CN105175231A - Method for preparing allyl alcohol through selective hydrogenation of propargyl alcohol - Google Patents
Method for preparing allyl alcohol through selective hydrogenation of propargyl alcohol Download PDFInfo
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- CN105175231A CN105175231A CN201510605754.4A CN201510605754A CN105175231A CN 105175231 A CN105175231 A CN 105175231A CN 201510605754 A CN201510605754 A CN 201510605754A CN 105175231 A CN105175231 A CN 105175231A
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
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Abstract
The invention provides a method for preparing allyl alcohol through selective hydrogenation of propargyl alcohol. According to existing methods for synthesis of allyl alcohol through hydrogenation of propargyl alcohol, an immobilized heterogeneous catalysis system is adopted mostly, and high conversion rate, high selectivity and low leftover rate are hard to realize at the same time. The method is characterized in that the weaknesses of an immobilized catalyst are avoided, and VIII-group water-soluble metal salt and a water-soluble ligand are adopted for complexing to form a complex catalyst so as to achieve water-organic biphasic hydrogenation reaction. The method comprises the steps of material charging, nitrogen and hydrogen replacement, and hydrogenation reaction. During material charging, 0.1-5 parts of water and 0.005-0.1 part of catalyst are added to a kettle, and then 1 part of propargyl alcohol is added. The conversion rate of propargyl alcohol is 99.9-99.99%, gas phase selectivity is high, and yield is high; the catalyst is evenly and stably dispersed, unit consumption is low, recycling can be conducted for more than 30 times, the catalyst, the product and a catalytic system are easy to separate, operation is easy, and the method is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of production VE main intermediate, DV chrysanthemumic acid (chrysanthemum ester intermediate), synthesise vitamins A, vitamin K1, carotenoid intermediate, the method of synthetic rubber monomer and spices, specifically for the method for allyl alcohol is prepared in the selective hydrogenation in water-organic biphasic of a kind of propargyl ethanol, belong to technical field of organic synthesis.
Background technology
Allyl alcohols is the method that fine chemistry industry produces intermediate and Chemicals thereof, mainly for the production of VE main intermediate, and DV chrysanthemumic acid (chrysanthemum ester intermediate), synthesise vitamins A, vitamin K1, carotenoid intermediate, synthetic rubber monomer and spices.
Its reaction expression is:
Wherein, R1, R2 are hydrogen or alkyl.
The selective hydrogenation of propargyl alcohols is corresponding allyl alcohols, Lindlar catalyzer is generally adopted in existing industrial technology application, Lindlar catalyzer is a kind of traditional effective catalyst for alkynes selective hydrogenation synthesizing cis alkene, and its preparation method is at CaCO by Pd load
3, BaSO
4or SiO
2on, then carry out poisoning with plumbic acetate etc. and obtain.In industrial application, Lindlar catalyzer is to a series of small molecules alkynes selective hydrogenation preparing cis olefine reaction display highly selectivies and higher activity.A kind of method being prepared phantol by dehydro aromatic laurolol selective hydrogenation is disclosed in the people such as Weng Yufei " fine chemistry industry " volume the 8th phase August the 20th in 2003 " Pd, a Bi modification Pd catalyzer synthesis phantol " literary composition, hydrogenation catalyst adopts the Lindlar catalyzer improved, with the CaCO of powdery
3for carrier, load active component metal Pd, Pb and Bi.Do not add the compound such as pyridine or quinoline in catalyzer or reactive system, best experimental result is that the transformation efficiency of dehydro aromatic laurolol reaches 99%, and the gas phase selectivity of phantol reaches 98%.
Reimer etc. describe a kind of noble metal catalyst with the selective hydrogenation of monosubstituted Long carbon chain alkynes of trying out.This catalyzer take metal fabric as carrier, by vapor deposition method or pickling process by Pd, Bi, Ag load on metal fabric.They prepare Pd-Bi/ metal fabric catalyzer by vapor deposition method, prepare Pd-Ag/ metal fabric catalyzer by pickling process.At intermittent type DHIP(dehydrogenation different vegetable alcohol) in selective hydrogenation, Pd-Ag/ metal fabric catalyzer shows the IP(different vegetable alcohol higher than 95%) selectivity, and Pd-Bi/ metal fabric catalyst selectivity is slightly low, is 93.2%.
