US3201215A - Production of combustible gas - Google Patents

Production of combustible gas Download PDF

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US3201215A
US3201215A US286296A US28629663A US3201215A US 3201215 A US3201215 A US 3201215A US 286296 A US286296 A US 286296A US 28629663 A US28629663 A US 28629663A US 3201215 A US3201215 A US 3201215A
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naphtha
stream
carbon
steam
gas
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John S Negra
Arnold R Bernas
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Chemical Construction Corp
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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
    • C10K3/02—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 catalytic treatment
    • C10K3/04—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 catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
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    • 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
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    • 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
    • C01B3/48—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 followed by reaction of water vapour with carbon monoxide
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0211—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step
    • C01B2203/0216—Processes for making hydrogen or synthesis gas containing a reforming step containing a non-catalytic reforming step containing a non-catalytic steam reforming step
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0255—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a non-catalytic partial oxidation step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0872—Methods of cooling
    • C01B2203/0877—Methods of cooling by direct injection of fluid
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    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C01B2203/1094—Promotors or activators
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
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    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • 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
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1288—Evaporation of one or more of the different feed components
    • 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
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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
    • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Definitions

  • NEGRA ETAL 3,201,215 I PRODUCTION OF COMBUSTIBLE GAS Filed June 7, 1963 JOHN s. NEGRA ARNOLD R. BERNAS INVENTORS.
  • Naphtha is gasified according to the process of the present invention without the concomitant formation of free carbon, by the suitable selection of several inter-related processvariables.
  • the reaction of naphtha with steam andair is controlled so asto produce a crude gas steam containing a substantial proportion of lower hydrocarbons as Well as carbon monoxide and hydrogen.
  • Unsaturated low hydrocarbons are hydrogenated in a preferred embodiment, so as to produce a stable town gas.
  • Naphtha is a relatively volatile petroleum refining product or intermediate, which is generally defined in terms of boiling range.
  • naphtha is defined as follows: Naphtha content (of crude oil) is the total distillate recovered in the US. Bureau of Mines routine analysis at a vapor ten perature of 392 F. A more detailed definition of naphtha appears in Petroleum Refining with Chemicals by Kalichevsky and Kobe (1956). A discussion of naphtha on p. 2123 of this text indicates that different naphthas may have boiling ranges from a low point of 122 F., to a maximum of 400 F.
  • naphtha is defined as a general term which is applied to fractions boiling in the gasoline of low kerosene range.
  • naphtha is a low-boiling and readily volatilized liquid hydrocarbon cut, derived from crude oil distillation in petroleum refining. This material consists mostly of straight chain parafiinics in C to C-9 range, however, up toabout 30% naphthenics together with up to 10% aromatics and unsaturates may also be present.
  • naphtha also generally contains a significant proportion of sulfur in the form of COS and mercaptans.
  • Naphtha may be utilized in a variety of Ways. Thus, crud-e naphtha may be further refined and upgraded to yield a variety of finished petroleum solvents. In many refineries, naphtha is reformed in the petroleum sense of the term. In this case, the crude naphtha is cracked,
  • naphtha is gasified With steam and air at elevated temperature, to produce a crude combustible gas. After further treatment such as hydrogenation of unsaturates, a finished town gas is produced.
  • a limited amount of process air is employed in the gasification stage of the present invention, to assist in the gasification of the naphtha and to provide a nitrogen gas component for ballast in the finished town gas.
  • the process of the present invention depends on a unique balance of reaction conditions to achieve the gasification of naphtha, since this is accomplished Without accumulated deposition of free carbon. In addition, no significant amount of unreacted hydrocarbon is present in the finalsynthesis gas.
  • the basic process is carried out in a gasificaion-conditioning stage followed by a quench step.
  • the gasification stage must be of short duration in order to prevent the reactants from reaching equilibrium with resultant deposition of free carbon in the catalyst bed. It has also been found that the reac tants must be preheated in order to provide a minimum temperature level in the gasification stage.
  • process streams of naphtha, steam and air are preheated and mixed. A partial reaction ensues, and the mixed process stream, now containing a varmonoxide and carbon dioxide.
  • Naphtha has also been utilized in the prior art as a hydrocarbon raw material for the manufacture of a combustible gas, such as town gas.
  • Town gas is generally defined as a stable gas stream free of gums or tars and containing saturated lower hydrocarbons,
  • the process of the present invention possesses several significant advantages.
  • a primary advantage is that naphtha is completely converted to a stable crude combustible gas without the concomitant accumulation of free carbon or tars. No recycle or said stream disposal is required.
  • the process is continuous rather than cyclic or intermittent.
