US3180902A - Process for the hydrogenolysis of light hydrocarbons - Google Patents

Process for the hydrogenolysis of light hydrocarbons Download PDF

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US3180902A
US3180902A US130478A US13047861A US3180902A US 3180902 A US3180902 A US 3180902A US 130478 A US130478 A US 130478A US 13047861 A US13047861 A US 13047861A US 3180902 A US3180902 A US 3180902A
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catalyst
hydrogenolysis
mol percent
hydrocarbons
hydrogen
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Holger C Andersen
Philip L Romeo
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BASF Catalysts LLC
Engelhard Industries Inc
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Engelhard Industries Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds 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
    • C07C2523/38—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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas

Definitions

  • the process involves passing an admixture of hydrogen and the light hydrocarbon into contact with a platinum group metal catalyst, preferably a supported catalyst, at an elevated temperature, preferably from about 80 C.600 C.
  • a platinum group metal catalyst preferably a supported catalyst
  • an elevated temperature preferably from about 80 C.600 C.
  • hydrogenolysis of the light hydrocarbon molecules is effected and the methane is produced.
  • the process is of merit because achieving the following advantages: (1) eifects hydrogenolysis of the light hydrocarbons cfiici'ently and with relative ease, cracking of light hydrocarbons heretofore being attended with relative difiiculty; and (2) produces a methane-containing product gas which is a good fuel gas and interchangeable with natural gas and other fuel gas.
  • Natural gas which consists mainly of CH is frequently used as a fuel for reasons of economy and convenience, and fuel burners using natural gas are adjusted for the proper intake of fuel and air. It has been one of the major problems of the utility gas industry to develop processes for peak-load substitutes for natural gas. Where a low molecular weight feed is available, this invention is eminently adapted for the production of CH It is also noteworthy that one of the major problems in developing a substitute for natural gas is the reduction of unsaturated hydrocarbons, since combustion of unsaturated hydro-carbons results in yellow-tipping and soot deposition. It has been difiicult to reduce the unsaturated hydrocarbons to CH i.e. it could be accomplished only at high temperatures with resultant high rates of carbon formation. According to this invention the unsaturated hydrocarbons react with H to form CH at relatively low temperatures.
  • the platinum group metals which are employed as catalysts in the present invention are preferably carried on a suitable support, for instance activated alumina, carbon, silica gel and di-atomaceous earth, and any combination thereof.
  • the platinum group metal is preferably rhodium, ruthenium, palladium, platinum and combinations of such metals, for instance ruthenium and platinum, ruthenium and palladium, and rhodium and platinum.
  • the catalyst metal is preferably present in amount of about 0.1 -5 weight percent, more preferably about 0.32 weight percent of the catalyst metal and support. The extent of the crackingv-aries with the particular catalyst used, the support, and the concentration of catalyst.
  • Temperatures of from about 0-600 C. are preferred in the present invention inasmuch as temperatures much above 600 C. tend to result in greater coke formation. Temperature-s much below 80 C. should be avoided, as the hydrogenolys-is will not be affected to any appreciable extent at such temperatures.
  • the optimum temperature employed depends upon the nature and concentration of the catalyst as well as the nature and concentration of the reactants. More preferably, for the hydrogenolysis of ethane-containing gas, temperatures between 200 C. and 300 C. are employed when utilizing arhodium catalyst, between C. and 400 C. when using a ruthenium catalyst, between 300 C. and 400 C. when employing a palladium catalyst, between 210 C. and 300 C. when employing a ruthenium-platinum catalyst, and between 220 C. and 450 C. when utilizing a ruthenium-palladium catalyst.
