GB2096595A - Process for producing C4-C10 ethylene alcohols - Google Patents
Process for producing C4-C10 ethylene alcohols Download PDFInfo
- Publication number
- GB2096595A GB2096595A GB8111342A GB8111342A GB2096595A GB 2096595 A GB2096595 A GB 2096595A GB 8111342 A GB8111342 A GB 8111342A GB 8111342 A GB8111342 A GB 8111342A GB 2096595 A GB2096595 A GB 2096595A
- Authority
- GB
- United Kingdom
- Prior art keywords
- catalyst
- weight
- hydrogen
- hydrogenation
- alcohols
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
- C07C33/025—Acyclic alcohols with carbon-to-carbon double bonds with only one double bond
- C07C33/035—Alkenediols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process of producing C4-C10 ethylene alcohols of the formula: <IMAGE> wherein (a) R1 is -CH2OH, and R2 = R3 = -H, or (b) R1 is -H, R2 = -CH3, and R3 = -CH3 or -C6H11, comprises effecting hydrogenation of the corresponding acetylene alcohols in the liquid phase on a membrane catalyst made of an alloy comprising palladium and ruthenium in a weight ratio of 90-94:10-6 respectively, wherein hydrogenation of the alcohols is effected by means of hydrogen diffusing through the membrane catalyst at a temperature of from 60 to 180 DEG C under atmospheric pressure of hydrogen.
Description
SPECIFICATION
Process for producing C4-Cro ethylene alcohols
The present invention relates to a process for producing C4-C10 ethylene alcohols. These alcohols comprise valuable intermediate products in organic synthesis and can be useful in the production of vitamins and cosmetics.
A process is known (cf. USSR Inventor's Certificate No. 311 887) for producing an ethylene alcohol, namely 2-butenediol-1,4, by hydrogenation of 2-butynediol-1,4 with hydrogen in an organic solvent medium in the presence of oxalic acid on a catalyst comprising a mixture of palladium black and black of a metal of the group of palladium (except platinum per se). In this process, wherein use is made of palladium black and ruthenium black, the process selectivity at a temperature of 20"C is equal, relative to 2-butenediol-1,4, to 96% at full conversion; the stereospecificity relative to cis-2-butenediol-1 4, is equal to 97%.
This prior art process has, however, the following disadvantages: (1) a pure starting alcohol and pure hydrogen must be used; (2) hydrogenation is conducted in an organic solvent medium in the presence of oxalic acid, thus adding to the production costs; (3) the mechanical strength of the catalyst in the form of a metal black is insufficient, as a result of which separation of the catalyst from the reaction mixture is hindered; (4) difficulties are encountered in regeneration of the catalyst after reduction of its activity.
Thermal treatment cannot be applied due to sintering of the black particles, as a result of which regeneration of the catalyst should be preferably effected by dissolution thereof to recover noble metals and subsequently prepare a fresh portion of the black. However, the regeneration scheme is labour-consuming.
In another known process (cf. German Patent No. 2 431 929; U.S. Patent No. 4 001 344;
British Patent No.1 504 187) 2-butenediol-1,4 is produced by hydrogenation, with hydrogen, of a technical product, namely a 30% aqueous solution of 2-butynediol-1,4, on a catalyst containing 0.05 to 2% weight of palladium, 0.05 to 1% by weight of zinc and cadmium supported by y-alumina at a temperature of from 60 to 75"C under a hydrogen pressure of from 1 to 1 6 atm. the yield of 2-butene-1,4-diol is 88 to 92.5% of the theoretical yield. The aboveindicated starting technical product is prepared by a conventional Reppe process using acetylene and an aqueous solution of formaldehyde in the presence of copper acetylenide.