  • the process is non-catalytic in the gasification stage, however as will appear infra a nickel catalyst may be provided if desired to increase the B.t.u. value of the final town gas.
  • Another object is to completely gasify naphtha in a continuous process, without accumulated deposition of tars or free carbon.
  • a further object is to react naphtha with steam and air Without reaching final reaction equilibrium, under conditions such that a stable intermediate stream containing lower hydrocarbons, carbon monoxide and hydrogen is produced.
  • An additional object is to produce a stable combustible town gas by the non-catalytic gasification of naphtha.
  • Still another object is to simultaneously crack, partially oxidize, and non-catalytically steam reform naphtha by reaction with steam and air under process conditions such that free carbon is not formed.
  • stream 1 is a liquid naphtha, derived from petroleum refining or other ty es of crude oil processing.
  • stream 1 consists principally of parafinic hydrocarbons in the C5 to C-9 range, together with naphthenics as well as minor amounts of aromatics and sulfur compounds.
  • the liquid stream it is vaporized and preheated in heater 2, to form naphtha vapor stream 3.
  • Vapor stream 3 may be produced at any suitable temperature, ranging from the boiling point of naphtha up to about 1000 F. Above this temperature level the naphtha vapor may become unstable, and certain portions or components will readily crack to smaller molecules with concomitant carbon deposition.
  • Stream 3 thus is preferably produced at a temperature ranging from 400 F. to 800 F.
  • Stream 4 consists of highly superheated steam, preheated usually to a temperature above l500 F. and preferably to the range of 1500 F. to 1700 F. Although lower ratios are feasible, it has been found that a range of molar steam/ carbon ratios between 3 and 6 is desirable in proportioning the relative flow rates of streams 4 and 3, in order to assure the avoidance of formation or accumulated deposition of carbon under normal operating conditions.
  • Stream 5 consists of air, preheated usually to a temperature above 800 F. and preferably to the range of 800 F. to 1200 F.
  • the proportion of air employed in the process is quite small, thus only enough air is used to provide the desired thermal effects of temperature elevation due to naphtha combustion.
  • the streams and 5 are preferably combined, to form a mixed steam-air stream 6 at a temperature of at least 1100 F.
  • Stream 6 is now combined with naphtha vapor stream 3, and the mixed stream 7 is immediately passed into residence or gasification chamber 8. It will be appreciated that streams 3, 4 and 5 may be separately passed into chamber however premixing of the air and steam to form stream 6 is a preferable procedure since this results in better and more rapid mixing of the several streams.
  • stream 3 is more rapidly dispersed and diluted due to the mixing with stream 6, prior to entry of the naphtha vapor into residence chamber 8. Consequently, the possibility of transient carbon formation or deposition due to cracking of the naphtha is reduced by the pre-mixing step.
  • the unstable lower hydrocarbons are selectively hydrogenated to a certain extent due to the in situ formation of hydrogen, which may possibly be formed in the nascent state.
  • the resultant gaseous stream 9 contains significant proportions of steam, nitrogen, hydrogen, carbon dioxide, carbon monoxide unsaturated hydrocarbons (mostly ethylene), methane and possibly ethane. It should be understood, however, that some of these components are present on a transient or instantaneous basis. If stream is allowed to reach stable equilibrium under these process conditions, significant formation and accumulated deposition of free carbon will take place.
  • the temperature in unit 8 may be in the range of 1450 F. to 1500 F. However, with such low reaction temperatures, the formation of free carbon may readily occur, especially after all the residual free oxygen is consumed, unless the residence time is kept I) oxide and hydrogen.
  • chamber 8 may actually, in terms of apparatus design, consist merely of an insulated pipe section extending between the point of mixing of the reactant streams and the entry of the gasified process stream into the following quench.
  • the competing reactions of naphtha combustion, cracking and non-catalytic thermal steam reform are carried out in the first stage of the process of the present invention. It has been determined that, by maintenance of reaction conditions within certain critical ranges, these competing reactionsmay be carried out without carbon accumulation.
  • the resulting unstable process stream when passed to the following quench step before further reaction ensues, is successfully stabilized to yield a crude combustible gas mixture without carbon accumulation.
  • the present invention essentially accomplishes the gasification of naphtha by a process using preheated air and steam. It has been determined that the resulting mixed gas stream may be successfully maintained as a stable crude combustible gas, if the mixed gas stream is quenched before final process equilibrium is reached.
  • the critical features of the present invention essentially involve the maintenance of several inter-related process variables within operating limits in which the new result of the present invention is achieved, namely the continuous gasification of naphtha.
  • Quench liquid stream 11 is any suitable coolant liquid and may consist of a stable heavy hydrocarbon oil, however stream 11 will preferably consist of water. Warmed quench liquid is removed via 12. The cooled process gas stream is removed via 13 at a temperature below 800 F., and consists of a crude combustible gas typically containing hydrogen, carbon monoxide, ethylene, methane, carbon dioxide and nitrogen.
  • Stream i3 is directly usable as a gaseous fuel in certain applications, however stream 13 is preferably further processed to saturate any unsaturated hydrocarbons such as, ethylene, which act as illuminants and thus are undesirable in town gas.
  • Carbon dioxide is also usually removed from the gas stream, in order to increase the Btu. content by decreasing the ballast or inerts content.
  • Stream 13 is first passed into water gas shift converter 14-, together with further steam which is supplied via 15 when required, to react with the carbon monoxide; content of stream 13. In some cases stream'i5 may be omitted, if sufficient steam is already present in stream 13.
  • Converter, 14- is provided with at least one bed to" of catalyst, usually consisting of active iron oxide plus alkali oxide promoter, deposited on a suitable carrier. Unit 14 may consist of the apparatus described in US. Patent No. 3,010,807, or other suitable apparatus.
  • Stream 17 is now passed through catalytic hydrogenation unit 18, which is provided with gauze layers 19 consisting of a platinum group metal such as platinum or palladium.
  • unit 18 may be provided with a catalyst bed consisting of platinum deposited on a suitable carrier.
  • catalytic hydrogenation ofunsaturates in the gas stream is carried out in unit 18.
  • ethylene addition of hydrogen to the unsaturated double bond produces ethane.
  • the resulting process stream 20 withdrawn from unit 18 has a negligible content of unsaturates.
  • Stream .20 is now passed through scrubber 21, Where the gas stream is contacted with a liquid scrubbing agent such as hot aqueous potassium carbonate solution or aqueous monoethanolamine solution, for removal of carbon dioxide.
  • a liquid scrubbing agent such as hot aqueous potassium carbonate solution or aqueous monoethanolamine solution, for removal of carbon dioxide.
  • the scrubbing unit 21 is provided with a packed section 22 for gas-liquid contact, alternatively bubble cap trays or grid trays may be provided for this purpose.
  • the scrubbing liquid solution is admitted via 23, and liquid solution containing absorbed carbon dioxide is removed via 24 for external regeneration.
  • the final gas stream of reduced carbon dioxide content is removed from unit 21 via 25, and may be subsequently cooled or otherwise treated by means not shown for the removal of Water vapor.
  • a finished town gas is produced, containing principally ethane, methane, hydrogen and nitrogen.
  • .Nitrogen is a desirable component in finished town gas, since it serves as ballast in diluting the gas stream to provide the proper B.t.u. value. Due to thehydrogenation in unit 18, the finished town gas is low in unsaturates, which are undesirable since these compounds act as illuminants during combustion and also have gum-forming tendencies.
  • a suitable catalyst such as metallic nickel rings may be provided in unit 8, in order to promote the formation of hydrogen by catalytic steam reform, thus yielding a final gas product of higher B.t.u. value.
  • operating pressure does not appear to be a significant variable in the process of the present invention.
  • pressure is notcritical, an operating pressure in the range of 1 to 22 atmospheres is preferable since reform plant equipment size is reduced, and also become subsequent compression costs are reduced.
  • gasification at elevated pressure yields a high pressure process gas which thus may range of 1450 F. to 1500 F.
  • the initial streams 3, 4 and 5 must be preheated to higher levels so as to provide a temperature range of 1650 F. to 1690 F. in chamber 8, in order to prevent accumulated deposition of free carbon in actual operation of the process.
  • a minimum steam/carbon ratio of 1.5 is generally required,in order to satisfy material balance considerations by providing snflicient steam for complete reaction with the naphtha.
  • a steam/carbon ratio in the range of 3 to 6 has been found to be optimum in providing complete reaction, satisfactory reaction rate, and minimum tendency for carbon formation due to process upsets. Higher proportions of process air will generally berequired if minimum steam/carbon ratios are adopted, in order to prevent carbon deposition.
  • the molar air/ carbon ratio Will range between 0.1 and 1.0.
  • Runs 1 and 2 were non-catalytic, while in run 3 a nickel type catalyst was provided in the gasification step. It is evident that a highercontent of free liydrogen was present in the exit gas from run 3, thus the B.t.u. value was somewhat greater due to the catalytic effect.
  • T bus the required minimum preheat temperature of the reactant streams piror to chamber 8 will depend principally on the residence time in 8 prior to entry of the mixed stream via 9 into quench unit 10. With lower residence times in the range of 0.05 to 0.10 second, it has been found that the process may be successfully carried out with a residence chamber temperature in the The final town gas product had a net heating value of 437 Btu/ft. and a specific gravity of 0.502.
  • a process for the gasification of naphtha to produce a combustible gas which comprises vaporizing and preheating naphtha to a temperature in the range of 122 F. to 1000" F., 'superheating steam, and preheating air;
  • a process forthe gasification of naphtha to produce a combustible gas which comprises vaporizing and preheating naphtha to a temperature of 400 F. to 800 F., preheating air to a temperature above 800 F. and supereating steam to a temperature above 1500 F.; combining said streams of naphtha, steam and air to form a mixed gaseous stream at a temperature of 1400 F. to 1700 F. and a total pressure in the range or" 1 to 22 atmospheres, said mixed gaseous stream having a steam to carbon molar ratio in the range of 1.5 to 6.0 and an air .to carbon molar ratio in the range of 0.1 to 1.0,
  • a process for the gasification of naphtha to produce a combustible town gas which comprises vaporizing and preheating naphtha to a temperature of. 400 F. to 800 F., preheating air to a temperature of 800 F. to 1200 F., and superheating steam to a temperature of 1500 F. to 1700 F; combining said streams of naphtha, steam and air to form a mixed gaseous stream at a temperature of 1400 F. to 1700 F.
  • said mixed gaseous stream having a steam to carbon molar ratio in the range of 3.0 to 6.0 and an air to carbon molar ratio in the range of 0.1 to 1.0, reacting said mixture in the presence of a nickel catalyst for a time interval between 0.05 to 0.33 second, whereby said naphtha is simultaneously oxidized, cracked and partially reformed without'accumulated deposition of free carbon, quenching the process gas stream to a temperature below 800 F.
  • a crude combustible gas mixture comprising carbon dioxide, carbon monoxide, ethylene, methane, hydrogen and nitrogen, without accumulated deposition of .tree carbon, catalytically reacting the carbon monoxide content of the gas mixture with water vapor to form further hydrogen and carbon dioxide by contacting the gas mixture with a Water gas shift catalyst comprising promoted iron oxide, catalytically hydrogenating the ethylene content of the gas mixture to ethane, and scrubbing the gas mixture with a liquid absorbent to remove carbon dioxide, whereby a stable combustible town gas is produced comprising ethane, methane, hydrogen and nitrogen.

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  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Description

Aug. 17, 1965 J. 5. NEGRA ETAL 3,201,215 I PRODUCTION OF COMBUSTIBLE GAS Filed June 7, 1963 JOHN s. NEGRA ARNOLD R. BERNAS INVENTORS.
mpg-$44!? AGENT United States Patent 3,201,215 PRODUCTHQN 0F C(EMEUSTEEILE GAS John S. Negrti, South Ptainfield, and Arnold R. Berries, Nixon, N..I., assignor to Chemical Construction Corporation, New York, N.Y., a corporation of Delaware Filed June '7, 1963, Ser. No. 286,296 7 Claims. (Cl. 43-215) This invention relates to the gasification of naphtha with steam andair, to produce astable combustible gas steam which may be further processed to a finished town gas with low content of illuminates such as ethylene. Naphtha is gasified according to the process of the present invention without the concomitant formation of free carbon, by the suitable selection of several inter-related processvariables. The reaction of naphtha with steam andair is controlled so asto produce a crude gas steam containing a substantial proportion of lower hydrocarbons as Well as carbon monoxide and hydrogen. Unsaturated low hydrocarbons are hydrogenated in a preferred embodiment, so as to produce a stable town gas.
Naphtha is a relatively volatile petroleum refining product or intermediate, which is generally defined in terms of boiling range. Thus, according to a crude oil survey in Industrial and Engineering Chemistry, 44, #11 (Nov. 1952), p. 2578. naphtha is defined as follows: Naphtha content (of crude oil) is the total distillate recovered in the US. Bureau of Mines routine analysis at a vapor ten perature of 392 F. A more detailed definition of naphtha appears in Petroleum Refining with Chemicals by Kalichevsky and Kobe (1956). A discussion of naphtha on p. 2123 of this text indicates that different naphthas may have boiling ranges from a low point of 122 F., to a maximum of 400 F. Thus naphtha" is defined as a general term which is applied to fractions boiling in the gasoline of low kerosene range. In general then, naphtha is a low-boiling and readily volatilized liquid hydrocarbon cut, derived from crude oil distillation in petroleum refining. This material consists mostly of straight chain parafiinics in C to C-9 range, however, up toabout 30% naphthenics together with up to 10% aromatics and unsaturates may also be present. In addition, naphtha also generally contains a significant proportion of sulfur in the form of COS and mercaptans.
