DE1213839B - Process for the partial hydrogenation of water-miscible Acetylenverbin fertilize to ethylene compounds - Google Patents

Process for the partial hydrogenation of water-miscible Acetylenverbin fertilize to ethylene compounds

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Publication number
DE1213839B
DE1213839B DE1964S0090982 DES0090982A DE1213839B DE 1213839 B DE1213839 B DE 1213839B DE 1964S0090982 DE1964S0090982 DE 1964S0090982 DE S0090982 A DES0090982 A DE S0090982A DE 1213839 B DE1213839 B DE 1213839B
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Prior art keywords
water
hydrogenation
percent
miscible
weight
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Pending
Application number
DE1964S0090982
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German (de)
Inventor
Dr. Marcello Massi Mauri San Donato Milanese Dr. Alesssandro di Cio (Italien)
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Snam SpA
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Snam SpA
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Publication of DE1213839B publication Critical patent/DE1213839B/en
Pending legal-status Critical Current

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    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
    • E04G19/00—Auxiliary treatment of forms, e.g. dismantling; Cleaning devices
    • 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
    • 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
    • B01J23/44—Palladium
    • 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
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/60—Platinum group metals with zinc, cadmium or mercury
    • 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
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Architecture (AREA)
  • Mechanical Engineering (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. α.:Int. α .:

C 07cC 07c

Deutsche KL: 12 ο-19/03German KL: 12 o-19/03

Nummer: 1213 839 Number: 1213 839

Aktenzeichen: S 90982IV b/12 ο File number: S 90982IV b / 12 ο

Anmeldetag: 8. Mai 1964Filing date: May 8, 1964

Auslegetag: 7. April 1966Opening day: April 7, 1966

Es ist bekannt, daß sich Acetylenverbindungen in Gegenwart eines Palladiumkatalysators selektiv zu Äthylenverbindungen hydrieren lassen. Dabei bilden sich jedoch mindestens 2 bis 3% gesättigte Verbindung. In Wirklichkeit ist bei dieser Verfahrensweise somit die Selektivität nie größer als 97 bis 98 %. Um größere Selektivitäten zu erzielen, wurde vorgeschlagen, den Palladiumkatalysator durch Imprägnieren oder gemeinsamen Niederschlag mit Blei-, Zink-, Quecksilber-, Cadmium-, Thorium-, Zinn- und anderen Salzen teilweise unwirksam zu machen.It is known that acetylene compounds are selective in the presence of a palladium catalyst Let ethylene compounds hydrogenate. However, at least 2 to 3% saturated compound is formed in the process. In reality, with this procedure, the selectivity is never greater than 97 to 98%. Around To achieve greater selectivities, it has been proposed to impregnate the palladium catalyst or common precipitation with lead, zinc, mercury, cadmium, thorium, tin and others To make salts partially ineffective.

Diese Imprägnier- oder Niederschlagverfahren sind jedoch in der Praxis schwierig durchzuführen, da die Entaktivierungsbedingungen für den Katalysator (Temperatur, Konzentration des Entaktivierungssalzes, Dauer des Vorgangs) sehr kritisch sind. Weicht man nämlich auch nur geringfügig von den optimalen Verfahrensbedingungen ab, dann erhält man Katalysatoren, die entweder nicht selektiv oder völlig unwirksam sind.However, these impregnation or deposition processes are difficult to carry out in practice because the Deactivation conditions for the catalyst (temperature, Concentration of the deactivating salt, duration of the process) are very critical. One dodges namely only slightly from the optimal process conditions, then you get catalysts, which are either not selective or completely ineffective.

Es ist ferner bekannt, daß man die Behandlung des Imprägnierens bzw. gleichzeitigen Niederschiagens bei verhältnismäßig hohen Temperaturen, d. h. etwa 80 bis 1000C, durchführen muß, um einen selektiven Katalysator zu haben, was insbesondere im Fall von Katalysatoren auf Trägern ungünstig ist.It is also known that the impregnation or simultaneous precipitation treatment must be carried out at relatively high temperatures, ie about 80 to 100 ° C., in order to have a selective catalyst, which is particularly unfavorable in the case of supported catalysts.