  • Hydrocarbons which are subjected to the hydrogenolysi-s of the present invention are non-cyclic aliphatic light hydrocarbons which may be saturated and/or unsaturated, and substituted and/or unsubstituted.
  • the number of carbon atoms per molecule of the hydrocarbon can range from 2-7.
  • Examples of such hydrocarbons include ethane, ethylene, propane, propylene, butane, 1- .butene, hexane, n-hexylene, pentane, l-pentene, heptane, heptylene, and 2,2-dimethyl butane.
  • the proportion of hydrogen in the. input mixture can be varied and the extent of the hydrogenolysis depends on the ratio of hydrocarbon to hydrogen in the input mixture. For greatest percentage yield of methane a quantity of hydrogen is utilized which is that stoic-hi0- metrically required for reaction with all the hydrocarbon to produce methane.
  • Exemplary hydrogenolysis reactions of this invention utilizing ethane as hydrocarbon in reaction (1) and pentane as hydrocarbonin reaction (2) are set forth below: i
  • Space velocities employed can range up to 20,000 standard volumes of gas per volume of catalyst per hour, preferably from about 1000 to 10,000 standard volumes arrests anemone gas per volume of catalyst per hour.
  • the reaction will proceed at pressures ranging from about 0-1000 p.s.i.g.
  • the invention will be further illustrated by reference to the following examples.
  • EXAMPLE I A mixture of 55 mol percent ethane and 45 mol percent hydrogen was metered through a rotameter into a reactor of 1" diameter containing 20 ml. of 0.5 percent Ru on activated A1 0 pellets at a temperature of about 220 C. The resultant gaseous products were analyzed by an infrared spectrophotometer and 85 mol percent methane was noted.
  • Table I The data in Table I show that a ruthenium catalyst in the presence of hydrogen promoted the cracking of light, aliphatic, saturated hydrocarbons to form methane.
  • Inlet mixture includes 0.9 mol percent C 114, 0.72 mol percent 00 outlet mixture includes 0.40 mol percent CgH4, trace of CO; 1.0 mol percent CO.
  • Outlet mol percent Catalyst Tgrgp V 00 H, CH4 0,11, can, o0 H, 01-1., 0 H; one,
  • Inlet mixture includes 0.07 mol percent 02. B N 01; analyzed The data in Table IV indicate that the ease of hydrogenolysis increases with the metal content of catalyst used.
  • the resultant gaseous products at various temperatures were analyzed by an infrared specpassed through a micro-bubbler filled with neohexane and over 20 ml. of Ru on A3 activated A1 0 pellets.
  • the space velocity was 4750 s.c.f.h./c.f.
  • the inlet mixture contained 45.5 mol percent neohexane and 54.5 mol percent H
  • a gas sampling bulb in series with a cold trap was used to collect the samples for analysis. Analysis of the etlluent gases showed that 4.0 mol percent CH was formed at 90 C. and considerable quantities of CH, were formed at higher temperatures.
  • Infrared analysis of the outlet mixtures, with temperatures ranging to 432 C. did not show the formation of reaction products other than CH No attempt was made to determine exact quantities, but considerable quantities of CH, were formed at temperatures below 200 C.
  • a process for the hydrogenolysis of non-cyclic aliphatic light hydrocarbons which comprises passing a gaseous admixture of hydrogen and a gas containing primarily a hydrocarbon from the group consisting of noncyclic saturated aliphatic light hydrocarbons having from 2-4 carbon atoms per molecule, ethylene, propylene,
  • a supported catalyst consisting essentially of a catalytic metal selected from the group consisting of ruthenium and a rutheniumpalladiurn combination, supported on activated alumina, at a temperature within the range of between 197 C. and 370 C. and a space velocity from about 1000 to 10,000 standard volumes of gas per volume of catalyst per hour, the catalytic metal being present in amount of about 0.1-5 weight percent based on catalytic metal plus sup port, whereby hydrogenolysis of the hydrocarbon occurs to produce gaseous reaction products comprising methane.
  • a supported catalyst consisting essentially of a catalytic metal selected from the group consisting of ruthenium and a rutheniumpalladiurn combination, supported on activated alumina, at a temperature within the range of between 197 C. and 370 C. and a space velocity from about 1000 to 10,000 standard volumes of gas per volume of catalyst per hour, the catalytic metal being present in amount of about 0.1-5 weight percent based on catalytic metal plus

