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US3479411A - Hydrogenation of alkynols and alkynediols - Google Patents

Hydrogenation of alkynols and alkynediols Download PDF

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Publication number
US3479411A
US3479411A US648222A US3479411DA US3479411A US 3479411 A US3479411 A US 3479411A US 648222 A US648222 A US 648222A US 3479411D A US3479411D A US 3479411DA US 3479411 A US3479411 A US 3479411A
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parts
weight
manganese
catalyst
hydrogenation
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Karl Adam
Erich Haarer
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BASF SE
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BASF SE
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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
    • C07C29/17—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

  • the invention relates to a process for the hydrogenation of alkynols and alkynediols to the corresponding saturated alcohols.
  • the saturated alcohols prepared by the said methods do not satisfy requirements as regards purity.
  • the rapid decline in the activity of the catalyst means that the hydrogenation proceeds only incompletely so that compounds which have been only partly hydrogenated or not at all, or other impurities, remain in the product and can only be removed by expensive distillation.
  • butanol are formed in the hydrogenation of butynediol.
  • the preferred starting materials are aliphatic alkynols or alkynediols having three to twelve, particularly three to six, carbon atoms.
  • the triple bond may be present once or more than once, for example twice, in the molecule.
  • Starting materials are also suitable which have substituents which are inert under the reaction conditions, such as alkyl radicals having one to four carbon atoms, if desired attached by ether bridging groups.
  • the following may be used, for example, for the hydrogenationzpropargyl alcohol, butyene (2) diol (1,4), hexadiyne (2,4) diol (1,6), 3,6 dimethyloctyne- (4) diol (3,6), hexyne (3) diol (2,5).
  • the process has particular importance for the hydrogenation of hutyne (2) diol (1,4) and hexadiyne (2,4) diol- (1,6).
  • Hydrogenation is carried out in general at temperatures of 20 to 180 0, preferably at temperatures of 50 to 120 C. It is advantageous to use pressures of 0 to 500 atmospheres gauge, particularly 50 to 450 atmospheres gauge, preferably 200 to 400 atmospheres gauge.
  • Hydrogenation may be carried out in the presence of inert media, such as water or alcohols, for example ethanol or butanol, as well as cyclic ethers, such as tetrahyrdofuran. It is advantageous to use for the hydrogenation the aqueous solutions in which the alkynols and alkynediols have been obtained, together with the hydrogenated reaction product.
  • inert media such as water or alcohols, for example ethanol or butanol
  • cyclic ethers such as tetrahyrdofuran
  • the catalysts contain nickel and/ or cobalt and an addition of copper and manganese and/or chromium in the ratio cobalt/nickelzcopper:manganese/chromium of 40- 89: 10-40: 1-20% by weight, particularly 55-84: 15-3521- 10% by weight, based on the metal content of the catalysts.
  • the catalysts also contain a pyroacid or polyacid in the form of the free acid and/or in the form of at least one salt of the said metals.
  • acids which change upon being heated into their pyro or poly form such as phosphoric acid, boric acid, molybdic acid or tungstic acid. It is particularly preferred to use phosphoric acid.
  • the acids or their salts are advantageously used in an amount of .5 to 15% by weight based on the metal content of the catalysts. Particularly good results are obtained with contents of 1 to 10% by weight. All the percentages refer to the contents of the individual components determined analytically in the finished catalysts, the metals being given as such and the pyroacids or polyacids or their salts being given as anhydrides, i.e. independently of the actual state of combination.
  • the catalysts may be used unsupported.
  • the individual constituents of the catalyst are mixed in the form of compounds which can be reduced with hydrogen at elevated temperatures, such as oxides, hydroxides, oxalates, ammoniates or formates, with the addition of the stated amounts of the said acids which change into their pyro or poly form when heated, heated preferably to 300 to 700 C. and then reduced with hydrogen at elevated temperature, advantageously at 200 to 400 C.
  • the metals and acids are precipitated together from a solution with alkali, such as sodium carbonate or sodium hydroxide, and the precipitate is heated, for example in a mufile furnace, at about 300 to 700 C. The mixture is then powdered and pressed into tablets or pellets and then reduced with hydrogen at elevated temperature.
  • metal salts and the acids to a carrier, such as fullers earth, silicic acid, silica gel, aluminum oxide or silicates, to heat them, for example in a muflle furnace, to about 300 to 700 C. and then to reduce them with hydrogen as described. It has proved to be particularly advantageous to effect precipitation of the metal components and the acids onto a powdered carrier, or to effect coprecipitation with the carrier from a solution, for example with sodium carbonate, to heat the precipitate at about 300 to 700 C. for example in a muflle furnace and then to reduce it with hydrogen as described.
  • a carrier such as fullers earth, silicic acid, silica gel, aluminum oxide or silicates