Die vorliegende Erfindung hat ein Verfahren zur partiellen Hydrierung von mit Wasser mischbaren Acetylenverbindungen zu Äthylenverbindungen in Gegenwart eines Palladiumkatalysators, gegebenenfalls auf einem Träger zum Gegenstand, das dadurch gekennzeichnet ist, daß man die Hydrierung bei 20 bis 6O0C und einem Druck von 1 bis 20 atü in Gegenwart von 0,01 bis 5 Gewichtsprozent der wäßrigen Lösung eines Zinksalzes durchführt.The present invention is a process for the partial hydrogenation of a water-miscible acetylene to Äthylenverbindungen in the presence of a palladium catalyst, optionally on a support to the object, which is characterized in that the hydrogenation is carried out at 20 to 6O 0 C and a pressure of 1 to 20 atü in the presence of 0.01 to 5 percent by weight of the aqueous solution of a zinc salt.

Bei diesem Verfahren nach der Erfindung braucht man somit, um eine 100°/oige Selektivität zu haben, den Palladiumkatalysator nicht der teuren und umständlichen Behandlung des Imprägnierens bzw. gleichzeitigen Niederschiagens zu unterwerfen, da das Zink dem Hydrierungsgemisch fortlaufend in Form einer löslichen Verbindung zugesetzt wird.In this method according to the invention one thus needs to have a 100 ° / o strength selectivity, not to subject the palladium catalyst of the expensive and cumbersome treatment of impregnation or simultaneous low ski agent, since the zinc continuously added to the hydrogenation mixture in the form of a soluble compound will.

Die Lebensdauer der erfindungsgemäß angewandten Katalysatoren bei vergleichsweise gleicher Selektivität ist langer als jene der bekannten entaktivierten Katalysatoren. The service life of the catalysts used according to the invention with comparatively the same selectivity is longer than that of the known deactivated catalysts.

Das Anion des Zinksalzes besitzt keinerlei Bedeutung, doch muß das Salz selbst in Wasser gut löslich sein. Zu diesem Zweck eignen sich gut das Chlorid, das Sulfat, das Nitrat, das Acetat und das Oxalat.The anion of the zinc salt is of no importance, but the salt itself must be readily soluble in water. The chloride, sulphate, nitrate, acetate and oxalate are well suited for this purpose.

Die Salzmenge kann zwischen 0,01 und 5 Gewichtsprozent, vorzugsweise zwischen 0,01 und 2 GewichtsThe amount of salt can be between 0.01 and 5 percent by weight, preferably between 0.01 and 2 percent by weight

Verfahren zur partiellen Hydrierung von
mit Wasser mischbaren Acetylenverbindungen
zu ÄthylenverbindungenProcess for the partial hydrogenation of
water-miscible acetylene compounds
to ethylene compounds

Anmelder:Applicant:

SNAM S. ρ. Α., Mailand (Italien)SNAM S. ρ. Α., Milan (Italy)

Vertreter:Representative:

Dr. F. Zumstein,Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. AssmannDipl.-Chem. Dr. rer. nat. E. Assmann

und Dipl.-Chem. Dr, R. Koenigsberger,and Dipl.-Chem. Dr, R. Koenigsberger,

Patentanwälte, München 2, Bräuhausstr. 4Patent Attorneys, Munich 2, Bräuhausstr. 4th

Als Erfinder benannt:
Dr. Alessandro die Cio,
Dr. Marcello Massi Mauri,
San Donato Milanese (Italien)Named as inventor:
Dr. Alessandro the Cio,
Dr. Marcello Massi Mauri,
San Donato Milanese (Italy)

Beanspruchte Priorität:Claimed priority:

Italien vom 10. Mai 1963 (9769)Italy 10 May 1963 (9769)

prozent, bezogen auf die Acetylenverbindung, schwanken. percent, based on the acetylene compound, vary.

