DE253160C - - Google Patents

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DE253160C
DE253160C DENDAT253160D DE253160DA DE253160C DE 253160 C DE253160 C DE 253160C DE NDAT253160 D DENDAT253160 D DE NDAT253160D DE 253160D A DE253160D A DE 253160DA DE 253160 C DE253160 C DE 253160C
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catalyst
metals
palladium
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platinum
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    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble 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
    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/10—Magnesium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/42—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/46—Ruthenium, rhodium, osmium or iridium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/48—Silver or gold
    • C07C2523/50—Silver
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/75—Cobalt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
    • C07C2523/74—Iron group metals
    • C07C2523/755—Nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Description

KAISERLICHESIMPERIAL

PATENTAMT.PATENT OFFICE.

PATENTSCHRIFTPATENT LETTERING

- Λ! 253160-KLASSE 12 o. GRUPPE - Λ! 253160- CLASS 12 or GROUP

Dr.WALTER KARO in BERLIN.Dr WALTER KARO in BERLIN.

eines Katalysators.a catalyst.

Patentiert im Deutschen Reiche vom 21. Mai 1911 ab.Patented in the German Empire on May 21, 1911.

In der Literatur finden sich Angaben darüber, daß Acetylen und Wasserstoff neben anderen Kohlenwasserstoffen auch Äthylen bilden. Die Reaktion geht mit erheblicher Geschwindigkeit in Gegenwart sogenannter Kontaktsubstanzen vor sich. Als solche sind bekannt einmal die Metalle der Platingruppe (Platin, Osmium, Iridium) und der Palladiumgruppe (Palladium, Rhodium, Ruthenium),In the literature there is information about the fact that acetylene and hydrogen in addition to other hydrocarbons also form ethylene. The reaction goes with considerable Speed in the presence of so-called contact substances in front of you. As such are once known the metals of the platinum group (platinum, osmium, iridium) and the palladium group (Palladium, rhodium, ruthenium),

ίο also eine Anzahl Edelmetalle schon aus der Patentschrift von Clemens Winkler (Nr. 4566), auf der anderen Seite aus den Arbeiten von S a b a t i e r und Sendereus (Comptes rendus de l'academie des sciences 124, 616 —18; 1358—61; 128, 1173—76; 130, 250—52, 1559—61, 1628—30, 1761 — 64; 131, 40—42, 187—90, 267 — 70) die Metalle Eisen, Nickel, Kobalt, Kupfer, Silber, Magnesium, Zink, Cadmium, Aluminium, d. h. relativ zu den obengenannten unedle Metalle.ίο So a number precious metals already known from the patent by Clemens Winkler, abatier on the other side from the work of S and Sendereus (Comptes rendus de l'Académie des sciences 124 616 -18 (No. 4566th); 1358-61; 128 , 1173-76; 130, 250-52, 1559-61, 1628-30, 1761-64; 131, 40-42, 187-90, 267-70) the metals iron, nickel, cobalt, copper, silver, magnesium , Zinc, cadmium, aluminum, ie relative to the base metals mentioned above.

Bei der Anwendung dieser Kontaktsubstanzen auf die oben angegebene Reaktion zwischen Acetylen und Wasserstoff ergeben sich aber Schwierigkeiten.When applying these contact substances to the above reaction but difficulties arise between acetylene and hydrogen.

Vertreter aus der zu zweit genannten Gruppe der wenig edlen Metalle bedürfen zu ihrer Wirksamkeit Temperaturen, bei denen das primär gebildete Äthylen schon in hohem Betrage weiter reagiert und sich polymerisiert, so daß es nur in geringer Ausbeute gelingt, das gewünschte Endprodukt zu fassen. Ferner aber verlangt die Darstellung dieser Kontaktkörper, ζ. B. des Nickelkatalysators, damit dieser wirklich und dauernd wirksam sei, die genaue Einhaltung subtiler Vorschriften, was den Wert eines solchen Katalysators für die Technik sehr beschränkt.Representatives from the group of less noble metals named two need theirs Effectiveness Temperatures at which the primarily formed ethylene continues to react and polymerize to a large extent, so that it is only possible to obtain the desired end product in a low yield. Further but requires the representation of this contact body, ζ. B. the nickel catalyst, so this is really and permanently effective, the strict observance of subtle rules of what the value of such a catalyst for technology is very limited.

Bei der Anwendung von Vertretern aus der Platin- und Palladiumgruppe zur kätalytischen Bildung von Äthylen zeigen sich zwar diese beiden Übelstände nicht; es tritt aber hier durch sogenannte Vergiftung, d. h. durch Absorption und Reaktion von Verunreinigungen der verwendeten Gase, eine Abnahme der kätalytischen Wirksamkeit ein, und dies um so eher und mehr, als man die angewandte Masse dieser aktiven Körper ihres hohen Preises wegen möglichst niedrig bemißt. Ferner ist bei Anwendung von Kontaktkörpern aus der Platin-Palladiumgruppe die Reaktion oft so stürmisch, daß auch hier wie bei der anderen Gruppe die Temperatur lokal über das erwünschte Maß steigt.When using representatives from the platinum and palladium groups for the catalytic These two evils do not show up in the formation of ethylene; but it occurs here by so-called poisoning, d. H. through absorption and reaction of impurities of the gases used, a decrease in the catalytic effectiveness, and this around so sooner and more than one can see the applied mass of these active bodies of their high Due to the low price. Furthermore, when using contact bodies, it is off The reaction of the platinum-palladium group is often so stormy that here, too, as with the other Group the temperature rises locally above the desired level.