A disadvantage of this known process for producing 2-butenediol-1 ,4 resides in the formation of resinuous products in an amount of from 7.5 to 12% by weight. Furthermore, other disadvantages are associated with a relatively low yield of the desired product, the necessity of separation thereof from the catalyst by filtration and accompanying losses of the noble metal (palladium), and difficulties of regeneration of the catalyst after reduction of its activity (the regeneration comprises the recovery of the noble metal from the spent catalyst and the preparation of a fresh portion of the catalyst). The obligatory stage of separation of the desired product from the catalyst and considerable labour-consumption in the regeneration stage complicate the process as a whole.
In a process disclosed in British Patent No. 888 999, acetylene alcohols in the form of commercial products, e.g. commercial 2,6-dimethylocten-2-in-7-ol-6 (dehydrolinalool) and commercial 2-methylbutyn-3-ol-2 (dimethylethylcarbinol) are selectively hydrogenated with hydrogen into corresponding ethylene alcohols under atmospheric pressure of hydrogen, optionally in a solvent medium, on a catalyst containing up to 20% by weight of palladium and 0.1 to 20% by weight of iead deposited on barium sulphate, calcium carbonate or barium carbonate, activated coal or magnesia at a temperature of from 10 to 75"C. The hydrogenation process is conducted discontinuously. Separation of the desired product from the catalyst is effected by the vacuum distillation method.The yield of 2,6-dimethyloctadien-2,7-ol-6 (linalool) is 90.5%, and that of 2methyl-buten-3-ol-2 (dimethylvinylcarbinol) is 97%, as calculated for the starting acetylene alcohol.
However, the discontinuous nature of the hydrogenation process and the use of vacuum distillation substantially increase the process duration. The vaccum distillation also necessitates the use of expensive process equipment and lowers the yield of the desired products.
It should be noted that the liquid phase hydrogenation of acetylene alcohols under continuous flow conditions on the catalysts employed in all the above-described prior art processes is impossible due to unavoidable high losses of noble metals of the catalyst. Furthermore, a common disadvantage of the above-mentioned prior art processes resides in the difficult regeneration of catalysts on carriers and catalysts in the form of noble metal blacks. Such regeneration involves dissolution of noble metals in a mixture of nitric acid, recovery of chlorides of noble metals and preparation of a fresh portion of the catalyst. All these operations take a long time and necessitate the use of sophisticated process equipment.
The present invention provides a process for producing C4-Cro ethylene alcohols of the formula:
wherein (a) R, is - CH20H, and R2 = R3 = - H, or (b) R, is - H, R2 is - CH3, and R3 is - CH3 or - C6H11, comprising effecting hydrogenation of acetylene alcohols of the formula:
wherein (a) R, is - CH2OH, and R2 = R3 = - H, or (b) R1 is - H, R2 is - CH3, and R3 is - CH or - C6H11, in the form of products in the liquid phase on a membrane catalyst made of an alloy comprising palladium and ruthenium in a weight ratio therebetween of 90-94::10-6 respectively, wherein hydrogenation of the said alcohols is effected by means of hydrogen diffusing through the membrane catalyst at a temperature of from 60 to 1 80 C and at atmospheric pressure of hydrogen.
The process according to the present invention has the following advantages over the prior art processes: (1) the use of a solid membrane catalyst comprising a structural element of a reactor eliminates losses of noble metals of the catalyst; (2) the use of a membrane catalyst of a palladium-ruthenium alloy makes it possible to hydrogenate commercial acetylene alcohols with higher yields of ethylere alcohols compared to the prior art processes, i.e. up to 99.2% of the theoretical yield; (3) the use of a membrane catalyst makes it possible to carry out hydrogenation of acetylene alcohols under conditions of continuous flow, thus intensifying the process as a whole in comparison with the prior art processes;; (4) production of ethylene alcohols is intensified due to elimination of vacuum distillation and filtration from the process scheme which in the prior art processes are used for the separation of the desired products from the catalyst; (5) regeneration of the membrane catalyst is effected in a substantially simpler manner than regeneration of catalysts supported on carriers or metal black catalysts; (6) the use of a membrane catalyst makes it possible to use non-purified technical hydrogen, since it becomes purified during its diffusion through the membrane catalyst.
