DE1161555B - Catalyst for the selective hydrogenation of acetylene - Google Patents
Catalyst for the selective hydrogenation of acetyleneInfo
- Publication number
- DE1161555B DE1161555B DEV21516A DEV0021516A DE1161555B DE 1161555 B DE1161555 B DE 1161555B DE V21516 A DEV21516 A DE V21516A DE V0021516 A DEV0021516 A DE V0021516A DE 1161555 B DE1161555 B DE 1161555B
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- acetylene
- palladium
- percent
- volume
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims description 32
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims description 20
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- 239000012876 carrier material Substances 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002823 nitrates Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- SZMZREIADCOWQA-UHFFFAOYSA-N chromium cobalt nickel Chemical compound [Cr].[Co].[Ni] SZMZREIADCOWQA-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J23/8906—Iron and noble metals
-
- 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
- C07C2521/04—Alumina
-
- 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
- C07C2523/48—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
- C07C2523/74—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
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Internat. Kl.: C 07 cBoarding school Class: C 07 c
Nummer:
Aktenzeichen:
Anmeldetag:
Auslegetag:Number:
File number:
Registration date:
Display day:
Deutsche Kl.: 12 ο-19/01 German class: 12 ο -19/01
V 21516 IVb/12 ο
28. Oktober 1961
23. Januar 1964V 21516 IVb / 12 ο
October 28, 1961
January 23, 1964
Bei der thermischen Zersetzung von Kohlenwasserstoffen zur Gewinnung von Äthylen werden äthylenreiche Spaltgase und in der nachgeschalteten Gastrennanlage äthylenhaltige Fraktionen erhalten, die neben Äthan noch Acetylen enthalten. Da für eine Reihe von chemischen Synthesen ein völlig acetylenfreies Äthylen benötigt wird, muß das Acetylen durch geeignete Verfahren daraus entfernt werden. Dies geschieht überwiegend durch katalytische Hydrierung.During the thermal decomposition of hydrocarbons for the production of ethylene, they become ethylene-rich Fission gases and ethylene-containing fractions received in the downstream gas separation plant, the contain acetylene in addition to ethane. As a completely acetylene-free one for a number of chemical syntheses If ethylene is required, the acetylene must be removed therefrom by suitable methods. this occurs mainly through catalytic hydrogenation.
Es ist bekannt, hierfür Katalysatoren zu verwenden, die als wirksamen Bestandteil Eisen, Kobalt, Nickel, Platin, Rhodium oder Kupfer in metallischer Form oder in Form von Oxyden enthalten. Außerdem sind Kombinationen, wie Nickel—Kupfer, Nickel—Chrom, Nickel—-Kobalt—Chrom, als Katalysatoren für die selektive Hydrierung von Acetylen bekannt. Die Selektivität aller dieser Katalysatoren ist jedoch ungenügend. Man verwendet daher in der Regel Trägerkatalysatoren, die Palladium sowie bestimmte Promotoren als wirksame Bestandteile enthalten und die gegenüber den anderen Kombinationen eine verbesserte Selektivität aufweisen. So ist es bekannt, Palladium auf einem katalytisch wirksamen Trägermaterial, wie aktiviertem Aluminiumoxyd, aufzubringen und als Promotoren Kupfer, Silber und Gold oder auch Eisen, Rhodium und Ruthenium zuzusetzen. Schließlich sind auch Katalysatoren bekannt, die Palladium auf einem katalytisch unwirksamen Trägermaterial, wie Diatomeenerde, enthalten. Als Promotoren für die Palladium auf einem inerten Trägermaterial enthaltenden Katalysatoren werden Kupfer, Silber oder Gold in der Literatur genannt. Die Gesamtmenge an katalytisch wirksamen Bestandteilen beträgt dabei 0,002 bis 5 Gewichtsprozent, bezogen auf die gesamte Katalysatormenge, wobei das -Gewichtsverhältnis von Palladium zu dem jeweiligen Promotor zwischen 99 : 1 und 60: 40 liegt.It is known to use catalysts for this purpose, which have iron, cobalt, nickel, Contains platinum, rhodium or copper in metallic form or in the form of oxides. Also are Combinations such as nickel-copper, nickel-chromium, Nickel —- cobalt — chromium, as catalysts for the selective hydrogenation of acetylene known. However, the selectivity of all of these catalysts is insufficient. Supported catalysts, such as palladium and certain ones, are therefore used as a rule Contain promoters as effective ingredients and which are improved over the other combinations Have selectivity. It is known to use palladium on a catalytically active support material, such as activated aluminum oxide, and copper, silver and gold as promoters or to add iron, rhodium and ruthenium. Finally, catalysts are also known which contain palladium on a catalytically inactive carrier material such as diatomaceous earth. as Promoters for the catalysts containing palladium on an inert support material Mentioned copper, silver or gold in the literature. The total amount of catalytically active ingredients is 0.002 to 5 percent by weight, based on the total amount of catalyst, where the weight ratio of palladium to the particular promoter is between 99: 1 and 60:40.
