US2953605A - Hydrogenation of 1, 4-butynediol to 1, 4-butanediol - Google Patents
Hydrogenation of 1, 4-butynediol to 1, 4-butanediol Download PDFInfo
- Publication number
- US2953605A US2953605A US704239A US70423957A US2953605A US 2953605 A US2953605 A US 2953605A US 704239 A US704239 A US 704239A US 70423957 A US70423957 A US 70423957A US 2953605 A US2953605 A US 2953605A
- Authority
- US
- United States
- Prior art keywords
- copper
- butynediol
- nickel catalyst
- hydrogenation
- butanediol
- 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.)
- Expired - Lifetime
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims description 12
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 title claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 title description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 9
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical class [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 1
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
- C07C29/172—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 with the obtention of a fully saturated alcohol
Definitions
- This invention relates to'the 'catalytic' hydrogenation of 1,4-butynediol, hereinafter referred toasbutynediolj to I I 1,4-butanediol, hereinafter referred to as'butanediol
- the hydrogenationof butynediol to butanegiiol in he presence of a number of different catalysts jand by' a: number of difierent proceduresisknown;However, such previously proposed processe slhavebeen deficient roar centrated solutions are preferred, an aqueous solution hav-( ing a concentration of at least about 20%, and prefer ably 35 to 40% having been found highly advantageous and convenient.
- 'Such solutionss are available commercially at a pH of about 2.5 to 6. If desired, undiluted liquid butynediol may be used.
- the nickel catalyst employed in the process of this invention is preferably maintained in the liquid butynediolreaction medium in finely divided form.
- a Raneytype nickel catalyst such catalysts are described in U.S.
- Patent No. -1,638,190 is preferred as yielding optimum results. This type of catalyst is readily prepared by treat-.
- the amount of nickel catalyst employed will generally range from about 0.:l to 10%, and preferably from about 0.5 to 3% by weight'ofthe butynediol,-*but such amount is not critical since-the catalyst.- is not deactivated during the hydrogenation: and may be reused. For a given amount of butynediol'to'behydrogenated, the rate of hydrogenation will vary directly with the amount of catalyst employed.
- the desired improved-results and advantages are obtained when the butynediol-nickel catalyst system also contains dispersed thereon about 3 to'l5% of copper by weight of the nickel catalyst, preferably as deposited from a soluble or dispersible-copper-compound.
- a water soluble copper compound is'preferablyaddedthereto, particularly the copper salts of strong acids such as copper sulfate, copper chlowhich may be carried out "at relatively low temperatures and pressures.
- Another objectjof this invention is the provision of a process for thehydrogenation ofibutynediol to butanediol in the presenceof a nickel catalyst at relatively low temperatures and pressures without substantial detriment to the yields ofthe-desired'product stantial amounts of undesirable by-products which would reduce the quality and yield of product desired.
- the instant inventive process for the catalytic hydrogenation of butynediol to butanediol comprising treating a solution of butynediol with hydrogen at a temperature of about 15 to 100 C. and a pressure of about 0 to 40 atmospheres gauge in the presence of a nickel catalyst carrying about 3 to 15% of copper by weight of the nickel catalyst. It has been found that the concurrent use of copper in the above defined process has little or no efli'ect on the activity of the nickel catalyst for hydrogenation but acts to suppress isomerization during the process which would tend to produce by-products having a detrimental effect upon the quality and yield of the desired butanediol.
- the use of copper in this process enables the attainment of large savings in cost of operation and equipment because of the relatively low pressures which may be employed.
- the catalyst maintains its activity much longer, possibly because of the lowering of the formation of by-products, including gamma-hydroxybutyraldehyde, tetrahydrofurane, dihydrofurane, propionaldehyde, and the like, and the poisoning produced thereby, and may accordingly be reused repeatedly.
- the butynediol is maintained in liquid condition at a pH of no more than about 7, preferably in solution in an inert solvent such as ethyl alcohol or other alcohols, dioxane, pr the like, but preferably in an aqueous solution.