The-membrane catalyst employed in the process according to the present invention comprises an alloy of 90-94% by weight of palladium with 6 to 10% by weight of ruthenium. At a content of ruthenium below 6% by weight, the alloy becomes brittle in the atmosphere of hydrogen. At a content of ruthenium of up to 10% by weight, its mechanical strength is increased Thus, the tensile strength is increased from 18.8 kgf/mm2 for pure palladium to 46 kgf/mm2 for an alloy with a content of ruthenium of 9.21% by weight. Alloys containing above 10% by weight of ruthenium have too low a permeability for hydrogen; thus, upon increasing the content of ruthenium in the alloy of from 10 to 12% by weight, the hydrogen permeability is halved.The highest hydrogen permeability in combination with a high mechanical strength and plasticity is inherent only in alloys containing ruthenium in an amount of from 6 to 10% by weight. Therefore, the use of palladium alloys with a content of ruthenium below 6% and above 10% by weight as hydrogen-permeable catalysts is undesirable.
The membrane catalyst utilized in the process according to the present invention preferably comprises a 20-100 pmthick foil of a thin-walled tube shaped as a helix with a wall thickness of from 50 to 200 ym, made of the alloy of the above-specified composition. At one side of the foil or outside the tube there is supplied the starting acetylene alcohol in the form of a technical product which is supplied either continuously or discontinuously, while along the other side of the foil or inside the tube pure or non-purified technical hydrogen is passed continuously; this hydrogen diffuses through the foil or tube wall towards the opposite surface to contact the compound to be hydrogenated.The hydrogenation process is carried out at a temperature of from 60 to 180"C under atmospheric pressure of hydrogen either discontinuously or continuously. The analysis of the catalyzate withdrawn from the reactor is effected by gas-liquid chromatography.
The starting materials, i.e. acetylene alcohols, are preferably used in the process according to the present invention as technical products. Such technical products are prepared in a conventional manner. Thus, a technical product comprising a 30-35% aqueous solution of 2butyndiol-1,4 is prepared by the Reppe method from acetylene and an aqueous solution of formaldehyde in the presence of copper acetylenide. Technical 2-methylbutyn-3-ol-2(dimethylethynylcarbinol) and 2, 6-dimethylocten-2.in-7-ol-6(dehydrolinalool) are prepared by known methods by ethynylation of acetone and 2-methylhepten-2-on-6 respectively. In the resulting commercial acetylene alcohols the content of the starting carbonyl compounds varies, as a rule, within the range of from 1.5 to 7% by weight.
It should be noted that the membrane catalyst made of an alloy comprising 90-94% by weight of palladium and 6 to 10% by weight of ruthenium retains its activity without regeneration under the process conditions during hydrogenation of 2-butynediol-1,4 for 30 hours, and during hydrogenation of technical dehydrolinalool for more that 400 hours.
Regeneration of the membrane catalyst is effected directly in a hydrogenation reactor (without discharge) of the catalyst) in a current of dry air at a temperature of 400"C for one hour, followed by treatment with hydrogen at the same temperature for one hour. After such regeneration the catalyst activity is fully restored. This regeneration method is not labourconsuming and comprises a simple process scheme.
The invention will be further described with reference to the following illustrative Examples.
Unless otherwise specified, all yields of the products in the Examples are expressed in per cent by weight.
EXAMPLE 1
Hydrogenation was conducted in a flow-type reactor consisting of two chambers separated from each other by means of a membrane catalyst made as a foil of an alloy consisting of 90% by weight of palladium and 10% by weight of ruthenium. The visible surface area of the membrane catalyst was 420 cm2, and the thickness of the catalyst was 20 ym. Into one of the chambers was continuously fed hydrogen under a pressure of 1 atm, while through the other chamber was continuously passed technical 2-butynediol-1,4 in the form of a 30% aqueous solution thereof containing formaldehyde in an amount of 1.5% and small amounts of formic acid and propargyl alcohol at a rate of 33 ml/hr. The hydrogenation was conducted at a temperature of 60"C.
