US3904388A - Process for the production of a high methane content town gas - Google Patents

Process for the production of a high methane content town gas Download PDF

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Publication number
US3904388A
US3904388A US444930A US44493074A US3904388A US 3904388 A US3904388 A US 3904388A US 444930 A US444930 A US 444930A US 44493074 A US44493074 A US 44493074A US 3904388 A US3904388 A US 3904388A
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gas
hydrogen
hot gas
cool
hot
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US444930A
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Haar Leonard W Ter
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Shell USA Inc
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Shell Oil Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/36—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using oxygen or mixtures containing oxygen as gasifying agents
    • 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

  • this invention is directed to an improved process for production of methanerich town gas by carburetion of the gaseous product of partial combustion with a volatile hydrocarbon wax in which an effective and economical means is employed to substantially increase the methane content of the product gas while at the same time suppressing the formation of soot and coke which traditionally occurs in such process employing carburetion.
  • the gas produced by partially combusting a carbonaceous fuel with an oxygen-containing gas normally has a temperature in the range of l300 to lU() although under certain operating conditions temperatures of as high as l 00C or as low as 1 150C are experienced. In any event, however, the temperature of the gas is too high to allow the gas to be directly carbureted with a hydrocarbon fraction and therefore it is first necessary that it be cooled. This cooling is necessary in view of the fact that if the gas is carbureted at a high temperature there is considerable tendency for the hydrocarbon fraction to form soot rather than the desired methane. The soot is then the source of operating troubles in the carburetor and subsequent plant.
  • the mixing of the hot gas product of partial combustion with the cool hydrogen-containing gas is suitably carried out by injecting a cool hydrogen-containing gas into a stream of hot gas.
  • a major advantage of the present invention is that cooling of the hot gas is primarily carried out by mixing with a hydrogen-containing gas whereby decomposition of methane in the manner previously discussed does not occur.
  • a further advantage is that since a high hydrogen partial pressure is proucked in the gas the formation of soot and coke during cracking of the hydrocarbon fraction in the carburetor is suppressed.
  • FIG. 1 is a diagrammatic representation of the process of the invention wherein hydrogen-containing gas is supplied from a source external to the process.
  • FIG. 2 is also a diagrammatic representation of an alternative embodiment of the process according to the invention wherein the hydrogen-containing gas is generated internally by certain modifications on the basic process.
  • the first step of the process according to the invention involves a typical partial combustion procedure wherein a conventional carbonaceous fuel source, such as for example, heavy fuel oil, petroleum distillates or residues or liquid fuel containing process soot is combined with less than the theoretical amount of oxygen present in an oxygen-containing gas at a temperatures in excess of l00()C, e.g., l l50l 700C, to yield a gaseous product containing as principal components, hydrogen and carbon monoxide.
  • Especially preferred fuel sources are the heavy oils and tars obtained from, for example, tar sands or oil shale. Since this step of the process is wholly conventional and quite well known by those skilled in the art it need not be detailed further herein.
  • the composition of the cool hydrogen-containing gas which is mixed with the hot gas emanating from the partial combustion reaction may vary widely. Accordingly, it may comprise substantially pure hydrogen or it may contain oxides of carbon, nitrogen, water vapor and/or hydrocarbons. Water gas or producer gas are suitably used as are also tail gas from hydroprocesses and refinery gas. In order to prevent a significant amount of soot and coke being formed as a result of the mixing of the hot partial combustion product gas with the cool hydrogen-containing gas it is preferable that no hydrocarbons heavier than butane are present in the said gas. The reason for this is that heavier hydrocarbons than butane, such as. for example. naphtha, tend to crack at high temperature to form soot and coke. This tendency is not shown to a significant extent by butane and lighter hydrocarbons.
  • a suitable method of mixing or combining the cool hydrogen-containing gas with the hot partial combustion product gas is to inject a stream of cool hydrogen-containing gas into the hot gas stream emanating from the partial combustion reactor.
  • the volume of cool hydrogen-eontaining gas which is required to be injected into the hot gas depends mainly on the temperature of the cool hydrogen-containing gas and the temperature to which the hot gas is required to be cooled. it also depends on whether or not it is desired from the point of view of hydrogen optimization to inject a low amount of steam into the hot gas since this will have a cooling effect on the hot gas. Since the temperature of the cool hydrogen-containing gas may vary widely, ranging preferably from ambient temperature to 500C, and the temperature to which the hot gas is to be cooled may also vary widely.
  • volume ratio of cool hydrogen-containing gas to hot gas varies over a wide range.
  • a preferred volume ratio of cool hydrogen-containing gas to hot gas used in the process according to the present invention lies between 1 2 and 5 i. In any case. it is preferred that the hot gas be cooled to a temperature in the range of from about 650 to about 950C.
  • the injection of the cool hydrogen-containing gas may take place in the partial combustion reactor. In this case it is preferably injected at a point near the hot gas exit where the partial combustion of the reactants is substantially completed. Most preferably, however. it is injected into the hot gas as it passes from the reac* tor to the carburetor. ln this way. better mixing of the hot gas and cool hydrogen-containing gas is achieved and also the injection of the cool hydrogen-containing gas does not interfere with the partial combustion reaction. Injection of part of the cool hydrogen-containing gas into the partial combustion reactor and the remaining part into the gas passing from the reactor to the car buretor may also be carried out if desired.
  • the inven tion part of the hot gas leaving the partial combustion reactor is cooled, the cooled gas is subjected to a catalytic CO-shift and the cool hydrogen-containing gas thus produced is injected into the remaining part of the hot gas.
  • hydrogen'containing gas from an external source is not required for cooling the hot gas.
  • the cooling of the part of the gas to be subjected to the catalytic CO- shift is suitably carried out in a waste heat boiler in which steam is raised.
  • the temperature to which the hot gas is cooled preferably lies in the range of 175C to 600C.
  • the hydrogen content of the gas is increased by the reaction of steam and carbon monoxide to give hydrogen and carbon dioxide.