Alle diese Übelstände vermeidet man, wenn man die Wirksamkeit der Vertreter dieser beiden Gruppen kombiniert, d. h. zur Bildung des Äthylens aus Wasserstoff und Acetylen einen Katalysator verwendet, der ein oder mehrere Metalle der ersten Gruppe mit einem oder mehreren der zweiten Gruppe derart verbindet, daß eine freie und durch ihre Struktur geeignete, aus Metallen beider Gruppen gebildete Oberfläche mit vielfacher und wechselnder Berührung ■ der Komponenten in ihr entsteht, und zwar am besten so, daß die unedleren Metalle im Überschuß, d. h. inOne avoids all of these evils if one considers the effectiveness of the representatives of this both groups combined, d. H. for the formation of ethylene from hydrogen and acetylene a catalyst used, the one or more metals of the first group with a or more of the second group connects in such a way that one free and through their Structure suitable, formed from metals of both groups surface with multiple and alternating contact ■ of the components in it, and preferably in such a way that the less noble metals in excess, d. H. in

ß. Auflage, ausgegeben am ri. Januar igiS.Iß. Edition, issued on ri. January igiS.I

vergleichsweise großer Menge zu den edleren in Anwendung kommen, für sie gleichsam das Lösungsmittel bilden.comparatively large amounts are used in addition to the more noble ones, for them that as it were Form solvent.

Erreicht ist damit, daß die unedlen Metalle als Schutzkörper für die edlen wirken, da sie ihrem ganzen chemischen Verhalten nach leichter mit den Gasverunreinigungen reagieren; dadurch ist eine längere Wirksamkeit des Katalysators gewährleistet. FernerWhat is achieved is that the base metals act as protective bodies for the noble ones, since their entire chemical behavior makes them easier to deal with the gas impurities react; this ensures a longer effectiveness of the catalyst. Further

ίο wirken die zugesetzten unedlen Metalle einer zu heftigen Einwirkung der edlen entgegen, der Prozeß verläuft gleichmäßiger und ruhiger, ohne daß man in das System irgendeine Substanz hineingebracht hat, die, am Prozeß ganz unbeteiligt, die Aktivität der Edelmetalle stark dämpft. Im Gegenteil, die auch den Metallen der unedlen Gruppe innewohnende katalytische Kraft wird durch die Edelmetalle gewissermaßen erregt und addiert sich zu deren Wirkung.ίο the added base metals have an effect too violent influence against the noble, the process runs more evenly and calmly, without introducing any substance into the system that, at the process completely uninvolved, strongly dampens the activity of the precious metals. On the contrary, they too Metals of the base group inherent catalytic power is provided by the noble metals to a certain extent arouses and adds to their effect.

Man hat so einen bei niedriger Temperatur gleichmäßig und dauernd wirksamen Katalysator für die Bildung
Acetylen und WasserstoffIn this way one has a catalyst for formation that is uniformly and continuously effective at low temperature
Acetylene and hydrogen

Darstellung auch keinerlei besondere Schwierigkeiten macht.Representation also no particular difficulties power.

Für die Ausführung erwies sich als besonders geeignet eine Kombination von fein verteiltem Nickel mit fein verteiltem Palladium im Mengenverhältnis 10 :i, derart hergestellt, daß man poröse Materialien, wie Kohle, Thon, Porzellan, Asbest, mit der Lösung erst des einen Metalls tränkt, dann trocknet, glüht, und, wenn nötig, reduziert und darauf mitA combination of finely divided was found to be particularly suitable for the execution Nickel with finely divided palladium in a ratio of 10: i, produced in this way that porous materials, such as coal, clay, porcelain, asbestos, can only be used with the solution soaks a metal, then dries, glows, and, if necessary, reduces and then with it

vonfrom

Äthylen aus gewonnen, dessen dem zweiten Metall, ebenso verfährt; ferner eine Kombination von metallischem Magnesium und fein darauf verteiltem Palladium, derart hergestellt, daß man kleine Magnesiumschnitzel durch Eintauchen in Palladiumlösung mit diesem Metall in feiner Verteilung überzieht; hierbei wird durch Auftreten sogenannter elektrischer Lokalelemente nur eine Oberfläche der Magnesiumscheibchen mit Palladium bedeckt, die andere Seite aber durch Auflösung von Magnesium aufgerauht und dadurch besonders wirksam. Mit beiden Anordnungen gelingt es, ein dauernd über den Katalysator geleitetes hälftiges Gemenge von Acetylengas und Wasserstoffgas bei einer Temperatur von 90 ° bis 100 ° C. so weit zu ver- 5°. einigen, daß das austretende Gas etwa 90 Prozent Äthylen enthält.Ethylene extracted from the second metal of which does the same; further a combination of metallic magnesium and finely distributed palladium, manufactured in such a way that small magnesium chips can be obtained by immersion in palladium solution coated with this metal in fine distribution; here is by occurrence of so-called electrical local elements only a surface of the magnesium disc with palladium covered, but the other side roughened by dissolving magnesium and therefore particularly effective. With both arrangements it is possible to produce half a mixture of acetylene gas and hydrogen gas that is continuously passed over the catalyst at one temperature from 90 ° to 100 ° C. as far as 5 °. agree that the escaping gas contains about 90 percent ethylene.