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Description

we? a j United States Patent 0 3,180,902 PRCCESS FOR THE HYDROGENOLYSiIiS GF LIGHT HYDRGCARBONS Holger C. Andersen, Morristown, and Philip L. Romeo, 01d Bridge, NJ, assignors to Engeihard Industries, inc, Newark, NJ a corporation of Delaware No Drawing. Filed Aug. 10, 1961, Ser. No. 130,478 2 Claims. (Cl. 260-676) In accordance with the present invention, a novel and meritorious process is provided for the hydrogenolysis of non-cyclic, aliphatic light saturated and/or unsaturated hydrocarbons characterized by having 2-7 carbon atoms per molecule, to produce methane. In its broader aspects, the process involves passing an admixture of hydrogen and the light hydrocarbon into contact with a platinum group metal catalyst, preferably a supported catalyst, at an elevated temperature, preferably from about 80 C.600 C. By reason of such catalytic contacting at a temperature within the range specified, hydrogenolysis of the light hydrocarbon molecules is effected and the methane is produced. The process is of merit because achieving the following advantages: (1) eifects hydrogenolysis of the light hydrocarbons cfiici'ently and with relative ease, cracking of light hydrocarbons heretofore being attended with relative difiiculty; and (2) produces a methane-containing product gas which is a good fuel gas and interchangeable with natural gas and other fuel gas.
Natural gas, which consists mainly of CH is frequently used as a fuel for reasons of economy and convenience, and fuel burners using natural gas are adjusted for the proper intake of fuel and air. It has been one of the major problems of the utility gas industry to develop processes for peak-load substitutes for natural gas. Where a low molecular weight feed is available, this invention is eminently adapted for the production of CH It is also noteworthy that one of the major problems in developing a substitute for natural gas is the reduction of unsaturated hydrocarbons, since combustion of unsaturated hydro-carbons results in yellow-tipping and soot deposition. It has been difiicult to reduce the unsaturated hydrocarbons to CH i.e. it could be accomplished only at high temperatures with resultant high rates of carbon formation. According to this invention the unsaturated hydrocarbons react with H to form CH at relatively low temperatures.
The attainment of hydrogenolysis of the light hydrocarbons of this invention with relative case was unexpected and surprising, inasmuch as heretofore cracking of such light hydrocarbons was difficult as compared with cracking of higher molecular weight hydrocarbons containing more than 7 carbons per molecule.v The hydrogenolysis of hydrocarbons having from 2-4 carbon atoms Patented Apr. 27, 1965 .per molecule with ease in accordance with this invention was deemed to be especially an achievement.
The platinum group metals which are employed as catalysts in the present invention are preferably carried on a suitable support, for instance activated alumina, carbon, silica gel and di-atomaceous earth, and any combination thereof. The platinum group metal is preferably rhodium, ruthenium, palladium, platinum and combinations of such metals, for instance ruthenium and platinum, ruthenium and palladium, and rhodium and platinum. The catalyst metal is preferably present in amount of about 0.1 -5 weight percent, more preferably about 0.32 weight percent of the catalyst metal and support. The extent of the crackingv-aries with the particular catalyst used, the support, and the concentration of catalyst.
Temperatures of from about 0-600 C. are preferred in the present invention inasmuch as temperatures much above 600 C. tend to result in greater coke formation. Temperature-s much below 80 C. should be avoided, as the hydrogenolys-is will not be affected to any appreciable extent at such temperatures. The optimum temperature employed depends upon the nature and concentration of the catalyst as well as the nature and concentration of the reactants. More preferably, for the hydrogenolysis of ethane-containing gas, temperatures between 200 C. and 300 C. are employed when utilizing arhodium catalyst, between C. and 400 C. when using a ruthenium catalyst, between 300 C. and 400 C. when employing a palladium catalyst, between 210 C. and 300 C. when employing a ruthenium-platinum catalyst, and between 220 C. and 450 C. when utilizing a ruthenium-palladium catalyst.
Hydrocarbons which are subjected to the hydrogenolysi-s of the present invention are non-cyclic aliphatic light hydrocarbons which may be saturated and/or unsaturated, and substituted and/or unsubstituted. The number of carbon atoms per molecule of the hydrocarbon can range from 2-7. Examples of such hydrocarbons include ethane, ethylene, propane, propylene, butane, 1- .butene, hexane, n-hexylene, pentane, l-pentene, heptane, heptylene, and 2,2-dimethyl butane.
