (en) * | 1974-12-26 | 1978-07-11 | Teijin, Limited | Process for hydrogenating unsaturated aldehydes to unsaturated alcohols |
| CN1422693A (en) * | 2001-12-07 | 2003-06-11 | 巴斯福股份公司 | Preparation of ruthenium/iron catalyst loaded onto carbon |
| CN1422834A (en) * | 2001-12-07 | 2003-06-11 | 巴斯福股份公司 | Selective liquid-phase hydrogenation of carbonyl compound under present of Pt/ZnO catalyst to obtain corresponding alcohol |
| CN101400632A (en) * | 2006-03-10 | 2009-04-01 | 索尔维亚斯股份公司 | Asymmetric catalytic hydrogenation of prochiral ketones and aldehydes |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100180A (en) * | 1974-12-26 | 1978-07-11 | Teijin, Limited | Process for hydrogenating unsaturated aldehydes to unsaturated alcohols |
| CN1422693A (en) * | 2001-12-07 | 2003-06-11 | 巴斯福股份公司 | Preparation of ruthenium/iron catalyst loaded onto carbon |
| CN1422834A (en) * | 2001-12-07 | 2003-06-11 | 巴斯福股份公司 | Selective liquid-phase hydrogenation of carbonyl compound under present of Pt/ZnO catalyst to obtain corresponding alcohol |
| CN101400632A (en) * | 2006-03-10 | 2009-04-01 | 索尔维亚斯股份公司 | Asymmetric catalytic hydrogenation of prochiral ketones and aldehydes |
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