- an inert solvent such as ethyl alcohol or other alcohols, dioxane, pr the like, but preferably in an aqueous solution.
- Conride; andncopper nitrate, and the copper salts of weak acids such .as copper cyanide, copper formate, copper acetate and copper carbonate.
- the .particular coppercompound employed-Lwill;ofcoursebe dependent upon the liquid reacand/ or without the simultaneous production of-any-sub-"'- tion-me.dium. .r
- Thenickel replaces the copper from the solutioiiand: any residual soluble copper is reduced during 1 the hydrogenation.
- the precipitated copper is dispersed:
- the hydrogenation of the butynediol in the reaction medium is carried out by maintaining an atmosphere of hydrogen over the surface of the reaction medium, contact therewith being facilitated by agitation as by rocking or shaking the reaction vessel, or by stirring the reaction medium with a high speed propeller or the like.
- an atmosphere of hydrogen over the surface of the reaction medium, contact therewith being facilitated by agitation as by rocking or shaking the reaction vessel, or by stirring the reaction medium with a high speed propeller or the like.
- the optimum temperature range is about 40 to 60 C.
- reduction is incomplete and considerable butenediol is produced, as disclosed and claimed in my copending application Serial No. 704,240 filed on even date herewith, unless pressures of more than 4 atmospheres gauge are employed. Apparently, at temperatures of over 60 C.
- a process for the catalytic hydrogenation of 1,4- butynediol to 1,4-butanediol comprising treating an aqueous solution of 1,4-butynediol' with hydrogen at a pH of no moreth-an about 7,.atemperatureof about 15to 100.
- a process for the catalytic hydrogenation of 1,4- butynediol to 1,4-butanediol comprising treating a solution containing 1,4-butynediol, a nickel catalyst and about 3 to.- 1-5 of copper, in the form of a water dispersible copper-compound by weight of the nickel catalyst, with.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent lice 2,953,605 e r I v p HYDROGENATION OF 1,4-BUTYNEDIOL T 1,4-BUTANEDIOL Eugene V. Hort, Westfield, 'N.'.l.,'"assignor to"( ;en eral I Aniline & Film Corporation,"New York, N.Y., a cor-, poration of Delaware 'fi jf, i; No Drawing. Filed Dec. 23, 1957, Ser. v
This invention relates to'the 'catalytic' hydrogenation of 1,4-butynediol, hereinafter referred toasbutynediolj to I I 1,4-butanediol, hereinafter referred to as'butanediol The hydrogenationof butynediol to butanegiiol"in he presence of a number of different catalysts jand by' a: number of difierent proceduresisknown;However, such previously proposed processe slhavebeen deficient roar centrated solutions are preferred, an aqueous solution hav-( ing a concentration of at least about 20%, and prefer ably 35 to 40% having been found highly advantageous and convenient. 'Such solutionss are available commercially at a pH of about 2.5 to 6. If desired, undiluted liquid butynediol may be used.
The nickel catalyst employed in the process of this inventionis preferably maintained in the liquid butynediolreaction medium in finely divided form. A Raneytype nickel catalyst (such catalysts are described in U.S.
Patent No. -1,638,190) is preferred as yielding optimum results. This type of catalyst is readily prepared by treat-.
