GB2175896A - Process for the manufacture of alcohols from aldehydes - Google Patents
Process for the manufacture of alcohols from aldehydes Download PDFInfo
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- GB2175896A GB2175896A GB8607420A GB8607420A GB2175896A GB 2175896 A GB2175896 A GB 2175896A GB 8607420 A GB8607420 A GB 8607420A GB 8607420 A GB8607420 A GB 8607420A GB 2175896 A GB2175896 A GB 2175896A
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- 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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
Aliphatic aldehydes are hydrogenated to form corresponding alcohols at a good conversion rate and with high selectivity in the co-presence of hydrogen and carbon monoxide by using a hydrogenating catalyst. The hydrogenating catalyst comprises (A) at least one element selected from the group consisting of iron and molybdenum and (B) at least one element selected from the group consisting of rhodium, palladium and iridium.
Description
SPECIFICATION
Process for the manufacture of alcohols from aldehydes
This invention relates to a process for the manufacture of an alcohol from an aldehyde. More particularly, the present invention relates to a process for the manufacutre of an alcohol from an aldehyde, characterized by using a catalyst containing iron and/or molybdenum and at least one element selected from the group consisting of rhodium, palladium and iridium.
For the industrial synthesis of aldehydes, the reaction of an olefin, carbon monoxide and hydrogen, namely, hydroformylation is already well known [C. K. Brown, G. Wilkinson, J. Chem.
Soc., A, 1970]. The reaction of an alcohol, carbon monoxide and hydrogen for the same purpose is also known [I. Wender, P. Piano, Organic Synthesis via Metal Carbonyl, Vol. 2, Wiley (1977)]. Particularly, the reaction of methanol, carbon monoxide and hydrogen provides acetaldehyde at a high selectivity. Aldehydes are important intermediates for the manufacture of alcohols which are a basic industrial product. Aldehydes which have been synthesized according to the above-mentioned raction are isolated and then converted to corresponding alcohols using a hydrogenation catalyst. Therefore, the industrial manufacture of alcohols is conducted according to a two step process consisting of (a) an aldehyde synthesis step and (b) a hydrogenation step.
Meanwhile, in order to manufacture alcohols more economically in one step, a process is under study wherein hydroformulation is conducted in the presence of a hydrogenation catalyst.
However, side-reactions occur and no desirable result has yet been obtained in this one step process. Besides this, a process has been disclosed for the manufacture of ethanol from a synthesis gas consisting of carbon monoxide and hydrogen using a catalyst comprising rhodium and iron [Belgium Patent No. 824823, and Japanese Patent Laid-open Publication No.
80807/1976]. However, the catalyst is low in ethanol selectivity and insufficient in activity and accordingly the process is not in industrial use. It has recently been disclosed that the addition of ruthenium to a cobalt catalyst in the homologation of methanol can produce ethanol in place of acetaldehyde, at a high selectivity, and this is attracting attention as a new process for ethanol manufacture [U.S. Patent No. 4,423,257 or Japanese Patent Publication No.
9529/1984]. In the above catalyst, however, it is necessary to strictly control the atomic ratio of cobalt/ruthenium and further the ruthenium catalyst has a problem of instability. Furthermore, this catalyst has a very low level of activity and selectivity for alcohols other than methanol.
Apart from such Group VIII elements as nickel, ruthenium, palladium, platinum, etc., rhenium has also been used as the catalyst in hydrogenation of aldehydes for conversion to corresponding alcohols [P. Rylander, "Catalytic Hydrogenation in Organic Synthesis", Academic Press, New
York, 1979]. However, all of these catalysts have been low in hydrogenating ability when hydrogen and carbon monoxide are used. The phosphine-added cobalt catalyst used in hydroformylation is also effective for the hydrogenation of aldehydes in the co-presence of hydrogen and carbon monoxide. However, a high temperature and a high pressure are required in order to allow the catalyst to express its high catalytic activity.
As stated above, no catalyst has yet been provided which can efficiently hydrogenate aldehydes in the co-presence of carbon monoxide and hydrogen for conversion to corresponding alcohols.
It is therefore an object of the present invention to provide a catalyst which can hydrogenate an aliphatic aldehyde in the co-presence of carbon monoxide and hydrogen for conversion to a corresponding alcohol at a good conversion rate and with a high selectivity.
Other objects and advanages of the present invention will become apparent to those skilled in the art from the following description and disclosure.