Doch auch die bekannten Palladiumkatalysatoren besitzen noch keine ausreichende Selektivität, zumindest nicht während der ersten 4 bis 6 Monate ihrer Betriebszeit.But even the known palladium catalysts do not yet have sufficient selectivity, at least not during the first 4 to 6 months of their operating time.
Um mit diesen Katalysatoren eine praktisch vollständige Entfernung des Acetylene zu erzielen, ist ein Volumenverhältnis von Wasserstoff zu Acetylen wie 3: 1 erforderlich. Es hat sich bei Anwendung dieses Mengenverhältnisses jedoch gezeigt, daß nach der katalytischen Behandlung das Gas keinen Wasserstoff mehr enthielt. Aus dieser Tatsache ergibt sich, daß gleichzeitig Äthylen zu Äthan hydriert wird.In order to achieve practically complete removal of the acetylene with these catalysts, is a volume ratio of hydrogen to acetylene such as 3: 1 is required. It has to be applied However, this quantitative ratio shows that after the catalytic treatment the gas does not contain hydrogen contained more. This fact shows that at the same time ethylene is hydrogenated to ethane.
Gegenstand der Erfindung ist ein Katalysator, der bereits nach einigen Betriebstagen eine Selektivität
besitzt, die von den bekannten Acetylenhydrier-Katalysator zur selektiven Hydrierung
von AcetylenThe invention relates to a catalyst which, after a few days of operation, has a selectivity that of the known acetylene hydrogenation catalyst for selective hydrogenation
of acetylene
Anmelder:Applicant:
VEB Leuna-Werke »Walter Ulbricht«,VEB Leuna-Werke »Walter Ulbricht«,
Leuna (Kr. Merseburg)Leuna (Kr.Merseburg)
Als Erfinder benannt:
Dr. Hermann Blume,
Dipl.-Chem. Joachim Münzing,
Ing.-Chem. Emanuel Pindur,
Leuna (Kr. Merseburg)Named as inventor:
Dr. Hermann Blume,
Dipl.-Chem. Joachim Münzing,
Ing.-Chem. Emanuel Pindur,
Leuna (Kr.Merseburg)
katalysatoren erst nach einigen Monaten Betriebszeit erreicht wird. Er bewirkt weder die Abscheidung von Polymerisationsprodukten noch die Bildung von Kohlenstoff. Hinsichtlich seiner Lebensdauer übertrifft er sämtliche bisher bekannten Acetylenhydrierungskatalysatoren. catalysts is only reached after a few months of operation. It does not cause the separation of Polymerization products nor the formation of carbon. Exceeds in terms of its service life he all known acetylene hydrogenation catalysts.