The proportion of hydrogen in the. input mixture can be varied and the extent of the hydrogenolysis depends on the ratio of hydrocarbon to hydrogen in the input mixture. For greatest percentage yield of methane a quantity of hydrogen is utilized which is that stoic-hi0- metrically required for reaction with all the hydrocarbon to produce methane. Exemplary hydrogenolysis reactions of this inventionutilizing ethane as hydrocarbon in reaction (1) and pentane as hydrocarbonin reaction (2) are set forth below: i
adsorption, it is frequently possible to regenerate the catalyst by burning offthe coke and/or sulfur by treatment with oxygen-containing gas.
Space velocities employed can range up to 20,000 standard volumes of gas per volume of catalyst per hour, preferably from about 1000 to 10,000 standard volumes arrests anemone gas per volume of catalyst per hour. The reaction will proceed at pressures ranging from about 0-1000 p.s.i.g. The invention will be further illustrated by reference to the following examples.
EXAMPLE I A mixture of 55 mol percent ethane and 45 mol percent hydrogen was metered through a rotameter into a reactor of 1" diameter containing 20 ml. of 0.5 percent Ru on activated A1 0 pellets at a temperature of about 220 C. The resultant gaseous products were analyzed by an infrared spectrophotometer and 85 mol percent methane was noted.
Other mixtures of hydrocarbon and hydrogen gases set forth in Table I, were similarly tested for hydrogenolysis with the ruthenium catalyst.
Results of these experiments are listed in Table I.
Table I The data in Table I show that a ruthenium catalyst in the presence of hydrogen promoted the cracking of light, aliphatic, saturated hydrocarbons to form methane.
In tabulating the data in Table I, minor ingredients in inlet and outlet gases are omitted to simplify interpretation of the data. Apparent discrepancies in the determination of yields and in the analysis of total product gases present are within the limits of experimental and analytical error with the methods used.
EXAMPLE II Using the procedure described in Example I, gas mixtures ranging from 5 mol percent ethane and 95 mol percent hydrogen to 99 mol percent ethane, 0.15 mol percent methane, 0.85 mol percent ethylene and no hydrogen were employed to determine the yield of methane at various temperatures.
CATALYTIC HYDRO GENOLYSIS OF HYDROCARBONS Catalyst: m1. of 0.5% Ru on W activated A1 0 pellets Pressure: 0 p.s.i.g. Space velocity: 2000-3000 s.c.f.h./c.i.
EFFECT OF CATALYST ON ETHANE-HYDROGEN MIX- TURES Catalyst: 0.5% Ru on 5 activated A1 0 pellets Conditions:
Pressure-O p.s.i.g.
Space vel0city2000-3000 s.c.f.h./c.i.
Inlet, mol percent 1 Outlet, mol percent Cale. temp.
for 100% yield of 1 Small amounts of C 11 present as impurities.
2 Not analyzed.
3 Inlet mixture includes 0.9 mol percent C 114, 0.72 mol percent 00 outlet mixture includes 0.40 mol percent CgH4, trace of CO; 1.0 mol percent CO.
From the data in Table II it is evident that in the hydrogenolysis of ethane, where the catalyst and other conditions are constant, the extent of the hydrogenolysis varies with the temperature and the concentrations of ethane and hydrogen in the input mixture.
It is also evident from Table II that the Ru catalyst in the presence of H promoted the cracking of ethane in a 82 mol percent ethane-l8 mol percent hydrogen input mixture, approaching maximum yield at a temperature of approximately C., while no appreciable cracking occurred in ethane (99 percent) through 383 C. in the absence of hydrogen.
EXAMPLE III Using the procedure described in Example I, a mixture of 41 mol percent C H and 49 mol percent hydrogen was metered into a reactor containing 10 ml. of 0.5 percent Ru on A3" activated A1 0 pellets. Similarly, mixtures of approximately the same proportions of gases were metered into other reactors containing other catalysts as listed in Table III.
Table III EFFECT OF CATALYSTS IN PROMOTING THE HYDROGENOLYSIS OF ETHANE [Amount of eata1yst-10ml.; space v'eloclty-4000 s.0.f.h./c.f.; pressurep.s.i.g.]
Inlet mol percent 1 Outlet mol percent Catalyst Tgrgp V 00 H, CH4 0,11, can, o0 H, 01-1., 0 H; one,
0.5% Ru on 14' activated A1201 pellets 174 0.48 49 14 1.5 41 06 17 47 .03 I 27 0.5% Rh on 16" activated A1203 pellets 210 0. 36 49 14 1. 7 41 0060 "0. 6 84 02 002 0.5% Pd on ,4 activated A1203 pellets. 360 0. a6 49 14 1.6 41 0005 20 40 02 32 400 0.36 49 14 1. a 41 0005 30 28 02 38 I 420. 0.36 40 14 1.6 41 0005 44 19 02 44 1% Pt on carbon 460 0.36 49 14 1. 6 41 0. 34 86 30 02 34 0.3% Pt'+0.2% Ru on z activated 1 A1 03 pellets 210 0 36 49 14 1 7 41 0060 6.6 79 02 10 0.4% Pd+0.1% Ru on 942' activated A1 0 pellets 240 0. 40 49 14 1. 6 41 0005 6. 0 75 02 11 490 0. 40 49 14 1. 6 41 50 4s 0. 69 45 5% Co on 14' A1 0; spheres 280-350 0. 3e 49 14 1. 6 41 0.26 45 14 03 42 Hopcalite (Ag-Mn) 160 0. 36 49 14 1. 3 42 0. 34 4s 15 1. 2 42 450 0. 36 40 14 1. 3 42 0. 36 4s 14 0. 40 43 Finely divided copper 370 0. 30 49 14 1.6 42- 0.28 47 14 .02 43 425 0. 36 49 14 1. 6 42 0. 24 47 14 02 43 1 Inlet mixture includes 0.07 mol percent 02. 2 Not analyzed. I 5