The present invention relates to a process for manufacturing an alcohol by hydrogenation an aliphatic aldehyde in the co-presence of hydrogen and carbon monoxide by using a hydrogenating catalyst which comprises (A) at least one element selected from the group consisting of iron and molybdenum and (B) at least one element selected from the group consisting of rhodium, palladium and iridium.
The present invention will be explained in detail below.
The following aldehydes are exemplified as being suitable for use in the present invention, namely, such aliphatic aldehydes as acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproicaldehyde, heptaldehyde, caprylaldehyde, pelargonaldehyde, capric aldehyde, acrolein, crotonaldehyde and the like.
The catalyst used in the present invention is obtained by dispersing the above-mentioned catalyst components on a carrier, as done in the preparation of an ordinary noble metal catalyst.
The catalyst of the present invention can be prepared in accordance with such methods as an impregnation method, an immersion method, an ion exchange method, a co-precipitation method, a kneading method and the like.
The material compounds for the preparation of the catalyst of the present invention contain (a) iron and/or molybdenum and (b) at least one element selected from rhodium, palladium and iridium and can be compounds ordinarily used in the preparation of metal catalysts, such as inorganic salts (e.g. oxides, chlorides, nitrates, carbonates), organic salts and chelate complexes (e.g. acetates, oxalates, acetylacetonate complexes, demethylglyoxime complexes, ethylenediamine acetate), carbonyl compounds, alkyl metal compounds and the like.
The preparation of the catalyst of the present invention will be explained below, focusing on the impregnation method. The required metal compounds as mentioned above are dissolved in a solvent such as water, methanol, ethanol, tetrahydrofuran, dioxane, hexane, benzene, toluene, ethyl acetate, dichloromethane or the like. In the resulting solution is immersed a carrier. The solvent is distilled off, and the residue is dried and, if necessary, is subjected to a treatement such a heating or the like, whereby the metal compounds are supported on the carrier.This support can be provided in accordance with various methods such as a method wherein all required metal compounds are dissolved together in a solvent and simultaneously suported on a carrier and a method wherein each metal compound is subjected, as necessary, to such treatment as reduction, heat treatment or the like and is sequentially supported on a carrier.
The preparation of the catalyst of the present invention can also be conducted in accordance with other methods such as an ion exchange method wherein metals are supported on a carrier by utilizing the ion exchangeability of the carrrier and a co-precipitation method.
The catalyst prepared as above is ordinarily subjected to a reduction treatment for activation and then used in reactions as a catalyst. The reduction is conveniently and preferably conducted at an increased temperature using a hydrogen-containing gas. The reduction may be conducted at temperatures at which rhodium, palladium and iridium can be reduced, namely, at 100 to 200"C. However, it is preferably conducted at temperatures between 200"C and 600"C for the catalyst of the present invention. This reduction by hydrogen may be conducted with the temperature being increased gradually or stepwide in order to attain thorough dispersion of each catalyst component.Alternatively, the reduction may be conducted chemically using a reducing agent such as a combination of carbon monoxide and water, hydrazine, a boron hydride compound or an aluminum hydride compound.
The carrier used in the present invention can be an ordinary carrier as long as it has a specific surface area of, preferably, 10 to 1,000 m2/g and a pore diameter of 10 A or larger. Specific examples of the carrier include silica-based carriers (e.g. silica, silica gel, a molecular sieve, diatomaceous earth), active carbon, etc.
The amount and ratio of each constituent component in the catalyst of the present invention can vary to a large extent. The ratio of rhodium, palladium and iridium to carrier is 0.001 to 0.5, preferably 0.001 to 0.3 by weight ratio in consideration of the specific surface area of the carrier. The ratio of rhodium, palladium and iridium to iron and/or molybdenum is 0.001 to 20, preferably 0.01 to 10.
The present invnetion can be applied to a flow type fixed bed reactor. A catalyst is firstly placed in a reactor and subsequently material aldehyde and a mixed gas consisting of hydrogen and carbon monoxide are introduced therein to cause a reaction. The products formed are separated out and the residual mixed gas can be purified and reused.
The present invention can be applied also to a fluidized bed reactor. Material aldehyde, a mixed gas and a fluidized catalyst are together fed into a reactor to cause a reaction. The present invention can further be applied to a liquid phase, non-uniform reaction wherein a catalyst is dispersed in a solvent and thereinto are fed material aldehyde and a mixed gas to cause a reaction.