Vorzugsweise wird dem Reaktionsgemisch Ammoniak in sehr geringen Mengen, die vorzugsweise geringer als 0,5 Gewichtsprozent der Acetylenverbindung sind, zugesetzt, obwohl auch größere Mengen, bis zu 20 bis 30%, die Umsetzung in keiner Weise negativ beeinflussen.Ammonia is preferably added to the reaction mixture in very small amounts, which is preferred less than 0.5 percent by weight of the acetylene compound are added, although larger amounts are also added, up to 20 to 30%, do not negatively affect the implementation in any way.

Das Verfahren gemäß der Erfindung läßt sich sowohl kontinuierlich als auch diskontinuierlich innerhalb weiter Temperaturbereiche, beispielsweise zwischen 20 und 6O0C, sowie Druckbereiche, beispielsweise zwischen 1 und 20 atü, durchführen. Es ist bemerkenswert, daß die Menge des dem Reaktionsgemisch zuzusetzenden Salzes innerhalb der bereits angegebenen Grenzen von der Reaktionsgeschwindigkeit, d. h. vom Wasserstoffdruck und von der Temperatur, abhängt, wie sich aus den folgenden Beispielen ergibt.The method of the invention can be either continuously or discontinuously within wide temperature ranges, for example between 20 and 6O 0 C, and pressure ranges, for example between atmospheres 1 and 20 and perform. It is noteworthy that the amount of salt to be added to the reaction mixture depends, within the limits already given, on the reaction rate, ie on the hydrogen pressure and on the temperature, as can be seen from the following examples.

Beispiel 1example 1

Bei der Hydrierung von 2-Methyl-3-butin-2-ol in azeotroper Mischung mit Wasser (26 Gewichtsprozent Wasser) und in Gegenwart von 1 Gewichtsprozent eines Palladiumkatalysators auf CaCO3 (5 % Pd) und von 0,1 Gewichtsprozent Ammoniak, bezogen auf dasIn the hydrogenation of 2-methyl-3-butyn-2-ol in an azeotropic mixture with water (26 percent by weight of water) and in the presence of 1 percent by weight of a palladium catalyst, based on CaCO 3 (5% Pd) and 0.1 percent by weight ammonia on the

609 557/340609 557/340

I 213 839I 213 839

Methylbutinol, in einem Autoklav unter Rühren und unter verschiedenen Temperatur- und Druckverhältnissen wurde stets eine 100°/0ige Selektivität und ein Anhalten der Reaktion nach Aufnahme des theoretisch der Hydrierung der dreiwertigen Verbindung allein entsprechenden Wasserstoffes erreicht, wobei die in der folgenden Tabelle angeführten Gewichtsanteile von Zinkacetat hinzugefügt wurden.Methylbutynol, in an autoclave with stirring and under different temperature and pressure conditions wherein the listed in the following table by weight always a 100 ° / 0 strength selectivity and stopping the reaction after recording was the theoretically alone reaches the hydrogenation of the trivalent compound corresponding hydrogen, of zinc acetate were added.

Temperaturtemperature Druckpressure Zn(C2H3Os)2 Zn (C 2 H 3 Os) 2 0C 0 C atüatü in Gewichtsprozentin percent by weight 11 3030th 11 0,050.05 22 3030th 55 0,200.20 33 5050 1010 0,800.80 44th 3030th 2020th 0,600.60

Beispiel 2Example 2

2-Methyl-3-butin-2-ol in azeotroper Mischung mit Wasser wurde bei 50° C und 1 atü mit den in der folgenden Tabelle angeführten Salzen hydriert, wobei stets eine 100°/0ige Selektivität erhalten wurde.2-methyl-3-butyn-2-ol in an azeotropic mixture with water was stirred at 50 ° C and 1 atm with the listed in the following table hydrogenated salts, always a 100 ° / 0 selectivity strength was obtained.