  • the process according to the invention may for eX- ample be carried out by forcing hydrogen to the point of saturation in a high pressure vessel into the alkynols or alkynediols to be hydrogenated in the presence of a catalyst of the said composition at the said temperature and pressure conditions.
  • the process is advantageously carried out continuously by charging a vertical high pressure tube with the catalyst, metering in alkynol or alkynediol at the top and supplying hydrogen countercurrent or cocurrent under the stated conditions at the same time.
  • the alkynols or alkynediols are fed into the top of the high pressure tube with about .5 to times the amount, preferably once to five times the amount, of hydrogenated product, with reference to the alkynols or alkynediols used.
  • the crude alcohols are fractionally distilled to purify them. They are distinguished 'by a particularly low iodine number.
  • Saturated alcohols prepared by the process according to this invention are suitable as solvents and for the production of high polymers (cf. J. Am. Chem. Soc., 72, 1674 (1950)).
  • Example 1 A solution of 3500 parts of cobalt nitrate having six molecules of water of crystallization (6H O), 769 parts of copper nitrate (3H O), 262 parts of manganese nitrate (6H O) and 47 parts of 85 by weight phosphoric acid in 8000 parts by volume of water is allowed to flow at C. while stirring into a solution of 1700 parts of anhydrous sodium carbonate and 8000 parts by volume of water. The precipitate is suction filtered and washed with water until as free as possible from alkali. The washed filter cake is dried and then heated to 300 C. The mixture is powered and shaped into pellets having a diameter of 4 mm.
  • the pellets are charged into a vertical high pressure tube having a capacity of 6360 parts 'by volume and reduced with hydrogen at 300 C.
  • the finished catalyst contains cobalt, copper and manganese in the ratio by weight 7112015 and 2.9% by weight of phosphorus pentoxide with reference to cobalt, copper and manganese.
  • Example 2 A solution of 864 parts of cobalt nitrate (6H O), 227 parts of copper nitrate (3H O), 46.6 parts of manganese nitrate (6H O) and 7 parts of 85 by Weight phosphoric acid in 4000 parts by volume of water is allowed to flow at 40 C. while stirring well into a solution of 460 parts of anhydrous sodium carbonate in which 752 parts of aluminum oxide powder is suspended. The precipitate is filtered off and further treated according to Example 1.
  • the finished catalyst contains cobalt, copper and manganese in the ratio by weight 17.5:6:.7 and 1.8% by weight of phosphorus pentoxide with reference to cobalt, copper and manganese.
  • Example 3 A solution of 5640 parts of aluminum nitrate, 864 parts of cobalt nitrate (6H O), 199 parts of copper nitrate (3H O), 36.5 parts of manganese nitrate (6H O) and 7.1 parts of by weight phosphoric acid in 20,000 parts by volume of water is allowed to flow at 50 C. with good stirring into a solution of 3150 parts of anhydrous sodium carbonate in 15,000 parts by volume of water. The precipitate is worked up as described in Example 1. The finished catalyst contains cobalt, copper and manganese in the weight ratio 17:5:.7 and 1.92% by weight of phosphorus pentoxide, with reference to cobalt, copper and manganese.
  • Example 4 Hydrogen is forced at 60 C. into a high pressure tube having a capacity of 1000 parts by volume which is rotating about its longitudinal axis and which has been charged with 50 parts of the catalyst described in Example 1 and 450 parts of propargyl alcohol, until the pressure is 300 atmospheres gauge. Absorption of hydrogen is ended after one hour. The catalyst is filtered off after it has cooled. The filtrate contains 99.8% by Weight of n-propanol according to gas chromatographic analysis.
  • Example 5 A solution of 493 parts of nickel nitrate (6H O), 395 parts of cobalt nitrate (6H O), 227 parts of copper nitrate (3H O), 37 parts of manganese nitrate (6H O) and 6 parts of phosphoric acid calculated at 100% in 10,000 parts by volume of Water is allowed to flow at 40 C. with good stirring into a solution of 437 parts of anhydrous sodium carbonate in 10,000 parts by volume of water in which 747 parts of precipitated silicic acids has been suspended. The precipitate is filtered off and further treated according to Example 1. The finished catalyst contains nickel, cobalt, copper and manganese in the weight ratio 10:8:6:.7 and 1.75% by weight of phosphorus pentoxide with reference to nickel, cobalt, copper and manganese.
  • Example 6 A solution of 888 parts of nickel nitrate (6H O), 227 parts of copper nitrate (3H O), 47 parts of manganese nitrate (61-1 0) and 9 parts of phosphoric acid calculated at 100% in 10,000 parts by volume of water is allowed to flow at 50 C. with good stirring into a solutionot' 440 parts of anhydrous sodium carbonate in 10,000 parts of water in which 742 parts of aluminum hydroxide is suspended.
  • the residue is worked up as described in Example 1.
  • the finished catalyst contains nickel, copper and manganese in the weight ratio 1826:.9 and 2.6% by weight of phosphorous pentoxide with reference to nickel, copper and manganese.
  • the catalyst contains, exclusive of any support, 1 to 10% by weight of a pyrophosphoric or polyphosphoric acid calculated as phosphorous pentoxide, said percent being based on the metal content of said catalyst.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US648222A 1966-06-29 1967-06-23 Hydrogenation of alkynols and alkynediols Expired - Lifetime US3479411A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1285992 1966-06-29
DEB87765A DE1285992B (de) 1966-06-29 1966-06-29 Verfahren zur Herstellung von gesaettigten Alkoholen durch Hydrierung von Alkinolen und Alkindiolen