The reaction conditions employed in the practice of the present invention are an appropriate combination of each reaction condition in order that an aldehyde is converted to a corresponding alcohol at a high yield and with high selectivity. The reaction pressure can be atmospheric pressure, namely, 0 kg/cm2 G, because the intended compound can be manufactured at a high yield and with high selectivity at that pressure. However, it can also be subjected to pressure in order to increase the space/time yield. Therefore, the reaction pressure can vary between 0 and 400 kg/cm2 G, preferably 0 and 300 kg/cm2 G. The reaction temperature is 150 to 450"C, preferably 180 to 350"C. The amount of aldehyde fed is preferably 0.01 to 100 mole per hour per 1 liter of catalyst. The space velocity (amount of hydrogen and carbon monoxide fed x volume of catalyst) is appropriately selected in the range between 10 h 1 and 106 h 1 when expressed in normal state conditions (0 C and 1 atm), depending on the reaction pressure, the reaction temperature and the hydrogen/carbon monoxide ratio used.
The present invention is explained in more detail below by way of Examples, but is in no way restricted by them.
Example 1
3.7 g (10 ml) of a silica gel (Davison X57 manufactured by Davison Co.) subjected in advance to calcination and degassing at 300"C for 2 hours under high vacuum was immersed in an ethanol solution containing 0.480 g of rhodium chloride (RhCl3H2O) and 0.109 g of ferrous chloride (FeCI2.4H20). Then, ethanol was distilled off using a rotary evaporator and the residue was dried under vacuum.This dried matter was placed in a Pyrex glass reaction tube and was subjected to activation treatment at 400"C for 4 hours at normal pressure in a current of a mixed gas consisting of H2 and N2 (H2: 60 ml/min, N2: 60 ml/min) to prepare a Fe-Rh/SiO2 catalyst. 3 ml of this catalyst was placed in the flow type reactor made of titanium and was subjected to a rereduction treatment at 300"C for 2 hours in a current of H2 gas of normal pressure. Thereafter, acetaldehyde, hydrogen and carbon monoxide were fed therein and a reaction was carried out under predetermined conditions shown in Table 1. Liquid products were gathreed by dissolving in water, after which these products were subjected to gas chromatography so as to conduct qualitative and quantitative analyses. Gaseous products were directly analyzed with the gas chromatography.The results are shown in Table 1.
Example 2
The same procedure as in Example 1 was repeated except that n-butyraldehyde was used in place of acetaldehyde. The results are shown in Table 1.
Example 3
30 ml of a silica gel subjected in advance to calcination and degassing at 300"C for 2 hours was immersed in an ethanol solution containing 0.240 g of rhodium chloride and 0.075 g of molybdenum chloride (MoCI6). The same treatment as in Example 1 was applied to prepare a
Mo-Rh/SiO2 catalyst. Using 4 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 4
30 ml of a silica gel subjected to calcination and degassing was immersed in an ethanol solution containing 0.240 g of rhodium chloride and 0.075 g of molybdenum chloride and 0.036 g of ferrous chloride. The same treatment as in Example 1 was applied to prepare a Fe-Mo
Rh/SiO2 catalyst. Using 4 ml of this catalyst, n-butyraldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 5
10 ml of a silica gel subjected in advance to calcination and degassing at 300"C for 2 hours under high vacuum was immersed in an ethanol solution containing 0.322 g of palladium chloride (PdCI2) and 0.109 g of ferrous chloride (FeCl24H2O). The same treatment as in Example 1 was applied to prepare a Fe-Pd/SiO2 catalyst. Using 5 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 6
The same procedure as in Example 5 was repeated except that n-butyraldehyde was used in place of acetaldehyde. The results are shown in Table 1.
Example 7
10 ml of a silica gel subjected in advance to calcination and degassing at 300"C for 2 hours was immersed in an ethanol solution containing 0.161 g of palladium chloride and 0.075 g of molybdenum chloride. The same treatment as in Example 1 was applied to prepare a Mo
Pd/SiO2 catalyst. Using 2 ml of this catalyst, n-butyraldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 8
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.161 g of palladium chloride, 0.075 g of molybdenum chloride and 0.036 g of ferrous chloride. The same treatment as in Example 1 was applied to prepare a Fe
Mo-Pd/SiO2 catalyst. Using 2 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 9
10 ml of a silica gel subjected in advance to calcination and degassing at 300"C for 2 hours was immersed in an ethanol solution containing 0.321 g of iridium chloride (lrCI4H2O) and 0.109 g of ferrous chloride. The same treatment as in Example 1 was applied to prepare a Fe-lr/SiO2 catalyst. Using 3 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Example 10
The same procedure as in Example 9 was repeated except that n-butyraldehyde was used in place of acetaldehyde. The results are shown in Table 1.