Versuchattempt Art des SalzesType of salt Menge des Salzes
in GewichtsprozentAmount of salt
in percent by weight 1
2
3
41
2
3
4th ZnSO4
Zn(NO3)2
ZnCl2
Zn(C2O4)ZnSO 4
Zn (NO 3 ) 2
ZnCl 2
Zn (C 2 O 4 ) 0,12
0,08
0,24
0,140.12
0.08
0.24
0.14

Beispiel 3Example 3

Um die Lebensdauer des Katalysators zu prüfen, wurden im Autoklav unter Rühren 100 g azeotropes 2-Methyl-3-butin-2-ol-Wasser-Gemisch, 1 g Pd/CaCO3 (5% Pd), 0,1g Zinkacetat und 0,1g NH3 bei 600C und unter einem Wasserstoffdruck von 1 atü bis zum Anhalten der Hydrierung behandelt. Anschließend wurde die Flüssigkeit durch Dekantieren, beseitigt und auf den am Boden des Autoklav verbliebenen Katalysator wurden neuerlich 100 g azeotropes Methylbutinol-Wasser-Gemisch, 0,02 g Zinkacetat und 0,1 g NH3 gebracht und Wasserstoff aufnehmen gelassen.To test the service life of the catalyst, 100 g of azeotropic 2-methyl-3-butyn-2-ol-water mixture, 1 g of Pd / CaCO 3 (5% Pd), 0.1 g of zinc acetate and 0 , 1g NH 3 at 60 0 C and treated under a hydrogen pressure of 1 atm until the hydrogenation stops. The liquid was then removed by decanting, and another 100 g of azeotropic methylbutynol / water mixture, 0.02 g of zinc acetate and 0.1 g of NH 3 were placed on the catalyst remaining at the bottom of the autoclave, and hydrogen was allowed to take up.

Dies wurde 50mal wiederholt, wobei die Umsetzung nach Aufnahme der theoretischen Wasserstoffmenge zur Bildung von Methylbutenol stets aufhörte, die Selektivität praktisch immer 100%ig und die Umsetzungsgeschwindigkeit bei allen Versuchen die gleiche war.This was repeated 50 times, the reaction taking place after the theoretical amount of hydrogen had been taken up the formation of methylbutenol always ceased, the selectivity practically always 100% and the rate of conversion was the same in all attempts.

Beispiel 4Example 4

Es werden unter Rühren bei 30° C und 1 atü im ίο Autoklav 500 g 2-Butin-l,4-diol, 20 g Wasser, 0,5 g Zn(C2H3O2).,, 5 g Pd/CaCO3 (5% Pd) und 0,1 g NH3 hydriert. Nach Aufnahme der theoretischen Wasserstoffmenge hört die Umsetzung auf, und man erhält mit quantitativer Ausbeute 2-Buten-l,4-diol.500 g of 2-butyne-1,4-diol, 20 g of water, 0.5 g of Zn (C 2 H 3 O 2 ). ,, 5 g of Pd / Hydrogenated CaCO 3 (5% Pd) and 0.1 g NH 3 . After the theoretical amount of hydrogen has been taken up, the reaction stops and 2-butene-1,4-diol is obtained with a quantitative yield.

Beispiel 5Example 5

In ein rohrförmiges Reaktionsgefäß, dessen Temperatur auf 500C gehalten wird, werden kontinuierlich, zusammen stündlich 301 azeotropes Methylbutinol-In a tubular reaction vessel, the temperature of which is kept at 50 0 C, are continuously, together every hour 301 azeotropic methylbutynol

ao Wasser-Gemisch, das 1% Pd/CaCO3 (5% Pd), 0,2% Zn(C2H3Oa)2 und 0,02 % NH3 enthält, sowie 5 Nm3 H2 eingeleitet. Es wird bei einem Druck von 6 atü gearbeitet, und man erhält ein Produkt, das keine gesättigte Verbindung und nur Spuren Acetylenalkohol enthält.ao water mixture containing 1% Pd / CaCO 3 (5% Pd), 0.2% Zn (C 2 H 3 Oa) 2 and 0.02% NH 3 , and 5 Nm 3 H 2 were introduced. A pressure of 6 atmospheres is used, and a product is obtained which contains no saturated compound and only traces of acetylene alcohol.