  • the cool hydrogen-containing gas thus produced is then injected into the hot gas.
  • the carbon dioxide is removed from the gas leaving the CO-shift before the latter is injected into the hot gas. This is suitably carried out by a hot carbonate wash.
  • the advantages of removing the carbon dioxide are that the gas which is injected into the hot gas has a higher hydrogen content and that there is no carbon dioxide present in the gas mixture which could react with hydrogen in the hot gas to form steam and carbon monoxide and thus reverse the CO-shift which has already been carried out.
  • the temperature of the cool hydrogen-containing gas which is injected into the hot gas lies in a broad range. As in the case of the general embodiment of the invention which has already been discussed this temperature preferably lies between ambient temperature and 500C. If the cool hydrogen-containing gas is injected into the hot gas directly from the CO-shift then its temperature normally lies between 250 and 450C. If a hot carbonate wash is used then the temperature of the gas injected normally lies between 50 and l50C. Of course, if the temperature of the gas to be injected is desired to be increased or decreased then this may be easily carried out by heating or cooling the gas leaving the CO-shift or the hot carbonate wash.
  • the hydrogen partial pressure which is desired to be created in the gas mixture passing to the carburetor is of importance. If a high hydrogen partial pressure is required then it may be that not sufficient cool hydrogen-containing gas can be injected into the hot gas to achieve this high hydrogen partial pressure while still remaining within the desired temperature range for carbureting the gas mixture. This may, for instance. occur if the cool hydrogen-containing gas has a temperature of 50C in which case it may not be possible to inject sufficient cool hydrogen-containing gas to achieve the desired hydrogen partial pressure in the gas mixture produced without cooling the gas mixture below the desired carbureting temperature. In such a case it is desirable to heat the hydrogen-containing gas before it is injected into the hot gas. This suitably is carried out by one or more heat exchangers.
  • the volume ratio of cool hydrogencontaining gas to hot gas varies over a broad range. Preferably it lies between 1 l0 and 5 i. From an economic and practical viewpoint it more preferably lies between 1 l0 and 3: l.
  • the carbureted gas produced according to this specific embodiment of the invention is to be catalytieally methanated then it is desirable to operate the process such that the ratio of hydrogen to carbon monoxide in the carbureted gas is 3 l, i.e., the stoichiometric ratio for the production of methane from hydrogen and carbon monoxide according to Sabatiers reaction.
  • the cooled gas is preferably carbureted within a temperature range of 650 to 950C.
  • soot and coke formation in the carburetor does not occur to a significant extent. and the heating value is promoted.
  • the hydrogen partial pressure in the cooled gas should be above 4 atmospheres and preferably substantially above that figure.
  • An attractive feature of the process according to the present invention is that a hydrogen partial pressure of above 4 atmospheres is always achieved in the cooled gas.
  • the partial pressure of hydrogen in the cooled gas lies between 7 and atmospheres although higher hydrogen partial pressures can be achieved. Accordingly, soot and coke formation does not occur to a significant extent in the car buretor.
  • Another advantage of the high hydrogen par tial pressures achieved according to the present invention is that the extent to which the gas can be carbureted without soot and coke forming is increased. Ac cordingly, the carbureted gas produced has a high calorific value.
  • Any suitable hydrocarbon fraction may be injected into the cooled gas in the carburetor.
  • a very suitable hydrocarbon fraction is a distillate fraction boiling below 350C. Gasoline fractions and kerosine fractions are well suited as hydrocarbon fractions.
  • the carbureting of the cooled gas in the carburetor is slightly exothermic it may be desirable in certain cases to stabilize the temperature of the gas by injecting small amounts of cool hydrogen-containing gas into the carburetor. This may be done, if desired. at a number of points within the carburetor. It may also be desirable to inject the hydrocarbon fraction into the carburetor at a number of points. In this case cool hydrogen-containing gas may suitable be injected into the carburetor in between the hydrocarbon injection points.
  • a preferred form of carburetor for this operation is a carburetor in the form of a U-pipe.
  • the methane-rich gas produced according to the present invention preferably contains more than 25% by volume of methane on a carbon dioxide free basis.
  • methane-rich gas having a substantially higher methane content than this is capable of being produced according to the process of the present invention.
  • methane contents of 35% and up to 60% are readily achieved.
  • the methane-rich gas also contains a certain amount of aromatics. These are ad vantageously removed before the gas is further treated and the removed aromatics may suitably be recycled to the reactor to be combusted.
  • FIG. I is a diagrammatic representation of a process for preparing a methane-rich gas in which the combustion gas leaving the reactor is cooled by the injection of a hydrogcn containing gas from an external source.
  • FIG. 2 shows another embodiment of the present invention in which part of the hot gas from the reactor is cooled. subjected to a CO-shift and subsequent CO removal and then injected into the remaining part of the hot gas.
  • a fuel is introduced via a line I and oxygen is introduced via a line 2 into a partial combustion reactor 3.
  • Hot gas leaves the reactor via a line 4 and is cooled by the injection of a cool hydrogen containing gas into line 4 via a line 5.
  • the cooled gas then passes to a carburetor 6 into which a hydrocarbon fraction is injected via a line 7.
  • Methane-rich gas leaves the carburetor via a line 8.
  • the integers l to 8 represent the same components of the process as in FIG. 1. Cooling of the hot gas is however carried out by bleeding off a part of the hot gas via a line 9 and cooling it in a waste heat boiler 10. The cooled gas then passes via a line 1 l to a catalytic CO-shifl reactor 12 in which a hydrogen and carbon dioxide-containing gas is produced. This gas leaves the catalytic CO-shift reactor via a line 13 and enters a carbon dioxide removal unit 14 in which the carbon dioxide is removed by a hot carbonate wash. The cooled hydrogen-containing gas thus produced is injected via the line 5 into the remaining part of the hot gas in the line 4.
  • the cooled gas which had a hydrogen partial pressure of 23 atmospheres was then passed to a carburetor into which a hydrocarbon frac tion boiling in the range of l40 to l60C was injected at a rate of 35 kg per hour. After removal of water. H S. soot, aromatics and part of the CO this operation resulted in 160 m"(NTP) carbureted gas having a caloric value of 5080 kcal/m (NTP) and a composition of:
  • a process for the production of a methane-rich town gas which comprises:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Industrial Gases (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US444930A 1973-03-19 1974-02-22 Process for the production of a high methane content town gas Expired - Lifetime US3904388A (en)