Example 11
10 ml of a silica gel subjected in advance to calcination and degassing at 300"C for 2 hours was immersed in an ethanol solution containing 0.321 g of iridium chloride, 0.109 g of ferrous chloride and 0.480 g of rhodium chloride (RhCl3.3H2O). The same treatment as in Example 1 was applied to prepare a Fe-Rh-lr/SiO2 catalyst. Using 3 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 1
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.480 g of rhodium chloride. The same treatment as in Example 1 was applied to prepare a Rh/SiO2 catalyst. Using 5 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 2
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.322 g of palladium chloride. The same treatment as in Example 1 was applied to prepare a Pd/SiO2 catalyst. Using 5 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 3
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.321 g of iridium chloride. The same treatment as in Example 1 was applied to prepare a Ir/SiO2 catalyst. Using 10 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 4
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.109 g of ferrous chloride. The same treatment as in Example 1 was applied to prepare a Fe/SiO2 catalyst. Using 5 ml of this catalyst, n-butyraldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 5
10 ml of a silica gel subjected in advance to calcination and degassing was immersed in an ethanol solution containing 0.075 g of molybdenum chloride. The same treatment as in Example 1 was applied to prepare a Mo/SiO2 catalyst. Using 2 ml of this catalyst, acetaldehyde was subjected to hydrogenation in the same manner as in Example 1. The results are shown in Table 1.
Comparative Example 6
Using 3 ml of the catalyst, Fe-Rh/SiO2, as prepared in Example 1, acetaldehyde was subjected to hydrogenation in the presence of hydrogen alone under the conditions shown in Table 1. The results are shown in Table 1.
Comparative Example 7
Using 3 ml of the catalyst, Mo-Pd/SiO2, as prepared in Example 7, acetaldehyde was subjected to hydrogenation in the presence of hydrogen alone under the conditions shown in Table 1. The results are shown in Table 1.
Comparative Example 8
Using 3 ml of the catalyst, Fe-lr/SiO2, as prepared in Example 9, n-butyraldehyde was subjected to hydrogenation in the presence of hydrogen alone under the conditions shown in Table 1. The results are shown in Table 1.
Table 1
Reaction Gas flow rate Aldehyde flow rate Alcohol selectivity Reaction Aldehyde temper- (Nl/hr) (mmol/hr) (%) Ex. Catalyst pressure conversion ature (kg/cm) (%) ( C) H2 CO CH3CHO n-C3H7CHO C2H5OH n-C4H9OH 1 Re-Rh/SiO2 50 270 80 40 43.2 - 92.3 97.1 2 Fe-Rh/SiO2 50 271 90 30 - 46.1 95.1 - 98.0 3 Mo-Rh/SiO2 50 270 80 40 47.5 - 97.2 95.4 4 Fe-Mo-Ir/SiO2 50 268 80 40 - 40.6 97.3 - 95.3 5 Fe-Pd/SiO2 30 280 150 50 52.4 - 85.1 96.2 6 Fe-Pd/SiO2 32 292 150 50 - 55.7 90.2 - 97.0 7 Mo-Pd/SiO2 30 290 150 50 - 54.1 96.3 - 98.1 8 Fe-Mo-Pd/SiO2 30 290 150 50 33.9 - 93.0 97.4 9 Fe-Ir/SiO2 50 276 80 40 33.0 - 93.6 97.5 10 Fe-Ir/SiO2 20 279 80 40 - 34.7 95.2 - 98.2 11 Fe-Rh-Ir/SiO2 50 279 80 40 45.2 - 95.2 98.5 Comp.
Rh/SiO2 50 274 80 40 36.1 - 15.2 93.5 Ex. 1 Table 1 (cont'd)
Reaction Gas flow rate Aldehyde flow rate Alcohol selectivity Reaction Aldehyde temper- (Nl/hr) (mmol/hr) (%) Ex. Catalyst pressure conversion ature (kg/cm) (%) ( C) H2 CO CH3CHO n-C3H-CHO C2H5OH n-C4H9OH Comp.
Pd/SiO2 30 290 150 50 51.8 - 7.5 95.6 Ex. 2 Comp.
Ir/SiO2 50 280 90 30 42.4 - 3.5 94.0 Ex. 3 Comp.
Fe/SiO2 30 290 150 50 - 56.1 14.1 - 92.3 Ex. 4 Comp.