Claims (1)

Patent-Anspruch:Patent claim: Verfahren zur Darstellung von Äthylen aus Acetylen und Wasserstoff in Gegenwart eines Katalysators, dadurch gekennzeichnet, daß man als Katalysator die Mischung von mindestens einem Metall der Platin- oder Palladiumgruppe (Platin, Osmium, Iridium, Palladium, Rhodium, Ruthenium) mit mindestens einem Metall der Reihe: Eisen, Nickel, Kobalt, Kupfer, Silber, Magnesium, Zink, Cadmium, Aluminium anwendet, und zwar in einer An-Ordnung, die eine ihrer Struktur nach geeignete freie Oberfläche beider Gruppen der Katalysatormetalle besitzt.Process for the preparation of ethylene from acetylene and hydrogen in the presence of a catalyst, characterized in that the catalyst is the Mixture of at least one metal from the platinum or palladium group (platinum, osmium, iridium, palladium, rhodium, Ruthenium) with at least one metal of the series: iron, nickel, cobalt, copper, Uses silver, magnesium, zinc, cadmium, aluminum in an order which, according to its structure, has a free surface of both groups of catalyst metals.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE912692C (en) * 1943-03-19 1954-06-03 Degussa Process for the production of olefins or their derivatives
DE1052979B (en) * 1956-12-31 1959-03-19 Dow Chemical Co Process for the removal of acetylene from a gas mixture predominantly containing ethylene by selective hydrogenation
DE1115238B (en) * 1957-02-05 1961-10-19 Basf Ag Process for the partial hydrogenation of acetylene compounds
DE1123423B (en) * 1958-03-31 1962-02-08 Engelhard Ind Inc Process and catalyst for hydrogenating unsaturated vegetable oils
DE1171901B (en) * 1958-07-15 1964-06-11 Girdler Suedchemie Katalysator Process for the removal of acetylenes and diolefins from hydrocarbon gases or their mixtures by selective hydrogenation
DE1289059B (en) * 1961-12-29 1969-02-13 Ethyl Corp Catalytic oxidation of unburned hydrocarbons and carbon monoxide from combustion engine exhaust gases
DE1793024B1 (en) * 1967-07-27 1972-03-09 Ici Ltd Process for selective catalytic hydrogenation
FR2160443A1 (en) * 1971-11-15 1973-06-29 Basf Ag
DE2431929A1 (en) * 1974-07-03 1976-01-22 Basf Ag CATALYST FOR PARTIAL HYDROGENATION
US6930068B2 (en) 1999-12-15 2005-08-16 Nissan Motor Co., Ltd. Methanol reforming catalyst

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE912692C (en) * 1943-03-19 1954-06-03 Degussa Process for the production of olefins or their derivatives
DE1052979B (en) * 1956-12-31 1959-03-19 Dow Chemical Co Process for the removal of acetylene from a gas mixture predominantly containing ethylene by selective hydrogenation
DE1115238B (en) * 1957-02-05 1961-10-19 Basf Ag Process for the partial hydrogenation of acetylene compounds
DE1123423B (en) * 1958-03-31 1962-02-08 Engelhard Ind Inc Process and catalyst for hydrogenating unsaturated vegetable oils
DE1171901B (en) * 1958-07-15 1964-06-11 Girdler Suedchemie Katalysator Process for the removal of acetylenes and diolefins from hydrocarbon gases or their mixtures by selective hydrogenation
DE1289059B (en) * 1961-12-29 1969-02-13 Ethyl Corp Catalytic oxidation of unburned hydrocarbons and carbon monoxide from combustion engine exhaust gases
DE1793024B1 (en) * 1967-07-27 1972-03-09 Ici Ltd Process for selective catalytic hydrogenation
FR2160443A1 (en) * 1971-11-15 1973-06-29 Basf Ag
DE2431929A1 (en) * 1974-07-03 1976-01-22 Basf Ag CATALYST FOR PARTIAL HYDROGENATION
DE2431929B2 (en) * 1974-07-03 1976-07-01 Basf Ag, 6700 Ludwigshafen CATALYST FOR PARTIAL HYDROGENATION
DE2431929C3 (en) * 1974-07-03 1981-04-02 Basf Ag, 6700 Ludwigshafen Partial hydrogenation catalyst
US6930068B2 (en) 1999-12-15 2005-08-16 Nissan Motor Co., Ltd. Methanol reforming catalyst

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