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GB1311473A GB1458666A (en) 1973-03-19 1973-03-19 Process for the preparation of a methane-rich gas

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JP (1) JPS5727920B2 (ja)
CA (1) CA1021358A (ja)
GB (1) GB1458666A (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006901A1 (en) * 1994-08-26 1996-03-07 Stork Comprimo B.V. Process for cooling a hot gas stream
US8648121B2 (en) 2011-02-23 2014-02-11 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2147913A (en) * 1983-10-14 1985-05-22 British Gas Corp Thermal hydrogenation of hydrocarbon liquids
GB2165551B (en) * 1984-10-10 1988-08-17 Shell Int Research Process for the production of synthesis gas
US7642293B2 (en) * 2004-07-29 2010-01-05 Gas Technologies Llc Method and apparatus for producing methanol with hydrocarbon recycling

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716597A (en) * 1951-06-12 1955-08-30 Koppers Co Inc Method and apparatus for the production of combustible gases from liquid fuels
US3784364A (en) * 1971-11-04 1974-01-08 Texaco Inc Production of fuel gas

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2716597A (en) * 1951-06-12 1955-08-30 Koppers Co Inc Method and apparatus for the production of combustible gases from liquid fuels
US3784364A (en) * 1971-11-04 1974-01-08 Texaco Inc Production of fuel gas

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996006901A1 (en) * 1994-08-26 1996-03-07 Stork Comprimo B.V. Process for cooling a hot gas stream
NL9401387A (nl) * 1994-08-26 1996-04-01 Comprimo Bv Werkwijze voor het koelen van een hete gasstroom, voor het verhogen van het rendement van de elektriciteitsproduktie, alsmede voor het reguleren van het koelproces van een synthesegasstroom, zodanig dat pieken in de elektriciteitsvraag kunnen worden opgevangen.
US8648121B2 (en) 2011-02-23 2014-02-11 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with nickel recovery

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GB1458666A (en) 1976-12-15
JPS49128002A (ja) 1974-12-07
CA1021358A (en) 1977-11-22
JPS5727920B2 (ja) 1982-06-14

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