Der Katalysator enthält auf einem inerten Trägermaterial als wirksame Bestandteile Palladium und Silber in Mengen von 0,002 bis 5 Gewichtsprozent, bezogen auf die gesamte Katalysatormenge, wobei der Anteil des Palladiums 99 bis 60 Gewichtsprozent, bezogen auf die Gesamtmenge der beiden Edelmetalle, beträgt, und besitzt erfindungsgemäß einen zusätzlichen Gehalt an Eisenoxyd in einer 20- bis 80fachen Gewichtsmenge, bezogen auf die Gesamtmenge an Palladium und Silber.The catalyst contains palladium and palladium as active ingredients on an inert support material Silver in amounts of 0.002 to 5 percent by weight, based on the total amount of catalyst, wherein the proportion of palladium 99 to 60 percent by weight, based on the total amount of the two precious metals, is, and according to the invention has an additional content of iron oxide in a 20- to 80-fold Amount by weight based on the total amount of palladium and silver.
Als inertes Trägermaterial verwendet man vorzugsweise «-Aluminiumoxyd.The inert carrier material used is preferably a -aluminum oxide.
Der Katalysator gemäß der Erfindung erfordert gegenüber den bekannten Acetylenhydrierungskatalysatoren keine speziellen Verfahrensbedingungen. Der Temperaturbereich seiner größten Wirksamkeit liegt bei 100 bis 140° C, also etwa 60 bis 100° C tiefer als die optimalen Betriebstemperaturen der bekannten Palladiumkatalysatoren. Im Gegensatz zu diesen benötigt der erfindungsgemäße Katalysator lediglich ein Volumenverhältnis von Wasserstoff zu Acetylen wie etwa 2:1. Das Gas weist nach der katalytischen Behandlung stets noch einen geringen Gehalt an Wasserstoff auf, was auf eine gute Selektivität des Katalysators schließen läßt.The catalyst according to the invention requires, compared to the known acetylene hydrogenation catalysts no special process conditions. The temperature range of its greatest effectiveness lies at 100 to 140 ° C, i.e. about 60 to 100 ° C lower than the optimal operating temperatures of the known Palladium catalysts. In contrast to these, the catalyst according to the invention only needs a volume ratio of hydrogen to acetylene such as about 2: 1. The gas points to the catalytic Treatment still has a low hydrogen content, which indicates a good selectivity of the Catalyst can close.
Die Herstellung des Katalysators erfolgt in bekannter Weise. So wird z. B. geformtes «-Aluminiumoxyd mit wässerigen Lösungen von Eisen-, Silber- undThe catalyst is produced in a known manner. So z. B. shaped "aluminum oxide with aqueous solutions of iron, silver and
309 780/283309 780/283
Palladiumsalzen getränkt und anschließend einer Temperaturbehandlung unterworfen. Von Vorteil ist es, die Herstellung in der Weise vorzunehmen, daß die Katalysatoren lediglich mit einer Lösung getränkt werden, die Eisen-, Silber- und Palladiumsalze gleichzeitig enthält, wobei als Salze vorteilhaft die entsprechenden Nitrate verwendet werden.Impregnated with palladium salts and then subjected to a temperature treatment. Is beneficial it to make the production in such a way that the catalysts are only impregnated with a solution containing iron, silver and palladium salts at the same time, the corresponding salts advantageously Nitrates are used.
100 ml gekörntes «-Aluminiumoxyd mit einer Korngröße von 3 bis 5 mm wurden mit 30 ml einer wässerigen Eisennitratlösung getränkt, die 81,5 g Eisen im Liter enthielt. Nachdem die gesamte Lösung vom Aluminiumoxyd aufgenommen war, wurde dieses 12 Stunden bei 105° C getrocknet und anschließend einer 4stündigen Temperaturbehandlung bei 450° C unterworfen. Das so vorbehandelte Material wurde alsdann mit 30 ml einer Lösung getränkt, die im Liter 2,34 g Palladium und 0,117 g Silber als Nitrate enthielt. Nach nochmaliger Trocknung und thermischer Behandlung bei den gleichen Temperaturen enthielt der Katalysator 0,1 % Palladium, 0,005 °/o Silber und 5°/o Eisenoxyd, gerechnet als Fe2O3.100 ml of granulated aluminum oxide with a grain size of 3 to 5 mm were impregnated with 30 ml of an aqueous iron nitrate solution which contained 81.5 g of iron per liter. After all the solution had been absorbed by the aluminum oxide, it was dried at 105 ° C. for 12 hours and then subjected to a temperature treatment at 450 ° C. for 4 hours. The material pretreated in this way was then impregnated with 30 ml of a solution which contained 2.34 g of palladium and 0.117 g of silver as nitrates per liter. After repeated drying and thermal treatment at the same temperatures, the catalyst contained 0.1% palladium, 0.005% silver and 5% iron oxide, calculated as Fe 2 O 3 .