ing an aluminum-nickel alloy with caustic soda to dissolve out the aluminum and leave the nickel in a highly divided and particularly effective form. The amount of nickel catalyst employed will generally range from about 0.:l to 10%, and preferably from about 0.5 to 3% by weight'ofthe butynediol,-*but such amount is not critical since-the catalyst.- is not deactivated during the hydrogenation: and may be reused. For a given amount of butynediol'to'behydrogenated, the rate of hydrogenation will vary directly with the amount of catalyst employed. ln 'accordance' with the instant process, the desired improved-results and advantages are obtained when the butynediol-nickel catalyst system also contains dispersed thereon about 3 to'l5% of copper by weight of the nickel catalyst, preferably as deposited from a soluble or dispersible-copper-compound. When an aqueous solution ofzb'utynediol isemployed, a water soluble copper compoundis'preferablyaddedthereto, particularly the copper salts of strong acids such as copper sulfate, copper chlowhich may be carried out "at relatively low temperatures and pressures. Another objectjof this invention isthe provision of a process for thehydrogenation ofibutynediol to butanediol in the presenceof a nickel catalyst at relatively low temperatures and pressures without substantial detriment to the yields ofthe-desired'product stantial amounts of undesirable by-products which would reduce the quality and yield of product desired. Other objects and advantages will appear as the description proceeds.
The attainment of the above objects is made possible by the instant inventive process for the catalytic hydrogenation of butynediol to butanediol comprising treating a solution of butynediol with hydrogen at a temperature of about 15 to 100 C. and a pressure of about 0 to 40 atmospheres gauge in the presence of a nickel catalyst carrying about 3 to 15% of copper by weight of the nickel catalyst. It has been found that the concurrent use of copper in the above defined process has little or no efli'ect on the activity of the nickel catalyst for hydrogenation but acts to suppress isomerization during the process which would tend to produce by-products having a detrimental effect upon the quality and yield of the desired butanediol. Further, the use of copper in this process enables the attainment of large savings in cost of operation and equipment because of the relatively low pressures which may be employed. The catalyst maintains its activity much longer, possibly because of the lowering of the formation of by-products, including gamma-hydroxybutyraldehyde, tetrahydrofurane, dihydrofurane, propionaldehyde, and the like, and the poisoning produced thereby, and may accordingly be reused repeatedly.
In carrying out the process of this invention, the butynediol is maintained in liquid condition at a pH of no more than about 7, preferably in solution in an inert solvent such as ethyl alcohol or other alcohols, dioxane, pr the like, but preferably in an aqueous solution. Conride; andncopper nitrate, and the copper salts of weak acids such .as copper cyanide, copper formate, copper acetate and copper carbonate. Copper oxide may also be usedLxSomeLof these'compounds are also solublein or- V ganic=solvents The .particular coppercompound employed-Lwill;ofcoursebe dependent upon the liquid reacand/ or without the simultaneous production of-any-sub-"'- tion-me.dium.=.r Thenickel replaces the copper from the solutioiiand: any residual soluble copper is reduced during 1 the hydrogenation. The precipitated copper is dispersed:
or coated on the nickel catalyst.
The hydrogenation of the butynediol in the reaction medium is carried out by maintaining an atmosphere of hydrogen over the surface of the reaction medium, contact therewith being facilitated by agitation as by rocking or shaking the reaction vessel, or by stirring the reaction medium with a high speed propeller or the like. Within the defined temperature range, use of a lower temperature yields a product of higher quality, but the reaction rate is lower. The optimum temperature range is about 40 to 60 C. At higher temperatures, reduction is incomplete and considerable butenediol is produced, as disclosed and claimed in my copending application Serial No. 704,240 filed on even date herewith, unless pressures of more than 4 atmospheres gauge are employed. Apparently, at temperatures of over 60 C. under the conditions of the hydrogenation, some substance present in the reaction medium acts to prevent complete reduction to the butanediol stage unless the pressure is increased as above noted. Such substance does not, however, poison the catalyst which may be reused repeatedly. Completion of the desired hydrogenation is indicated when absorption of hydrogen ceases, contact with the hydrogen bieng preferably continued for a further period to insure completion of this reaction.