The yield of 2-butenediol-1 ,4 was equal to 98.6% of the theoretical value (stereoselectivity relative to cis-2-butenediol-1,4 was equal to 93.8%), that of butanediol-1,4 was 0.4%, and that of resinous substances was below 1%. The amount of unreacted 2-butyndiol-1,4 was less than 0.1 % of the starting value. The catalyst productivity was 255 g (2.9 moles) of cis-2-butenediol1,4 from 1 m2 of the catalyst per hour.
EXAMPLE 2
There was placed in a reaction vessel, together with technical 2-butynediol-1,4 (the composition of the commercial product was similar to that described in Example 1), a thin-walled tube in the shape of a helix made of an alloy consisting of 94% by weight of palladium and 6% by weight of ruthenium. The tube had a visible outer surface area of 30 cm2, an outside diameter of 1 mm, and a wall thickness of 100 ym. The temperature in the reaction vessel was elevated to 90"C, whereafter technical hydrogen containing 5% by volume of air was fed into the tube under a pressure of 1 atm.
After absorption of 1 mole of hydrogen per 1 mole of 2-butynediol-1,4 there was obtained 2butenediol-1,4 in a yield of 95.6% of the theoretical value (stereo-selectivity relative to cis-2butenediol-1,4 was equal to 96.2%), butanediol-1,4 in a yield of 1.2%, and resinous products in a yield of 3.2%. The amount of unreacted 2-butynediol-1,4 was less than 0.1% of the starting value. The catalyst productivity was 200 g (2.3 moles) of cis-butenediol-1.4 from 1 m2 of the catalyst per hour.
EXAMPLE 3
Technical 2-butynediol-1,4 (the composition of the commercial product was similar to that described in Example 1) was subjected to hydrogenation on a membrane catalyst in the form of a foil of an alloy consisting of 92% by weight of palladium and 8% by weight of ruthenium.
The foil thickness was 100 ym, and the visible surface area of the foil was 10 cm2. The hydrogenation process was conducted discontinuously at a temperature of 72"C under a pressure of hydrogen of 1 atm.
The yield of 2-butenediol -1,4 was equal to 95.5% of the theoretical value (stereoselectivity relative to cis-2-butenediol-1 ,4 was equal to 96.8%), that of butanediol-1 ,4 was 1.5%, and that of resinous substances was 2.0%. The amount of unreacted 2-butynediol-1,4 was 1.0% of the starting value. The catalyst productivity was 106 g (1.2 mol) of cis-2-butenediol-1 ,4 from 1 m2 of the catalyst per hour.
EXAMPLE 4
Commercial 2-methylbutyn-3-ol-2 (dimethylethynylcarbinol) containing 5% by weight of acetone was hydrogenated in a flow-type reactor similar to that described in Example 1 on a membrane catalyst shaped as a foil of an alloy consisting of 90% by weight of palladium and 10% by weight of ruthenium. The visible surface area of the catalyst was 22 cm2, and the foil thickness was 30 pm. The hydrogenation process was carried out at a temperature of 90"C at a rate of the alcohol supply of 3 ml/hr.
The yield of 2-methyl-butene-3-ol-2 (dimethylvinylcarbinol) was 99.2% of the theoretical value, and the yield was tert.amyl alcohol was 0.7%. The amount of the unreacted dimethylethynylcarbinol was less than 0.1% of the starting value. The catalyst productivity was 1.9 kg (13.8 moles) of dimethylvinylcarbinol from 1 m2 of the catalyst per hour.
EXAMPLE 5
Technical 2,6-dimethylocten-2-in-7-ol-6 (dehydrolinalool) containing 6.5% by weight of 2methylhepten-2-on-6 was hydrogenated as described in Example 2 on a membrane catalyst of an alloy consisting of 94% by weight of palladium and 6% by weight of ruthenium at a temperature of 90on.