Über diesen Katalysator wurden bei einer Temperatur von 130° C unter einem Druck von 30 at 1000 l/h (drucklos gemessen) eines Gases geleitet, das zu 77 Volumteilen aus Äthylen, zu 22 Volumteilen aus Äthan und zu 1,15 Volumteilen aus Acetylen bestand und dem entsprechend einem Volumen verhältnis von Wasserstoff zu Acetylen wie 2:1 2,30 Volumprozent Wasserstoff beigemischt worden waren. Das hydrierte Gas enthielt weniger als 0,001 Volumprozent Acetylen und 0,40 Volumprozent Wasserstoff.About this catalyst were at a temperature of 130 ° C under a pressure of 30 at 1000 l / h (measured without pressure) of a gas, 77 parts by volume of ethylene, 22 parts by volume Ethane and 1.15 parts by volume of acetylene and the corresponding volume ratio of Hydrogen to acetylene as 2: 1 2.30 percent by volume hydrogen had been added. The hydrogenated Gas contained less than 0.001 volume percent acetylene and 0.40 volume percent hydrogen.
100 ml «-Aluminiumoxyd in Form von Tabletten mit 5 mm Durchmesser und Höhe wurden entsprechend der Wasseraufnahmefähigkeit des Trägermaterials mit 30 ml einer wässerigen Lösung getränkt, die im Liter 81,5 g Eisen, 2,34 g Palladium und 0,117 g Silber in Form ihrer Nitrate enthielt. Nachdem die gesamte Lösung von den Aluminiumoxydtabletten aufgenommen war, wurden diese 12 Stunden bei 105° C getrocknet und anschließend einer 4stündigen Temperaturbehandlung bei 450° C unterworfen.100 ml of aluminum oxide in the form of tablets with a diameter and height of 5 mm were used accordingly the water absorption capacity of the carrier material soaked with 30 ml of an aqueous solution, which contained 81.5 g of iron, 2.34 g of palladium and 0.117 g of silver per liter in the form of their nitrates. After this the entire solution was absorbed by the aluminum oxide tablets, they lasted for 12 hours dried at 105 ° C and then subjected to a 4-hour heat treatment at 450 ° C.
Über den so hergestellten Katalysator, der 0,1 % Palladium, 0,005% Silber und 5% Eisenoxyd, gerechnet als Fe2O3, enthielt, wurden bei einer Temperatur von 110° C unter einem Druck von 30 at 600 l/h (drucklos gemessen) des im Beispiel 1 beschriebenen Gases geleitet, dem entsprechend einem Volumenverhältnis von Wasserstoff zu Acetylen wie etwa 2,2: 1 noch 2,6 Volumteile Wasserstoff zugemischt worden waren. Das hydrierte Gas enthielt weniger als 0,001 Volumprozent Acetylen und noch 1,06 Volumprozent Wasserstoff.The catalyst prepared in this way, which contained 0.1% palladium, 0.005% silver and 5% iron oxide, calculated as Fe 2 O 3 , was used at a temperature of 110 ° C. under a pressure of 30 at 600 l / h (without pressure measured) of the gas described in Example 1, to which 2.6 parts by volume of hydrogen had been added, corresponding to a volume ratio of hydrogen to acetylene such as about 2.2: 1. The hydrogenated gas contained less than 0.001 volume percent acetylene and still 1.06 volume percent hydrogen.