The results tabulated in Table III indicate that the ease v 01 hydrogenolysis of ethane varies with the catalyst. Fur- EXAMPLE V thcrmore, it is evident that ruthenium and rhodium are particularly effective in promoting this reaction at relatively low temperatures, and, ruthenium in combination with platinum, and ruthenium in combination with palladium are effective catalysts.
EXAMPLE IV Using the procedure described in Example I, mixtures of ethane and hydrogen were passed over 10 n11. of Pd catalyst. As indicated in Table IV, the metal content of catalyst was varied.
Table IV The following experiments are set forth to show the promotion of hydrogenolysis of an unsaturated and of a branched, aliphatic light hydrocarbon to form methane by a platinum group metal catalyst in the presence of hydrogen. The experiments were conducted at 0 p.s.i.g.
Using the procedure described in Example I, approximately 41 mol percent C l-I 14 mol percent CH 1.5 mol percent C H 0.48 mol percent CO, 0.07 mol percent 0 and the balance H was metered through a rotameter into a reactor containing 10 ml. of 0.5 percent Ru on activated A1 0 pellets. The space velocity EFFECT OF VARIATION OF CATALYST METAL CONTENT ON HYDROGENOLYSIS OF ETHANE Catalyst-1O ml. Conditions:
Pressure0 p.s.i.g.
1 Inlet mixture includes 0.07 mol percent 02. B N 01; analyzed The data in Table IV indicate that the ease of hydrogenolysis increases with the metal content of catalyst used.
The general comments in Example I regarding reported data apply also to Tables 11, Ill and IV.
Inlet mol percent 1 Outlet mol percent Catalyst Tgrgp,
' 00 H; CH4 CzH 02116 CO H; CH C2114 C 11 0.5% Pd on $6 activated A1203 pellets- 360 0.36 49 14 1. G 41 0005 40 02 32 400 0.36 49 14 1. 6 41 0005 28 02 38 420 0.36 49 14 1. 6 41 0005 44 19 02 44 2% Pd on activated A1 0 pellets" 300-390 0.36 49 14 1. 6 41 0. 13 2 0 85 02 0020 0.4% Pd+0.1% Ru on 042" activated A1201 240 0.40 49 14 1. 6 41 0005 6 0 75 02 11 pellets. 490 0. 49 14 1. 6 41 0.50 48 15 0 69 was 4000 s.c.f.h./c.f. The resultant gaseous products at various temperatures were analyzed by an infrared specpassed through a micro-bubbler filled with neohexane and over 20 ml. of Ru on A3 activated A1 0 pellets. The space velocity was 4750 s.c.f.h./c.f. The inlet mixture contained 45.5 mol percent neohexane and 54.5 mol percent H A gas sampling bulb in series with a cold trap was used to collect the samples for analysis. Analysis of the etlluent gases showed that 4.0 mol percent CH was formed at 90 C. and considerable quantities of CH, were formed at higher temperatures. Infrared analysis of the outlet mixtures, with temperatures ranging to 432 C., did not show the formation of reaction products other than CH No attempt was made to determine exact quantities, but considerable quantities of CH, were formed at temperatures below 200 C.
It will be obvious to those skilled in the art that many modifications may be made within the scope of the present invention without departing from the spirit thereof, and this invention includes all such modifications.
What is claimed is:
1. A process for the hydrogenolysis of non-cyclic aliphatic light hydrocarbons which comprises passing a gaseous admixture of hydrogen and a gas containing primarily a hydrocarbon from the group consisting of noncyclic saturated aliphatic light hydrocarbons having from 2-4 carbon atoms per molecule, ethylene, propylene,
l-butene, and mixtures of the saturated and olefin hydrocarbons aforesaid, into contact with a supported catalyst consisting essentially of a catalytic metal selected from the group consisting of ruthenium and a rutheniumpalladiurn combination, supported on activated alumina, at a temperature within the range of between 197 C. and 370 C. and a space velocity from about 1000 to 10,000 standard volumes of gas per volume of catalyst per hour, the catalytic metal being present in amount of about 0.1-5 weight percent based on catalytic metal plus sup port, whereby hydrogenolysis of the hydrocarbon occurs to produce gaseous reaction products comprising methane.
2. A process in accordance with claim 1 wherein the gas admixed with the hydrogen contains primarily ethane.
References Cited by the Examiner UNITED STATES PATENTS 2,854,401 9/58 Weisz 208112 2,909,578 10/59 Anderson et a1 26067 7 2,964,462 12/60 Thomas et a1. 208-112 3,000,809 9/61 Ridgway et a1. 260676 3,046,317 7/62 Myers 260676 3,048,536 8/62 Coonradt et al 208l 12 OTHER REFERENCES Beeck: Faraday Society--Discussions, 1950, No. 8, pages 118-128.
ALPHONSO D. SULLIVAN, Primary Examiner.
DANIEL E. WYMAN, Examiner.