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691093A (en) * 1969-02-12 1972-09-12 Du Pont Efficiency of nickel-aluminum catalysts by water washing
US3950441A (en) * 1970-09-16 1976-04-13 Gaf Corporation Process and catalyst for preparing 1,4-butanediol
US4048116A (en) * 1975-08-14 1977-09-13 Basf Aktiengesellschaft Catalyst for the hydrogenation of acetylene alcohols
US4200501A (en) * 1978-03-24 1980-04-29 Basf Wyandotte Corporation Silicate fouling control during dihydric alcohol distillation
US4361495A (en) * 1981-03-13 1982-11-30 Gaf Corporation Regeneration of supported-nickel catalysts
US4371723A (en) * 1980-04-16 1983-02-01 Gaf Corporation Process of producing a distilled butanediol product of high quality in high yield
US4384147A (en) * 1979-04-27 1983-05-17 Basf Aktiengesellschaft Preparation of catalysts and their use for the hydrogenation of acetylene-alcohols
USRE32072E (en) * 1980-04-16 1986-01-28 Gaf Corporation Process of producing a distilled butanediol product of high quality in high yield
US20100016643A1 (en) * 2007-02-15 2010-01-21 Basf Se Process for preparing 1,4-butanediol
CN102161615A (zh) * 2011-02-22 2011-08-24 重庆大学 一种回收1,4-丁二醇的工艺

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0264636B1 (de) * 1984-10-12 1990-12-27 BASF Aktiengesellschaft Verfahren zur Herstellung von Propanol
EP0304696B1 (de) * 1987-08-08 1992-04-29 BASF Aktiengesellschaft Verfahren zur Herstellung von 1,4-Butandiol und/oder Tetrahydrofuran
EP3679006A1 (de) 2017-09-06 2020-07-15 Basf Se Verfahren zur regelung der katalytischen hydrierung von 1,4-butindiol über den gehalt von co und/oder ch4 im abgasstrom

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2335795A (en) * 1939-04-04 1943-11-30 Gen Aniline & Film Corp Production of aliphatic alcohols
US2908722A (en) * 1956-09-07 1959-10-13 Air Reduction Process for preparing saturated monohydric alcohols
US3184513A (en) * 1960-08-17 1965-05-18 Allied Chem Production of hexamethylene glycol
US3271299A (en) * 1959-09-03 1966-09-06 Exxon Research Engineering Co Compositions containing stable aluminum phosphate gel and methods of using same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2335795A (en) * 1939-04-04 1943-11-30 Gen Aniline & Film Corp Production of aliphatic alcohols
US2908722A (en) * 1956-09-07 1959-10-13 Air Reduction Process for preparing saturated monohydric alcohols
US3271299A (en) * 1959-09-03 1966-09-06 Exxon Research Engineering Co Compositions containing stable aluminum phosphate gel and methods of using same
US3184513A (en) * 1960-08-17 1965-05-18 Allied Chem Production of hexamethylene glycol

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691093A (en) * 1969-02-12 1972-09-12 Du Pont Efficiency of nickel-aluminum catalysts by water washing
US3950441A (en) * 1970-09-16 1976-04-13 Gaf Corporation Process and catalyst for preparing 1,4-butanediol
US4048116A (en) * 1975-08-14 1977-09-13 Basf Aktiengesellschaft Catalyst for the hydrogenation of acetylene alcohols
US4200501A (en) * 1978-03-24 1980-04-29 Basf Wyandotte Corporation Silicate fouling control during dihydric alcohol distillation
US4384147A (en) * 1979-04-27 1983-05-17 Basf Aktiengesellschaft Preparation of catalysts and their use for the hydrogenation of acetylene-alcohols
US4371723A (en) * 1980-04-16 1983-02-01 Gaf Corporation Process of producing a distilled butanediol product of high quality in high yield
USRE32072E (en) * 1980-04-16 1986-01-28 Gaf Corporation Process of producing a distilled butanediol product of high quality in high yield
US4361495A (en) * 1981-03-13 1982-11-30 Gaf Corporation Regeneration of supported-nickel catalysts
US20100016643A1 (en) * 2007-02-15 2010-01-21 Basf Se Process for preparing 1,4-butanediol
US7759531B2 (en) 2007-02-15 2010-07-20 Basf Aktiengesellschaft Process for preparing 1,4-butanediol
CN102161615A (zh) * 2011-02-22 2011-08-24 重庆大学 一种回收1,4-丁二醇的工艺
CN102161615B (zh) * 2011-02-22 2013-06-19 重庆大学 一种回收1,4-丁二醇的工艺

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DE1285992B (de) 1969-01-02

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