Zu Vergleichszwecken wurde über 100 ml eines Katalysators, der lediglich 0,1 % Palladium und 0,005 °/o Silber auf Λ-Aluminiumoxyd enthielt, bei einer Temperatur von 100° C und einem Druck von 30 at das gleiche Gas in einer Menge von 600 l/h (drucklos gemessen) geleitet. Das hydrierte Gas enthielt weniger als 0,001 Volumprozent Acetylen, aber praktisch keinen Wasserstoff mehr, woraus hervorgeht, daß gleichzeitig auch Äthylen hydriert wordenFor comparison purposes, over 100 ml of a catalyst containing only 0.1% palladium and 0.005% silver on Λ-aluminum oxide contained, at a temperature of 100 ° C and a pressure of 30 at the same gas in an amount of 600 l / h (measured without pressure). The hydrogenated gas contained less than 0.001 volume percent acetylene, but practically no more hydrogen, which shows that ethylene was also hydrogenated at the same time
130 ml «-Aluminiumoxyd mit einer Korngröße von 2 bis 4 mm wurden mit 40 ml einer wässerigen Lösung getränkt, die 115 g Fe, 2,0 g Pd und 0,1 g Ag pro Liter in Form der Nitrate enthielt. Nachdem die Lösung vom Aluminiumoxyd vollständig aufgenommen war, wurde dieses 12 Stunden bei 105° C getrocknet und die so erhaltene Katalysatormasse anschließend einer 4stündigen Temperaturbehandlung bei 450° C unterworfen. Der fertige Katalysator enthielt 0,085% Pd, 0,004% Ag und 7% Eisenoxyd, gerechnet als Fe2O3.130 ml of aluminum oxide with a grain size of 2 to 4 mm were impregnated with 40 ml of an aqueous solution which contained 115 g Fe, 2.0 g Pd and 0.1 g Ag per liter in the form of the nitrates. After the solution of aluminum oxide had been completely absorbed, it was dried for 12 hours at 105.degree. C. and the catalyst mass thus obtained was then subjected to a 4-hour temperature treatment at 450.degree. The finished catalyst contained 0.085% Pd, 0.004% Ag and 7% iron oxide, calculated as Fe 2 O 3 .
Bei einer Temperatur von 200° C wurden über 100 ml dieses Katalysators unter einem Druck von 30 at 600 l/h eines Gases geleitet, das aus 73,8 Volumprozent Äthylen, 21,5 Volumprozent Äthan, 2,7 Volumprozent Wasserstoff und 1,4 Volumprozent Acetylen bestand. Das hydrierte Gas enthielt 0,002 Volumprozent Acetylen und 0,5 Volumprozent Wasserstoff.At a temperature of 200 ° C over 100 ml of this catalyst were under a pressure of 30 at 600 l / h of a gas which consists of 73.8 percent by volume of ethylene, 21.5 percent by volume of ethane, 2.7 Percent by volume hydrogen and 1.4 percent by volume acetylene. The hydrogenated gas contained 0.002 Volume percent acetylene and 0.5 volume percent hydrogen.
Claims (2)
USA.-Patentschrift Nr. 2 927 141.Considered publications:
U.S. Patent No. 2,927,141.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV21516A DE1161555B (en) | 1961-10-28 | 1961-10-28 | Catalyst for the selective hydrogenation of acetylene |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV21516A DE1161555B (en) | 1961-10-28 | 1961-10-28 | Catalyst for the selective hydrogenation of acetylene |
| GB1225/62A GB926263A (en) | 1962-01-12 | 1962-01-12 | Catalyst for selective hydrogenation of acetylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1161555B true DE1161555B (en) | 1964-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEV21516A Pending DE1161555B (en) | 1961-10-28 | 1961-10-28 | Catalyst for the selective hydrogenation of acetylene |
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| Country | Link |
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| DE (1) | DE1161555B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2927141A (en) * | 1957-03-04 | 1960-03-01 | Engelhard Ind Inc | Catalyst for the selective hydrogenation of acetylene |
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1961
- 1961-10-28 DE DEV21516A patent/DE1161555B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2927141A (en) * | 1957-03-04 | 1960-03-01 | Engelhard Ind Inc | Catalyst for the selective hydrogenation of acetylene |
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