Claims (1)

1. A PROCESS FOR THE HYDROGENEOLYSIS OF NON-CYCLIC ALIPHATIC LIGHT HYDROCARBONS WHICH COMPRISES PASSING A GASEOUS ADMIXTURE OF HYDROGEN AND A GAS CONTAINING PRIMARILY A HYDROCARBON FROM THE GROUP CONSISTING OF NONCYCLIC SATURATED ALIPHATIC LIGHT HYDROCARBONS HAVING FROM 2-4 CARBON ATOMS PER MOLECULE, ETHYLENE, PROPYLENE, 1-BUTENE, AND MIXTURES OF THE SATURATED AND OLEFIN HYDROCARBONS AFORESAID, INTO CONTACT WITH A SUPPORTED CATALYST CONSISTING ESSENTIALLY OF A CATALYTIC METAL SELECTED FROM THE GROUP CONSISTING OF RUTHENIUM AND A RUTHENIUMPALLADIUM COMBINATION, SUPPORTED ON ACTIVATED ALUMINA, AT A TEMPERATURE WITHIN THE RANGE OF BETWEEN 197*C. AND 370*C. AND A SPACE VELOCITY FROM ABOUT 1000 TO 10,000 STANDARD VOLUMES OF GAS PER VOLUME OF CATALYST PER HOUR, THE CATALYTIC METAL BEING PRESENT IN AMOUNT OF ABOUT 0.1-5 WEIGHT PERCENT BASED ON CATALYTIC METAL PLUS SUPPORT, WHEREBY HYDROGENOLYSIS OF THE HYDROCARBON OCCURS TO PRODUCE GASEOUS REACTION PRODUCTS COMPRISING METHANE.
US130478A 1961-08-10 1961-08-10 Process for the hydrogenolysis of light hydrocarbons Expired - Lifetime US3180902A (en)