Chinese patent 96110670.0 also discloses the catalyzer of a kind of Pd loaded metal cloth or tinsel, it passes through heat carrier in atmosphere, palladium metal is coated on carrier and obtains the fixed bed carried type catalyzer being used for this reaction by decompression, and support of the catalyst adopts the metallic carrier of metal braid or tinsel situation.This patented technology needs to add a certain amount of CO gas, just can have good product selectivity.Be applied to the liquid phase alkynes that dehydro aromatic laurolol selective hydrogenation prepares phantol and carry out the method for sequential portion Hydrogenation for alkene, within 100 days, turn afterwards and still can keep higher transformation efficiency, the excessive hydrogenation control of product is 1.2%.
The people such as LyudmilaM.Bronstein (journalofcatalysis196,302-314(2000)) active ingredient is adopted to be the bimetal of PdAu, PdPt, PdZn, with PS-b-P4VP nanoparticle (polyethylene and poly-4-vinylpyridine segmented copolymer) for carrier, second metal (Au, Pt, or Zn) as the properties-correcting agent to Pd, in PS-b-P4VP, pyridine unit carries out chemical modification in nanoparticle surface simultaneously, makes this catalyzer have high conversion and highly selective.
prior art has the following disadvantages:
(1) propargyl alcohols transformation efficiency, allyl alcohol selectivity is low, and excessive hydrogenation selectivity of product is high, high pin material, low yield.
(2) solid-carrying type catalyst system is adopted in prior art, reaction system is solid-liquid-gas three phase reaction, reaction needs the stirring of high strength that catalyzer just can be made to be dispersed in system, catalyst cupport is uneven or disperse uneven meeting to cause local catalytic level too high, and its result causes low selectivity and high pin material.
(3) catalyst separating is complicated, needs long-time sedimentation, filtration, and catalyst loss is serious, and operating process is loaded down with trivial details.
Summary of the invention
The present invention, for solving above technical problem, provides a kind of propargyl ethanol selective hydrogenation to prepare the method for allyl alcohol, to realize following goal of the invention:
(1) propargyl ethanol transformation efficiency >=99.9%, allyl alcohol selectivity >=99.0%, excessive hydrogenation selectivity of product < 1.0%, pin material rate < 0.8%, yield > 98.5%.
(2) the present invention reacts in water-organic biphasic system, and stirring intensity is low, and catalyzer is uniformly dispersed; And because adopting water to make solvent, do not bring other organic solvents into, environmentally friendly.
(3) catalyst stabilization of the present invention's use, catalyst consumption is low.
(4) product of the present invention and catalyst system easily separated, simple to operate.
For solving the problems of the technologies described above, the present invention by the following technical solutions:
A method for allyl alcohol is prepared in propargyl ethanol selective hydrogenation, and described method, comprises and feeding intake, nitrogen, hydrogen exchange, hydrogenation reaction; Complex catalyst is adopted to carry out hydrogenation reaction at water-organic biphasic.
Below the further improvement to technique scheme:
Described catalyzer is the complex compound that the water-soluble salt of group VIII metal and water soluble ligand are formed.
The water-soluble salt of described group VIII metal be Palladous chloride, Palladous nitrate, palladous sulfate, tetrachloro-palladium potassium chlorate, dichloro four ammonia palladium, platinum chloride, platinum nitrate, Platinic chloride, potassium platinochloride, ammonium chloroplatinate, ammonium chloroplatinite, tetranitro potassium platinate, dichloro four ammino platinum one or more.
Described water soluble ligand is water-soluble phosphine ligand; Described water-soluble phosphine ligand is preferably one or more in potassium sulfonate between sodium sulfonate between triphenylphosphine, triphenylphosphine, three-(2,4-dimethyl-5-sodium sulfonate phenyl) phosphines, three-(2 methoxyl group-3-sodium sulfonate phenyl) phosphines, three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphines, ethyl sulfonic acid sodium base diphenylphosphine, three-(2-sodium sulfonate dibenzofuran group) phosphines.
Describedly to feed intake, 0.1 ~ 5 part of water, 0.005 ~ 0.1 part of catalyzer are joined in still, then adds 1 part of propargyl ethanol.
Described propargyl ethanol is the one of methylbutynol, dehydro aromatic laurolol, dehydrogenation nerolidol, dehydrogenation different vegetable alcohol.
The mass ratio of described VIIIth race's water-soluble metal salt and water soluble ligand is 0.001 ~ 0.01:1.
Described hydrogenation reaction, hydrogen pressure is 0.5 ~ 3.0MPa, and temperature of reaction is 40 ~ 120 DEG C; Under the condition of mixing speed 100 ~ 1000rpm, compressive reaction 2 ~ 20h.
Described hydrogenation reaction, until propargyl ethanol transformation efficiency > 99.9%, stopped reaction.
The transformation efficiency of propargyl ethanol is 99.9-99.99%, and the selectivity of allyl alcohol is 99.10-99.65%, and yield is 98.51-98.83%.
The present invention compared with prior art, has following beneficial effect:
(1) the present invention uses water soluble metal complexes catalyst system, catalyzer is uniformly dissolved completely and is scattered in aqueous phase, reaction is surface reaction, traditional immobilized AlCl_3 catalyst can be avoided to cause because local catalytic level is too high seriously crossing hydrogen and high pin material phenomenon, the transformation efficiency of propargyl ethanol of the present invention is 99.9-99.99%, and the gas phase selectivity of allyl alcohol is 99.10-99.65%, and yield is 98.51-98.83%, the selectivity of excessive hydrogenation product is 0.33-0.68%, and pin material rate is 0.51-0.6%.
(2) the present invention reacts in water-organic biphasic system, and mixing speed is low, and be 100 ~ 1000rpm, catalyzer is uniformly dispersed; And because adopting water to make solvent, do not bring other organic solvents and promotor into, environmentally friendly.
(3) catalyst stabilization of the present invention's use, catalyst consumption is low, is applicable to suitability for industrialized production: catalyst system can realize the cyclical operation of more than 30 times, when catalyst system applies mechanically 30 times, the transformation efficiency of propargyl ethanol is 99.93%, and the selectivity of allyl alcohol is 99.34%, and yield is 98.73%.
(4) the present invention uses water-oily two phase reaction, after completion of the reaction layering, directly obtains product, simple to operate, energy-conservation.
(5) by product of the present invention-excessive hydrogenation selectivity of product is low, and its principal product, as spices, contributes to promoting flavouring essence quality.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
the method of allyl alcohol is prepared in embodiment 1 one kinds of propargyl ethanol selective hydrogenations
Described propargyl ethanol is methylbutynol, and described allyl alcohol is methyl butenol.
Described method, comprises the following steps:
(1) feed intake
The complex catalyst of sodium sulfonate between 3g ammonium chloroplatinite and triphenylphosphine, 100g water are joined in the 1L autoclave of band magnetic agitation and temperature controller, then adds methylbutynol 200g; In complex compound, between platinum chloride and triphenylphosphine, the mass ratio of sodium sulfonate is 0.01:1.
(2) nitrogen, hydrogen exchange
With nitrogen replacement three times, hydrogen exchange three times.
(3) hydrogenation reaction
Be heated to 70 DEG C, hydrogen pressure adds to 2.0MPa, stirs 200rpm, reacts 8 hours, sampling analysis methyl butyne alcohol conversion > 99.9%, stopped reaction.
(4) Reaction Separation
Water cooling, extrudes reaction solution, stratification, and the aqueous phase containing catalyzer can continue to apply mechanically down to be criticized, and organic phase is methyl butenol.
Through gas chromatographic analysis, the transformation efficiency of methylbutynol is 99.99%, and the selectivity of methyl butenol is 99.65%, and crossing hydrogen product methyl butanol selectivity is 0.33%.
Organic phase obtains finished product 203.04g by rectification under vacuum, and pin material is 1.22g, and calculated yield is: 98.83%.
the method of allyl alcohol is prepared in embodiment 2 one kinds of propargyl ethanol selective hydrogenations
Described propargyl ethanol is dehydro aromatic laurolol, and described allyl alcohol is phantol.
Described method, comprises the following steps:
(1) feed intake
6g Palladous chloride and three-complex catalyst of (2,4-dimethyl-5-sodium sulfonate phenyl) phosphine, 200g water are joined in the 1L autoclave of band magnetic agitation and temperature controller, then adds dehydro aromatic laurolol 200g; The mass ratio of complex compound Palladous chloride and three-(2,4-dimethyl-5-sodium sulfonate phenyl) phosphine is 0.008:1.
(2) nitrogen, hydrogen exchange
With nitrogen replacement three times, hydrogen exchange three times.
(3) hydrogenation reaction
Be heated to 80 DEG C, hydrogen pressure adds to 2.0MPa, stirs 400rpm, reacts 15 hours, sampling analysis dehydro aromatic laurolol transformation efficiency > 99.9%, and reaction terminates.
(4) Reaction Separation
Water cooling, extrudes reaction solution, stratification, and the aqueous phase containing catalyzer can continue to apply mechanically down to be criticized, and organic phase is phantol.
Through gas chromatographic analysis, the transformation efficiency of dehydro aromatic laurolol is 99.94%, and the selectivity of phantol is 99.35%, and crossing hydrogen product dihydrolinalool selectivity is 0.51%.
Organic phase obtains finished product 201.25g by rectification under vacuum, and pin material is 1.08g, and calculated yield is: 98.73%.
the method of allyl alcohol is prepared in embodiment 3 one kinds of propargyl ethanol selective hydrogenations
Described propargyl ethanol is dehydrogenation nerolidol, and described allyl alcohol is nerolidol.
Described method, comprises the following steps:
(1) feed intake
8g Palladous chloride and three-complex catalyst of (2-sodium sulfonate dibenzofuran group) phosphine, 200g water are joined in the 1L autoclave of band magnetic agitation and temperature controller, then adds dehydrogenation nerolidol 200g; The mass ratio of complex compound Palladous chloride and three-(2-sodium sulfonate dibenzofuran group) phosphine is 0.006:1.
(2) nitrogen, hydrogen exchange
With nitrogen replacement three times, hydrogen exchange three times.
(3) hydrogenation reaction
Be heated to 80 DEG C, hydrogen pressure adds to 2.0MPa, stirs 400rpm, reacts 17 hours, sampling analysis dehydrogenation nerolidol transformation efficiency > 99.9%.
(4) Reaction Separation
Water cooling, extrudes reaction solution, stratification, and the aqueous phase containing catalyzer can continue to apply mechanically down to be criticized, and organic phase is nerolidol.
Through gas chromatographic analysis, the transformation efficiency of dehydrogenation nerolidol is 99.93%, and the selectivity of nerolidol is 99.16%, and crossing hydrogen product methyl butenol selectivity is 0.62%.
Organic phase obtains finished product 200.48g by rectification under vacuum, and pin material is 1.02g, and calculated yield is: 98.57%.
the method of allyl alcohol is prepared in embodiment 4 one kinds of propargyl ethanol selective hydrogenations
Described propargyl ethanol is dehydrogenation different vegetable alcohol, and described allyl alcohol is different vegetable alcohol.
Described method, comprises the following steps:
(1) feed intake
The complex catalyst of potassium sulfonate between 10g Palladous chloride and triphenylphosphine, 200g water are joined in the 1L autoclave of band magnetic agitation and temperature controller, then adds dehydrogenation different vegetable alcohol 200g; Between complex compound Palladous chloride and triphenylphosphine, the mass ratio of potassium sulfonate is 0.004:1.
(2) nitrogen, hydrogen exchange
With nitrogen replacement three times, hydrogen exchange three times.
(3) hydrogenation reaction
Be heated to 90 DEG C, hydrogen pressure adds to 2.0MPa, stirs 800rpm, reacts 20 hours, sampling analysis dehydrogenation different vegetable alcohol transformation efficiency > 99.9%.
(4) Reaction Separation
Water cooling, extrudes reaction solution, stratification, and the aqueous phase containing catalyzer can continue to apply mechanically down to be criticized, and organic phase is different vegetable alcohol.