The yield of 2,6-dimethyloctadien-2,7-ol-6 (linalool) was 99.0% of the theoretical value, and that of 2,6-dimethylocten-2-ol-6 (dihydrolinalool) was 0.9%. The amount of unreacted dehydrolinalool was less than 0.1 % of the starting value. The catalyst productivity was 620 g (4.0 moles) of linalool from 1 m2 of the catalyst per hour.
EXAMPLE 6
Technical dehydrolinalool having the same composition as in the foregoing Example 5 was hydrogenated in a flow-type reactor of the type described in Example 1 on a membrane catalyst made as a foil from an alloy consisting of 94% by weight of palladium and 6% by weight of ruthenium. The visible surface area of the catalyst was 360 cm2, and the foil thickness was 50 ym. The hydrogenation process was carried out at a temperature of 180"C at a rate of supply of dehydrolinalool of 145 ml/hr.
The yield of linalool was 95.2%. of the theoretical value (the selectivity relative to linalool was 97%), and the yield of dihydrolinalool was 3.2%. The amount of unreacted dehydrolinalool was 1.6% of the starting value. The catalyst productivity was 3.46 kg (22.5 moles) of linalool from I m2 of the catalyst per hour.
Claims (2)
1. A process for producing C4-Cro ethylene alcohols of the formula:
wherein (a) R1 is - CH2OH, and R2 = R3 = - H, or
(b) R1 is - H, R2 is - CH3, and R3 is - CH3 or - C6H11, comprising effecting hydrogenation of acetylene alcohols of the formula:
wherein (a) R, is - CH2OH, and R2 = R3 = - H, or
(b) R, is - H, R2 is - CH3, and R3 is - CH3 or - C6H11, in this form of products in the liquid phase on a membrane catalyst made of an alloy comprising palladium and ruthenium in weight ratio therebetween of 90-94: :10-6 respectively, wherein hydrogenation of the said alchols is effected by means of hydrogen diffusing through the membrane catalyst at a temperature of from 60 to 1 80 C and at atmospheric pressure of hydrogen.
2. A process according to Claim 1 for producing C4-C10 ethylene alcohols, substantially as herein described in any of the foregoing Examples.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3114240A DE3114240C2 (en) | 1981-04-08 | 1981-04-08 | Process for the production of alkenols |
| GB8111342A GB2096595B (en) | 1981-04-08 | 1981-04-10 | Process for producing c4-c10 ethylene alcohols |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3114240A DE3114240C2 (en) | 1981-04-08 | 1981-04-08 | Process for the production of alkenols |
| GB8111342A GB2096595B (en) | 1981-04-08 | 1981-04-10 | Process for producing c4-c10 ethylene alcohols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2096595A true GB2096595A (en) | 1982-10-20 |
| GB2096595B GB2096595B (en) | 1985-04-24 |
Family
ID=25792556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8111342A Expired GB2096595B (en) | 1981-04-08 | 1981-04-10 | Process for producing c4-c10 ethylene alcohols |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE3114240C2 (en) |
| GB (1) | GB2096595B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661646A (en) * | 1983-09-24 | 1987-04-28 | Bayer Aktiengesellschaft | Process for the preparation of 1-butene-3,4-diol |
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4532020A (en) * | 1983-03-09 | 1985-07-30 | Daikin Kogyo Co., Ltd. | Process for preparing a β-(fluoroalkyl or fluoroalkenyl)-β-hydroxyalkyne |
| DE4333293A1 (en) * | 1993-09-30 | 1995-04-06 | Basf Ag | Process for the selective hydrogenation of butynediol-1,4 to butene-2-diol-1,4 and suitable catalyst |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD16912A (en) * | ||||