The examples in the following table in which parts are by weight unless otherwise indicated are illustrative of the instant invention and are not to be regarded as limitative. In each of the examples, a rocking autoclave containing 3.0 moles of technical 35% aqueous butynediol and 6.0 g. (solids) of Raney-type nickel in the form of a 50% aqueous paste is held at 40 C. while Patented Sept. 20, 1960 maintaining therein the indicated hydrogen pressure in pounds'per square inch gauge (p.s.i.g.)' for three hours after the indicated time when hydrogen absorption ceased. In. each. case, the product. is. filtered. from. the. catalyst,
fractionall'y distilled, and the yield of the desired butanediol', and its properties, determined. In Examples 2,. 4.
and 6,. 2.0 g. of copper acetate is added to the. solution prior to hydrogenation.
In the above table, the refractive index of each product is given in the right-hand column, and the solidification point in the column adjacent thereto. Pure butane diol has a solidification point of about 20.9 C.. and. a
refractive index of about 1.4446. The results shown in: the table indicate that Examples 2, 4 and 6 carried out.
in the presence of copper in accordance with the instant invention, enable the attainment of improved yields: of
purer product as compared with comparative Examples 1, 3 and in which no copper was used.
This invention has been disclosed with respect. tocertain preferred embodiments, and there will become ohvious to persons skilled in. the art various modifications,-
equivalents or variations thereof which. are intended; to be included within the spirit and scope of this invention.
Iclaim: l. A process for the catalytic hydrogenation of 1,4- butynediol to 1,4-butanedio1 comprising treating. l,4--
butynediol in liquid. form with hydrogen at a pH of? no more than about 7, a temperature of about: 15 to 100 C- and a pressure of about 0 to 40 atmospheres gauge-inthe.
presence of a nickel catalyst carrying. about 3 to 15% of' copper by weight of the nickel catalyst, the pressure being.
more than 4 atmospheres gauge at temperatures of 6.0 to
2. A process as defined in claim 1 wherein the nickel catalyst" is a'Raney-type nickel catalyst.
3. A process as defined in claim 1 wherein the copper is derived from copper acetate.
4. A process for the catalytic hydrogenation of 1,4- butynediol to 1,4-butanediol comprising treating an aqueous solution of 1,4-butynediol' with hydrogen at a pH of no moreth-an about 7,.atemperatureof about 15to 100.
C. and a pressure of about 0 to 40' atmospheres gauge in the presence of. a. nickel catalyst carrying about 3 to 15% of copper by weight of the nickel catalyst, the pressure being more than 4 atmospheres gauge at. temperatures of so to 100 c.
5. A process as defined in claim 4 wherein the nickel catalyst is a Raney-type nickel catalyst.
6. A process for the catalytic hydrogenation of 1,4- butynediol to 1,4-butanediol comprising treating a solution containing 1,4-butynediol, a nickel catalyst and about 3 to.- 1-5 of copper, in the form of a water dispersible copper-compound by weight of the nickel catalyst, with.
hydrogen at a pHof no more than about 7, a temperature of about 15' to 100 C. and a pressure of about 0 to 40 atmospheres gauge, the pressure being more than 4 atmospheres gauge at temperatures of to C.
'7'. A process as defined inclaim- 6 wherein the nickel catalyst, is a Raney-type nickel. catalyst.
8'. A. process as defined in claim 6 wherein the copper compound is copper acetate.
References. Cited. in the file of. this patent UNITED STATES PATENTS 2,1573365 Vaughn May 9, 1939 2,319,707 Reppe'et al May 18, 1943 2,335,795" Reppe et al Nov. 30, 1943 2,737,534 Taylor et' a1. Mar. 6, 1956 FOREIGN PATENTS 508,944 Great Britain June 26', 1939 869,053 Germany Mar. 2, 1953 OTHER REFERENCES I Campbell. etal: Chemical Reviews, vol. 3 1, pp. 5.1-. .1942).