Through gas chromatographic analysis, the transformation efficiency of dehydrogenation different vegetable alcohol is 99.91%, and the selectivity of nerolidol is 99.10%, and crossing hydrogen product methyl butenol selectivity is 0.68%.
Organic phase obtains finished product 199.98g by rectification under vacuum, and pin material is 1.07g, and calculated yield is: 98.51%.
Catalyzer in embodiment 2, solvent are applied mechanically, its experimental result is as following table:
Shown in upper table, catalyzer is applied mechanically after 30 and is still had higher transformation efficiency and selectivity.
Through test of many times, adopt the technical parameter of each step of following method, technical qualification, all can realize goal of the invention of the present invention:
a method for allyl alcohol is prepared in propargyl ethanol selective hydrogenation, comprises the following steps:
(1) feed intake
1 part of propargyl alcohols, 0.1 ~ 5 part of water and 0.005 ~ 0.1 part of catalyzer are joined in autoclave.
Described catalyzer is the complex compound that the water-soluble salt of group VIII metal and water soluble ligand are formed.
The water-soluble salt of described group VIII metal be Palladous chloride, Palladous nitrate, palladous sulfate, tetrachloro-palladium potassium chlorate, dichloro four ammonia palladium, platinum chloride, platinum nitrate, Platinic chloride, potassium platinochloride, ammonium chloroplatinate, ammonium chloroplatinite, tetranitro potassium platinate, dichloro four ammino platinum one or more.
Described water soluble ligand is water-soluble phosphine ligand; Described water-soluble phosphine ligand is preferably one or more in potassium sulfonate between sodium sulfonate between triphenylphosphine, triphenylphosphine, three-(2,4-dimethyl-5-sodium sulfonate phenyl) phosphines, three-(2 methoxyl group-3-sodium sulfonate phenyl) phosphines, three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphines, ethyl sulfonic acid sodium base diphenylphosphine, three-(2-sodium sulfonate dibenzofuran group) phosphines.
(2) nitrogen, hydrogen exchange
Nitrogen replacement three times, hydrogen exchange three times.
(3) hydrogenation reaction
Then react under hydrogen pressure 0.5 ~ 3.0MPa pressure, temperature of reaction is 40 ~ 120 DEG C, reacts 2 ~ 20h, until propargyl alcohols transformation efficiency reaches 99.9% under stirring the condition of 100 ~ 1000rpm.
(4) Reaction Separation
After reaction terminates, stratification, aqueous phase is applied mechanically to lower batch reaction, and organic phase is allyl alcohol.
Except as otherwise noted, the percentage ratio adopted in the present invention is weight percentage, and ratio of the present invention, is mass ratio.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (10)
1. a method for allyl alcohol is prepared in propargyl ethanol selective hydrogenation, it is characterized in that: described method, comprises and feeding intake, nitrogen, hydrogen exchange, hydrogenation reaction; Described method adopts complex catalyst to carry out hydrogenation reaction at water-organic biphasic.
2. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 1, it is characterized in that: described catalyzer is the complex compound that the water-soluble salt of group VIII metal and water soluble ligand are formed.
3. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 2, it is characterized in that: the water-soluble salt of described group VIII metal be Palladous chloride, Palladous nitrate, palladous sulfate, tetrachloro-palladium potassium chlorate, dichloro four ammonia palladium, platinum chloride, platinum nitrate, Platinic chloride, potassium platinochloride, ammonium chloroplatinate, ammonium chloroplatinite, tetranitro potassium platinate, dichloro four ammino platinum one or more.
4. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 2, it is characterized in that: described water soluble ligand is water-soluble phosphine ligand; Described water-soluble phosphine ligand is preferably one or more in potassium sulfonate between sodium sulfonate between triphenylphosphine, triphenylphosphine, three-(2,4-dimethyl-5-sodium sulfonate phenyl) phosphines, three-(2-methoxyl group-3-sodium sulfonate phenyl) phosphines, three-(4-methoxyl group-3-sodium sulfonate phenyl) phosphines, ethyl sulfonic acid sodium base diphenylphosphine, three-(2-sodium sulfonate dibenzofuran group) phosphines.
5. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 1, it is characterized in that: described in feed intake, 0.1 ~ 5 part of water, 0.005 ~ 0.1 part of catalyzer are joined in still, then add 1 part of propargyl ethanol.
6. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 5, it is characterized in that: described propargyl ethanol is the one of methylbutynol, dehydro aromatic laurolol, dehydrogenation nerolidol, dehydrogenation different vegetable alcohol.
7. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 2, it is characterized in that: the mass ratio of described VIIIth race's water-soluble metal salt and water soluble ligand is 0.001 ~ 0.01:1.
8. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 1, and it is characterized in that: described hydrogenation reaction, hydrogen pressure is 0.5 ~ 3.0MPa, and temperature of reaction is 40 ~ 120 DEG C; Under the condition of mixing speed 100 ~ 1000rpm, compressive reaction 2 ~ 20h.
9. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 1, it is characterized in that: described hydrogenation reaction, until propargyl ethanol transformation efficiency > 99.9%, and stopped reaction.
10. the method for allyl alcohol is prepared in a kind of propargyl ethanol selective hydrogenation according to claim 1, it is characterized in that: the transformation efficiency of propargyl ethanol is 99.9-99.99%, and the selectivity of allyl alcohol is 99.10-99.65%, and yield is 98.51-98.83%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107089900A (en) * | 2017-04-28 | 2017-08-25 | 山东新和成药业有限公司 | A kind of preparation method of β benzyl carbinols |
| CN109622049A (en) * | 2018-12-21 | 2019-04-16 | 万华化学集团股份有限公司 | The catalyst and its preparation method of allyl alcohol are prepared for propargyl alcohol moieties plus hydrogen |
| CN111185237A (en) * | 2020-02-19 | 2020-05-22 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
| CN113620778A (en) * | 2021-08-17 | 2021-11-09 | 万华化学集团股份有限公司 | Method for preparing allyl alcohol compound by reduction of propargyl alcohol compound |
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| CN103342627A (en) * | 2013-06-27 | 2013-10-09 | 山东新和成药业有限公司 | Method for selective hydrogenation synthesis of nerol and geraniol mixture by using citral in water-organic two-phase system |
| CN103360215A (en) * | 2013-06-27 | 2013-10-23 | 山东新和成药业有限公司 | Method for synthesizing isopentenol from 3-methyl-3-butene-1-ol through catalytic transposition in water-organic two-phase system |
| CN103566932A (en) * | 2013-11-01 | 2014-02-12 | 山东新和成药业有限公司 | Powdered Pd/SiO2 catalyst and preparation method and applications thereof |
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| CN103342627A (en) * | 2013-06-27 | 2013-10-09 | 山东新和成药业有限公司 | Method for selective hydrogenation synthesis of nerol and geraniol mixture by using citral in water-organic two-phase system |
| CN103360215A (en) * | 2013-06-27 | 2013-10-23 | 山东新和成药业有限公司 | Method for synthesizing isopentenol from 3-methyl-3-butene-1-ol through catalytic transposition in water-organic two-phase system |
| CN103566932A (en) * | 2013-11-01 | 2014-02-12 | 山东新和成药业有限公司 | Powdered Pd/SiO2 catalyst and preparation method and applications thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107089900A (en) * | 2017-04-28 | 2017-08-25 | 山东新和成药业有限公司 | A kind of preparation method of β benzyl carbinols |
| 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 |
| CN109622049A (en) * | 2018-12-21 | 2019-04-16 | 万华化学集团股份有限公司 | The catalyst and its preparation method of allyl alcohol are prepared for propargyl alcohol moieties plus hydrogen |
| CN111185237A (en) * | 2020-02-19 | 2020-05-22 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
| CN111185237B (en) * | 2020-02-19 | 2020-11-06 | 浙江大学 | Selective hydrogenation catalyst, preparation method and application thereof |
| WO2021164099A1 (en) * | 2020-02-19 | 2021-08-26 | 浙江大学 | Selective hydrogenation catalyst, preparation method therefor and use thereof |
| CN113620778A (en) * | 2021-08-17 | 2021-11-09 | 万华化学集团股份有限公司 | Method for preparing allyl alcohol compound by reduction of propargyl alcohol compound |
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