| US2989567A (en) * | 1957-12-12 | 1961-06-20 | Air Reduction | Process for the production of olefinic carbinols |
| US3177258A (en) * | 1960-02-24 | 1965-04-06 | Engelhard Ind Inc | Hydrogenation process using rutheniumcontaining catalysts |
| GB936321A (en) * | 1960-11-17 | 1963-09-11 | Engelhard Ind Inc | Low pressure hydrogenolysis of acetylenic diols to produce aliphatic monohydric alcohols |
| DE2431929C3 (en) * | 1974-07-03 | 1981-04-02 | Basf Ag, 6700 Ludwigshafen | Partial hydrogenation catalyst |
| DE2710277C3 (en) * | 1977-03-09 | 1981-01-08 | Institut Neftechimitscheskogo Sinteza Imeni A.V. Toptschieva Akademii Nauk Ssr | Process for the production of a hydrogen-permeable membrane catalyst based on palladium or its alloys for the hydrogenation of unsaturated organic compounds |
| SU764314A1 (en) * | 1978-04-05 | 1983-02-15 | Институт нефтехимического синтеза им.А.В.Топчиева | Process for purifying terephthalic acid |
-
1981
- 1981-04-08 DE DE3114240A patent/DE3114240C2/en not_active Expired
- 1981-04-10 GB GB8111342A patent/GB2096595B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661646A (en) * | 1983-09-24 | 1987-04-28 | Bayer Aktiengesellschaft | Process for the preparation of 1-butene-3,4-diol |
| US8071503B2 (en) | 2006-07-27 | 2011-12-06 | Johnson Matthey Public Limited Company | Catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3114240A1 (en) | 1982-11-04 |
| DE3114240C2 (en) | 1984-11-08 |
| GB2096595B (en) | 1985-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4388479A (en) | Process for producing C4 -C10 ethylene alcohols | |
| JP2566115B2 (en) | Hydrogenation catalyst, method for producing the same and use thereof | |
| CA1191870A (en) | Catalytic hydrogenolysis of alditols | |
| US6706928B2 (en) | Aldol condensation reaction and catalyst therefor | |
| US5756864A (en) | Process for preparing D,L-menthol from D-menthol | |
| US4383124A (en) | Method for the preparation of aldehydes | |
| GB2096595A (en) | Process for producing C4-C10 ethylene alcohols | |
| SA00201006B1 (en) | A catalytic hydrogenation method in the liquid phase to convert aldehydes into corresponding alcohols. | |
| US2004350A (en) | Condensation of alcohols | |
| US4450300A (en) | Process for the continuous manufacture of n-butyraldehyde by selective hydrogenation of crotonaldehyde in the liquid phase in the presence of a palladium-aluminum oxide catalyst | |
| US20020019573A1 (en) | Process for the preparation of d,l-menthol | |
| Gryaznov et al. | Process for Producing C4-C10 Ethylene Alcohols | |
| US4400549A (en) | Hydroformylation of olefinically unsaturated compounds | |
| US11365168B2 (en) | Preparation of 5-aryl-pentanols | |
| JP2002037754A (en) | Method for producing higher ketone from unsaturated aldehyde | |
| CN114853585A (en) | Heterogeneous catalysis double bond isomerization method | |
| Takagi et al. | Yields of Methylcyclohexanone Intermediates in the Hydrogenation of Isomeric Cresols over Ruthenium and Palladium Catalysts | |
| JPH08310984A (en) | Preparation of d,l-menthol | |
| US11407701B2 (en) | Method for continuous production of 2,3-butanediol | |
| JPH11228467A (en) | Production of saturated alcohol | |
| JP2000517326A (en) | Process for producing alkyne diol or a mixture of alkyne diol and alkyne monool | |
| JP3795970B2 (en) | Method for producing α, β-unsaturated aldehyde | |
| US4599453A (en) | Process for the single-stage production of higher aliphatic ketones | |
| JP2019065040A (en) | Method for producing aldehyde | |
| JP3805435B2 (en) | Process for producing 6-methyl-3-hepten-2-one |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |