Classifications

• • 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
  • C01B3/38—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 catalysts
  • C01B3/384—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 catalysts the catalyst being continuously externally heated
• • 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
  • C01B3/38—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 catalysts
• • 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
  • C01B3/38—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 catalysts
  • C01B3/40—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 catalysts characterised by the catalyst
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• • 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts

Definitions

• the gaseous mixture from the first stage is passed through at least one pair of stages consisting of, first, an externally fired preheater and, secondly, a reforming stage in which the preheated gases are subjected to the action of a reforming catalyst at a temperature above 550 C. to bring about the conversion of methane contained therein by reaction with steam to form carbon monoxide and hydrogen.
• the present invention relates to processes for the production of combustible gases.
• the gas so produced contains more methane than is required for town gas and a second stage is disclosed in this prior specification wherein the methane-containing gas resulting from the first stage together with the nudecomposed steam are passed through a further bed of nickel catalyst operated at a temperature above 500 C. to bring about the conversion of methane by reaction with steam into carbon monoxide and hydrogen to the extent required to reduce the methane content as desired.
• This reaction is endothermic and the required heat can be supplied, for example, by adding oxygen or air to the gases to liberate the heat by internal combustion or by designing the catalyst vessel so that heat can be supplied to it from outside.
• the carbon monoxide may be converted by reaction with steam to carbon dioxide and hydrogen and the carbon dioxide removed; these subsequent stages may be carried out by means that are well-known.
• This process has the feature that a low proportion of steam to hydrocarbon can be used, for example 1.6 or 2 lb. per lb. of distillate, which is near the theoretical minimum imposed by the need to avoid carbon deposition by the decomposition of the carbon monoxide formed.
• the present invention is concerned with a further method of supplying the heat which is absorbed by the endothermic second-stage reactions, namely, as sensible Patented Apr. 29, 1969 "ice heat in the ingoing gaseous mixture, imparted by passing the mixture leaving the first gasification stage through at least one further stage which comprises an externallyfired preheater.
• the invention provides -a process for the production of gases containing methane by reaction of the vapour of parafiinic hydrocarbons having an average of from 4 to 15 carbon atoms per molecule with steam, which process comprises passing the hydrocarbon vapour with steam at a temperature of at least 350 C. into a bed of a nickel catalyst, whereby the maximum temperature in the catalyst bed is maintained at not more than 600 C. and substantially no carbon deposition takes place on the catalyst, passing the gaseous mixture produced in this gasification stage through at least one pair of stages being, first, an externally fired preheater, and, secondly, a reforming stage in which the preheated gases are subjected to the action of a reforming catalyst at such a temperature above 550 C.
• the preheater providing heat which is absorbed by this endothermic reaction. It is preferred that the maximum temperature in the catalyst bed in the gasification stage shall be maintained at not more than 575 C. or 550 C.
• the thermal capacity of the mixture of hydrogen, carbon oxides, methane and undecomposed steam produced by the gasification stage is generally insufiicient for the method of the present invention within the limits described.
• some increase in the proportion of steam in the mixture supplied to the reforming stage or stages provided either by adding the additional steam to the mixture of gases and nudecomposed steam emerging from the gasification stage, or by increasing the proportion of steam to hydrocarbon in the mixture supplied to the gasification stage, for example, to at least 2.0 lb./lb., supplying the heat for the endothermic reforming reactions by preheat becomes practicable.
• the heat which is supplied by preheating the mixture of gases and undecomposed steam is entirely sufiicient for the reactions in the reforming stage or stages.
• the present process avoids the necessity of consuming energy in compressing the air.
• nitrogen is not a component of the final gas, which accordingly has a higher flame speed; and less carbon dioxide has to be removed in attaining the desired gas composition.