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US130478A US3180902A (en) 1961-08-10 1961-08-10 Process for the hydrogenolysis of light hydrocarbons
FR906453A FR1330665A (en) 1961-08-10 1962-08-08 Process for the hydrogenolysis of light hydrocarbons
DE19621443768 DE1443768A1 (en) 1961-08-10 1962-08-09 Hydrogenation process
GB30633/62A GB1016033A (en) 1961-08-10 1962-08-09 Improvements in or relating to the hydrogenolysis of light hydrocarbons

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US3481722A (en) * 1964-05-15 1969-12-02 Engelhard Ind Inc Process for producing hydrogen
US3506417A (en) * 1966-05-13 1970-04-14 Phillips Petroleum Co Hydrocarbon reforming
US3904554A (en) * 1972-01-27 1975-09-09 British Gas Corp Catalyst of ruthenium and zinc oxide on alumina carrier for steam reforming hydrocarbons
US4331825A (en) * 1978-11-16 1982-05-25 Imperial Chemical Industries Limited Production of methane by hydrogenolysis of hydrocarbons and ruthenium catalysts therefor
US20080115935A1 (en) * 2006-01-06 2008-05-22 Mango Frank D In situ conversion of heavy hydrocarbons to catalytic gas
US20110077445A1 (en) * 2006-01-06 2011-03-31 Mango Frank D Generating natural gas from heavy hydrocarbons
US8727006B2 (en) 2010-05-04 2014-05-20 Petroleum Habitats, Llc Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations
GB2525286A (en) * 2014-03-06 2015-10-21 Johnson Matthey Plc Apparatus and process for treating natural gas

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US3046317A (en) * 1960-03-21 1962-07-24 Phillips Petroleum Co Hydrocracking liquid alkanes with a catalyst consisting of a platinum metal in admixture with boria and zirconia
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US2909578A (en) * 1957-04-26 1959-10-20 Engelhard Ind Inc Hydrogenation of acetylene
US2964462A (en) * 1958-01-31 1960-12-13 Sinclair Refining Co Cracking process employing a noble metal, aluminum halide and alumina catalyst
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481722A (en) * 1964-05-15 1969-12-02 Engelhard Ind Inc Process for producing hydrogen
US3506417A (en) * 1966-05-13 1970-04-14 Phillips Petroleum Co Hydrocarbon reforming
US3904554A (en) * 1972-01-27 1975-09-09 British Gas Corp Catalyst of ruthenium and zinc oxide on alumina carrier for steam reforming hydrocarbons
US4331825A (en) * 1978-11-16 1982-05-25 Imperial Chemical Industries Limited Production of methane by hydrogenolysis of hydrocarbons and ruthenium catalysts therefor
US20080115935A1 (en) * 2006-01-06 2008-05-22 Mango Frank D In situ conversion of heavy hydrocarbons to catalytic gas
US20100200234A1 (en) * 2006-01-06 2010-08-12 Mango Frank D In Situ Conversion of Heavy Hydrocarbons to Catalytic Gas
US20110077445A1 (en) * 2006-01-06 2011-03-31 Mango Frank D Generating natural gas from heavy hydrocarbons
US8091643B2 (en) 2006-01-06 2012-01-10 Petroleum Habitats, Llc In situ conversion of heavy hydrocarbons to catalytic gas
US8273937B2 (en) 2006-01-06 2012-09-25 Petroleum Habitats, Llc Generating natural gas from heavy hydrocarbons
US8727006B2 (en) 2010-05-04 2014-05-20 Petroleum Habitats, Llc Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations
GB2525286A (en) * 2014-03-06 2015-10-21 Johnson Matthey Plc Apparatus and process for treating natural gas
GB2525286B (en) * 2014-03-06 2016-05-25 Johnson Matthey Plc Apparatus and process for treating natural gas

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FR1330665A (en) 1963-06-21
DE1443768A1 (en) 1968-12-19
GB1016033A (en) 1966-01-05

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