Claims (3)

Patentansprüche:Patent claims: 1. Verfahren zur partiellen Hydrierung von mit Wasser mischbaren Acetylenverbindungen zu Äthylenverbindungen in Gegenwart eines Palladiumkatalysators, gegebenenfalls auf einem Träger, dadurch gekennzeichnet, daß man die Hydrierung bei 20 bis 6O0C und einem Druck von 1 bis 20 atü in Gegenwart von 0,01 bis 5 Gewichtsprozent der wäßrigen Lösung eines Zinksalzes durchführt.1. A process for the partial hydrogenation of acetylenic compounds to water-miscible Äthylenverbindungen in the presence of a palladium catalyst, optionally on a support, characterized in that the hydrogenation atm at 20 to 6O 0 C and a pressure of 1 to 20 in the presence of 0.01 Carries out up to 5 percent by weight of the aqueous solution of a zinc salt. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Hydrierung in Gegenwart von 0,01 bis 2 Gewichtsprozent der wäßrigen Lösung eines Zinksalzes durchführt.2. The method according to claim 1, characterized in that the hydrogenation is carried out in the presence carries out from 0.01 to 2 percent by weight of the aqueous solution of a zinc salt. 3. Verfahren nach Anspruch 1 bis 2, dadurch gekennzeichnet, daß man die Hydrierung in Gegenwart von höchstens 0,5 Gewichtsprozent Ammoniak durchführt.3. The method according to claim 1 to 2, characterized in that the hydrogenation is carried out in the presence carries out no more than 0.5 percent by weight of ammonia. In Betracht gezogene Druckschriften:
Deutsche Auslegeschriften Nr. 1139 832, 1115 238.Considered publications:
German Auslegeschriften No. 1139 832, 1115 238. 609 557/340 3.66 © Bundesdruckelei Berlin609 557/340 3.66 © Bundesdruckelei Berlin
DE1964S0090982 1963-05-10 1964-05-08 Process for the partial hydrogenation of water-miscible Acetylenverbin fertilize to ethylene compounds Pending DE1213839B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT976963 1963-05-10

Publications (1)

Publication Number Publication Date
DE1213839B true DE1213839B (en) 1966-04-07

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Country Link
BE (1) BE647710A (en)
CH (1) CH438269A (en)
DE (1) DE1213839B (en)
GB (1) GB1024318A (en)
LU (1) LU46049A1 (en)
NL (1) NL6405225A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207146A2 (en) * 2000-11-20 2002-05-22 Council of Scientific and Industrial Research Process for the conversion of 1,4 butynediol to 1, 4 butenediol

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9324784D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324823D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324786D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324782D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324785D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324783D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324753D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process
GB9324752D0 (en) * 1993-12-02 1994-01-19 Davy Mckee London Process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1115238B (en) * 1957-02-05 1961-10-19 Basf Ag Process for the partial hydrogenation of acetylene compounds
DE1139832B (en) * 1961-05-11 1963-05-16 General Aniline &. Film Corporation, New York, N Y. (V. St. A.) Process for the partial hydrogenation of butyne- (2) -diol- (l, 4) to butene- (2) diol- (l, 4)

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1115238B (en) * 1957-02-05 1961-10-19 Basf Ag Process for the partial hydrogenation of acetylene compounds
DE1139832B (en) * 1961-05-11 1963-05-16 General Aniline &. Film Corporation, New York, N Y. (V. St. A.) Process for the partial hydrogenation of butyne- (2) -diol- (l, 4) to butene- (2) diol- (l, 4)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1207146A2 (en) * 2000-11-20 2002-05-22 Council of Scientific and Industrial Research Process for the conversion of 1,4 butynediol to 1, 4 butenediol
EP1207146A3 (en) * 2000-11-20 2003-11-19 Council of Scientific and Industrial Research Process for the conversion of 1,4 butynediol to 1, 4 butenediol

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BE647710A (en) 1964-11-09
GB1024318A (en) 1966-03-30
LU46049A1 (en) 1965-11-09
NL6405225A (en) 1964-11-11
CH438269A (en) 1967-06-30

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E77 Valid patent as to the heymanns-index 1977