• narrower tubes can be used when it is the gas mixture alone which is heated; the tubes can accordingly be thinner in the wall and so be subject to less thermal stress.
• One preferred embodiment of the invention is thus a process for the production of combustible gas containing methane, for example town gas, and, in particular, town gas of calorific value 500 B.t.u. per cu. ft., in which the vapour of light petroleum distillate or similar mixture of hydrocarbons containing an average of 4 to or carbon atoms per molecule substantially free from sulphur compounds is mixed with steam and the mixture is preheated, for example, to 550 C. or 600 C.
• Carbon monoxide conversion and partial carbon dioxide removal results in the production of gas of calorific value 500 B.t.u. per cu. ft. and Wobbe Number 715.
• the methane-rich gas leaving the gasification stage is preheated in a first preheater, passed over a bed of catalyst in a first reforming stage, preheated again in a second preheater and passed over another bed of catalyst in a second reforming stage.
• These pairs of operations need not be limited in number although normally two will sufiice.
• the plurality of preheating stages may be heated in the same furnace, with preheat at each step to the same temperature, but this is not necessary. The procedure enables more heat to be supplied for reforming within the same limits of temperature than when there is only one preheating operation.
• Outlet Stage 1 Outlet reformer stages (gasifieation) N o. 1 No. 2
• Carbon monoxide conversion and partial carbon dioxide removal results in the production of gas of calorific value 500 B.t.u. per cu. ft. and Wobbe Number 715.
• the hydocarbon feedstock was substantially completely freed from sulphur compounds after evaporation and before admixture with steam for the gasification stage of the process. This is a normal step where nickel catalysts are used. The tests described are much shorter than was possible, for steady conditions were established which would have persisted for as long as the nickel catalyst of the gasification stage remained active.
• the catalyst used in the gasification stage in both examples was the co-precipitated alkali-containing nickelalumina catalyst E described in our application No. 351,- 190.
• the reforming catalyst used in all the reforming stages was a commercially available nickel catalyst made by the firm of Girdler and known as G. 56.
• EXAMPLE 3 The experiment illustrates the embodiment of the invention in which only one reforming stage is used. Operating conditions were maintained steady for 470 hours before the test was terminated and the results were obtained during a sampling period which began about 250 hours after the start.
• Town gas can be produced from the gas leaving the reforming stage by carbon monoxide conversion, partial carbon dioxide removal, and condensation of undecomposed steam.
• EXAMPLE 4 The experiment illustrates the embodiment of the invention in which there are two reforming stages with preheat to the mixture of gases and steam before each stage. Operating conditions were maintained steady for 468 hours before they were deliberately altered and the results were obtained during a sampling period which began 336 hours after the start.
• a process for the production of town gas containing methane by reaction of the vapor of paraffinic hydrocarbons having an average of from 4 to 15 carbon atoms per molecule with steam which process comprises passing a mixture of steam and a hydrocarbon vapor in the ratio of 2.42 to 3.5 :1 lbs. and at a temperature between 525 and 540 C. into a bed of a nickel catalyst, the maximum temperature in the catalyst bed being maintained at not more than 600 C.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• General Health & Medical Sciences (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Catalysts (AREA)

Applications Claiming Priority (1)

Publications (1)

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Cited By (9)

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Citations (3)

• 1964
  • 1964-06-08 GB GB2369864A patent/GB1043377A/en not_active Expired
• 1965
  • 1965-06-02 US US460816A patent/US3441395A/en not_active Expired - Lifetime
  • 1965-06-03 DE DEG43785A patent/DE1256350B/de active Pending
  • 1965-06-04 SE SE7325/65A patent/SE324855B/xx unknown
  • 1965-06-04 CH CH783465A patent/CH436236A/fr unknown
  • 1965-06-04 DK DK284165AA patent/DK119418B/da unknown
  • 1965-06-04 NL NL6507157A patent/NL6507157A/xx unknown
  • 1965-06-04 AT AT511165A patent/AT253661B/de active
  • 1965-06-05 ES ES0313860A patent/ES313860A1/es not_active Expired
  • 1965-06-05 FR FR19780A patent/FR1455141A/fr not_active Expired
  • 1965-06-08 BE BE665064D patent/BE665064A/xx unknown

Patent Citations (3)

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