Mo/SiO2 30 290 150 50 50.5 - 2.5 90.6 Ex. 5 Comp.
Fe-Rh/SiO2 21 280 80 - 26.7 - 98 7 Ex. 6 Comp.
Mo-Pd/SiO2 20 280 80 - 27.1 - 98 1 Ex. 7 Comp.
Fe-Ir/SiO2 20 280 80 - - 21.5 97 - 17 Ex. 8 Amount of aldehyde fed (mmol) - Amount of aldehyde recovered (mmol) (1) Aldehyde conversion (%) = x 100
Amount of aldehyde fed (mmol)
Amount of alcohol produced (mmol) (2) Alcohol selectivity (%) = x 100
Amount of aldehyde fed (mmol) - Amount of aldehyde recovered (mmol)
Claims (5)
1. In a process for the manufacture of an alcohol by hydrogenating an aliphatic aldehyde in the co-presence of hydrogen and carbon monoxide by using a hydrogenating catalyst, the improvement wherein said hydrogenating catalyst comprises (A) at least one element selected from the group consisting of iron and molybdenum and (B) at least one element selected from the group consisting of rhodium, palladium and iridium.
2. The process of Claim 1 wherein the catalyst comprises (A) at least one element selected from the group consisting of iron and molybdenum and (B) rhodium.
3. The process of Claim 1 wherein the catalyst comprises (A) at least one element selected from the group consisting of iron and molybdenum and (B) palladium.
4. The process of Claim 1 wherein the catalyst comprises (A) iron and (B) iridium.
5. The process of Claim 1 wherein the aliphatic aldehyde is selected from the group consisting of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, caproicaldehyde, heptaldehyde, caprylaldehyde, pelargonaldehyde, capric aldehyde, acrolein, and crotonaldehyde.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60071047A JPS61230741A (en) | 1985-04-05 | 1985-04-05 | Aldehyde hydrogenating catalyst |
| JP60071048A JPS61230738A (en) | 1985-04-05 | 1985-04-05 | Catalyst for hydrogenating aldehyde |
| JP60071049A JPS61230739A (en) | 1985-04-05 | 1985-04-05 | Catalyst for hydrogenating aldehyde |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8607420D0 GB8607420D0 (en) | 1986-04-30 |
| GB2175896A true GB2175896A (en) | 1986-12-10 |
| GB2175896B GB2175896B (en) | 1988-04-27 |
Family
ID=27300516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8607420A Expired GB2175896B (en) | 1985-04-05 | 1986-03-25 | Process for the manufacture of alcohols from aldehydes |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2175896B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035844A1 (en) * | 1998-12-18 | 2000-06-22 | The Dow Chemical Company | Process for making 2,3-dihalopropanols |
| WO2009003047A1 (en) * | 2007-06-27 | 2008-12-31 | H R D Corporation | Method of hydrogenating aldehydes and ketones |
-
1986
- 1986-03-25 GB GB8607420A patent/GB2175896B/en not_active Expired
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035844A1 (en) * | 1998-12-18 | 2000-06-22 | The Dow Chemical Company | Process for making 2,3-dihalopropanols |
| US6350922B1 (en) | 1998-12-18 | 2002-02-26 | The Dow Chemical Company | Process for making 2,3-dihalopropanols |
| KR100715882B1 (en) * | 1998-12-18 | 2007-05-09 | 다우 글로벌 테크놀로지스 인크. | Process for making 2,3-dihalopropanols |
| WO2009003047A1 (en) * | 2007-06-27 | 2008-12-31 | H R D Corporation | Method of hydrogenating aldehydes and ketones |
| US7914745B2 (en) | 2007-06-27 | 2011-03-29 | Synfuels International, Inc. | Method of hydrogenating aldehydes and ketones |
| US8168836B2 (en) | 2007-06-27 | 2012-05-01 | H R D Corporation | Method of hydrogenating aldehydes and ketones |
| US8378155B2 (en) | 2007-06-27 | 2013-02-19 | H R D Corporation | Method of hydrogenating aldehydes and ketones |
| EA021574B1 (en) * | 2007-06-27 | 2015-07-30 | ЭйчАДи КОПЭРЕЙШН | System and method of hydrogenating aldehydes, ketones and mixtures thereof |
| EA021574B8 (en) * | 2007-06-27 | 2015-10-30 | Эйч А Ди Корпорейшн | System and method of hydrogenating aldehydes, ketones and mixtures thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2175896B (en) | 1988-04-27 |
| GB8607420D0 (en) | 1986-04-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19950325 |