Claims (1)
1. A PROCESS FOR THE CATALYTIC HYDROGENATION OF 1,4BUTYNEDIOL TO 1,4-BUTANEDIOL COMPRISING TREATING 1,4BUTYNEDIOL IN LIQUID FORM WITH HYDROGEN AT A PH OF NO MORE THAN ABOUT 7, A TEMPERATURE OF ABOUT 15 TO 100*C. AND A PRESSURE OF ABOUT 0 TO 40 ATMOSPHERES GAUGE IN THE PRESENCE OF A NICKEL CATALYST CARRYING ABOUT 3 TO 15% OF COPPER BY WEIGHT OF THE NICKEL CATALYST, THE PRESSURE BEING MORE THAN 4 ATMOSPHERES GUAGE AT TEMPERATURES OF 60 TO 100*C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US704239A US2953605A (en) | 1957-12-23 | 1957-12-23 | Hydrogenation of 1, 4-butynediol to 1, 4-butanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US704239A US2953605A (en) | 1957-12-23 | 1957-12-23 | Hydrogenation of 1, 4-butynediol to 1, 4-butanediol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2953605A true US2953605A (en) | 1960-09-20 |
Family
ID=24828668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US704239A Expired - Lifetime US2953605A (en) | 1957-12-23 | 1957-12-23 | Hydrogenation of 1, 4-butynediol to 1, 4-butanediol |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2953605A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3184513A (en) * | 1960-08-17 | 1965-05-18 | Allied Chem | Production of hexamethylene glycol |
| US4153578A (en) * | 1978-07-31 | 1979-05-08 | Gaf Corporation | Catalyst comprising Raney nickel with adsorbed molybdenum compound |
| FR2430926A1 (en) * | 1978-07-12 | 1980-02-08 | Gaf Corp | PROCESS AND CATALYST FOR PRODUCING HIGH QUALITY BUTANEDIOL |
| US4213000A (en) * | 1979-05-29 | 1980-07-15 | E. I. Du Pont De Nemours And Company | Reducing color formers in 1,4-butanediol |
| US4864066A (en) * | 1987-05-23 | 1989-09-05 | Basf Aktiengesellschaft | Preparation of alkanediols from alkynols |
| US4876401A (en) * | 1988-03-18 | 1989-10-24 | Shell Oil Company | Process for the preparation of alkanediols |
| US5037793A (en) * | 1989-04-27 | 1991-08-06 | Basf Aktiengesellschaft | Catalyst for the hydrogenation of unsaturated aliphatic compounds |
| US5714644A (en) * | 1994-07-06 | 1998-02-03 | Basf Aktiengesellschaft | Process and catalyst for the selective hydrogenation of butynediol to butenediol |
| US5959163A (en) * | 1997-09-04 | 1999-09-28 | The Dow Chemical Company | Process for the preparation of 1,4-butenediol from epoxybutene |
| WO2018054755A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for providing a catalytically active fixed bed for hydrogenating organic compounds |
| WO2018054754A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for the hydrogenation of organic compounds in the presence of co and a fixed catalyst bed which contains monolithic shaped catalyst body |
| WO2018054740A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for providing a fixed catalyst bed containing a doped structured shaped catalyst body |
| WO2018054759A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies |
| WO2019057533A1 (en) | 2017-09-20 | 2019-03-28 | Basf Se | METHOD FOR PRODUCING A CATALYST SHAPED BODY |
| CN115667520A (en) * | 2020-03-30 | 2023-01-31 | 格雷斯公司 | Catalyst, its preparation method and selective hydrogenation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2157365A (en) * | 1936-11-06 | 1939-05-09 | Carbide & Carbon Chem Corp | Process for producing 1, 4-ethylenic glycols |
| GB508944A (en) * | 1937-12-24 | 1939-06-26 | George William Johnson | Improvements in the manufacture and production of butanediol-1.4 and its derivatives containing two hydroxy groups |
| US2319707A (en) * | 1938-04-16 | 1943-05-18 | Gen Aniline & Film Corp | Production of aliphatic dihydric alcohols |
| US2335795A (en) * | 1939-04-04 | 1943-11-30 | Gen Aniline & Film Corp | Production of aliphatic alcohols |
| DE869053C (en) * | 1942-05-02 | 1953-03-02 | Basf Ag | Process for the production of higher molecular weight glycols |
| US2737534A (en) * | 1951-01-17 | 1956-03-06 | Ici Ltd | Production of aromatic hydrocarbons from six carbon aliphatic diols |
-
1957
- 1957-12-23 US US704239A patent/US2953605A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2157365A (en) * | 1936-11-06 | 1939-05-09 | Carbide & Carbon Chem Corp | Process for producing 1, 4-ethylenic glycols |
| GB508944A (en) * | 1937-12-24 | 1939-06-26 | George William Johnson | Improvements in the manufacture and production of butanediol-1.4 and its derivatives containing two hydroxy groups |
| US2319707A (en) * | 1938-04-16 | 1943-05-18 | Gen Aniline & Film Corp | Production of aliphatic dihydric alcohols |
| US2335795A (en) * | 1939-04-04 | 1943-11-30 | Gen Aniline & Film Corp | Production of aliphatic alcohols |
| DE869053C (en) * | 1942-05-02 | 1953-03-02 | Basf Ag | Process for the production of higher molecular weight glycols |
| US2737534A (en) * | 1951-01-17 | 1956-03-06 | Ici Ltd | Production of aromatic hydrocarbons from six carbon aliphatic diols |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3184513A (en) * | 1960-08-17 | 1965-05-18 | Allied Chem | Production of hexamethylene glycol |
| FR2430926A1 (en) * | 1978-07-12 | 1980-02-08 | Gaf Corp | PROCESS AND CATALYST FOR PRODUCING HIGH QUALITY BUTANEDIOL |
| US4153578A (en) * | 1978-07-31 | 1979-05-08 | Gaf Corporation | Catalyst comprising Raney nickel with adsorbed molybdenum compound |
| US4213000A (en) * | 1979-05-29 | 1980-07-15 | E. I. Du Pont De Nemours And Company | Reducing color formers in 1,4-butanediol |
| US4864066A (en) * | 1987-05-23 | 1989-09-05 | Basf Aktiengesellschaft | Preparation of alkanediols from alkynols |
| US4876401A (en) * | 1988-03-18 | 1989-10-24 | Shell Oil Company | Process for the preparation of alkanediols |
| US5037793A (en) * | 1989-04-27 | 1991-08-06 | Basf Aktiengesellschaft | Catalyst for the hydrogenation of unsaturated aliphatic compounds |
| US5714644A (en) * | 1994-07-06 | 1998-02-03 | Basf Aktiengesellschaft | Process and catalyst for the selective hydrogenation of butynediol to butenediol |
| US5959163A (en) * | 1997-09-04 | 1999-09-28 | The Dow Chemical Company | Process for the preparation of 1,4-butenediol from epoxybutene |
| WO2018054755A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for providing a catalytically active fixed bed for hydrogenating organic compounds |
| WO2018054754A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for the hydrogenation of organic compounds in the presence of co and a fixed catalyst bed which contains monolithic shaped catalyst body |
| WO2018054740A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for providing a fixed catalyst bed containing a doped structured shaped catalyst body |
| WO2018054759A1 (en) | 2016-09-23 | 2018-03-29 | Basf Se | Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies |
| WO2019057533A1 (en) | 2017-09-20 | 2019-03-28 | Basf Se | METHOD FOR PRODUCING A CATALYST SHAPED BODY |
| CN115667520A (en) * | 2020-03-30 | 2023-01-31 | 格雷斯公司 | Catalyst, its preparation method and selective hydrogenation method |
| JP2023521597A (en) * | 2020-03-30 | 2023-05-25 | ダブリュー・アール・グレース・アンド・カンパニー－コーン | Catalyst, method for its preparation, and selective hydrogenation process |
| EP4127177A4 (en) * | 2020-03-30 | 2024-03-13 | W. R. Grace & Co.-Conn | Catalysts, preparation method thereof, and selective hydrogenation processes |
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