Naphtha may be utilized in a variety of Ways. Thus, crud-e naphtha may be further refined and upgraded to yield a variety of finished petroleum solvents. In many refineries, naphtha is reformed in the petroleum sense of the term. In this case, the crude naphtha is cracked,
and hydrocarbon molecules are re-assembled in the presulfur naphtha is described in US. Patent No. 2,711,419. ireheated naphtha vapor, air and steam are reacted in the presence of a nickel-type catalyst. Accumulated carbon and sulfur deposited on the catalyst are removed by a pcriodic burning-oft period. lumerous other prior art procedures for the catalytic or non-catalytic gasification 0f naphtha have been proposed in the prior art. Generally speaking, the formation of free carbon, tars and gums remains as a problem, principally because of the difiiculty of cracking the naphtha to form lower hydrocarbons without the concomitant formation of these undesirable side-products.
in the present invention, naphtha is gasified With steam and air at elevated temperature, to produce a crude combustible gas. After further treatment such as hydrogenation of unsaturates, a finished town gas is produced. A limited amount of process air is employed in the gasification stage of the present invention, to assist in the gasification of the naphtha and to provide a nitrogen gas component for ballast in the finished town gas. The process of the present invention depends on a unique balance of reaction conditions to achieve the gasification of naphtha, since this is accomplished Without accumulated deposition of free carbon. In addition, no significant amount of unreacted hydrocarbon is present in the finalsynthesis gas. The basic process is carried out in a gasificaion-conditioning stage followed by a quench step. It has been found that the gasification stage must be of short duration in order to prevent the reactants from reaching equilibrium with resultant deposition of free carbon in the catalyst bed. It has also been found that the reac tants must be preheated in order to provide a minimum temperature level in the gasification stage. Thus, in the present invention, process streams of naphtha, steam and air are preheated and mixed. A partial reaction ensues, and the mixed process stream, now containing a varmonoxide and carbon dioxide.
sence of platinum or other suitable catalyst, so as to yield Y a substantial proportion of branched chain or aromatics molecules. This material is then blended with other refinery cuts for gasoline usage.
Naphtha has also been utilized in the prior art as a hydrocarbon raw material for the manufacture of a combustible gas, such as town gas. An improved process for the gasification of naphtha to produce a combustible town gas in provided in the present invention. Town gas is generally defined as a stable gas stream free of gums or tars and containing saturated lower hydrocarbons,
;hydrogen, carbon monoxide and inert ballast gas component, with a heating valve in the range of 400 to 1000 "B.t.u./ft. and a specific gravity (air=1) of 05:0.05. A typical prior art procedure for producing a-combustible gas such as town gas from naphtha is described in British Patent No. 923,385. In this process, naphtha or light distillate" is reformed with steam, in the presence of a specific catalyst composition. It is claimed that the formation of free carbon, tars and gums is prevented. A cyclic process for the production of fuel gas from highiety of intermediate components but not in final reaction equilibrium, is passed to a quench step. The resulting crude combustible gas stream consists of a gas mixture containing methane, ethylene, hydrogen, nitrogen, carbon The stream is essentially free of unreacted hydrocarbons or solid particulate carbon.
The process of the present invention possesses several significant advantages. A primary advantage is that naphtha is completely converted to a stable crude combustible gas without the concomitant accumulation of free carbon or tars. No recycle or said stream disposal is required. The process is continuous rather than cyclic or intermittent. The process is non-catalytic in the gasification stage, however as will appear infra a nickel catalyst may be provided if desired to increase the B.t.u. value of the final town gas.
it is an object of the present invention to produce a combustible gas by the gasification of naphtha.
Another object is to completely gasify naphtha in a continuous process, without accumulated deposition of tars or free carbon.
A further object is to react naphtha with steam and air Without reaching final reaction equilibrium, under conditions such that a stable intermediate stream containing lower hydrocarbons, carbon monoxide and hydrogen is produced.
An additional object is to produce a stable combustible town gas by the non-catalytic gasification of naphtha.
Still another object is to simultaneously crack, partially oxidize, and non-catalytically steam reform naphtha by reaction with steam and air under process conditions such that free carbon is not formed. a i
These and other objects and advantages of the present invention will becomejevident from the description which follows. Referring to the figure, stream 1 is a liquid naphtha, derived from petroleum refining or other ty es of crude oil processing. Thus, as described supra, stream 1 consists principally of parafinic hydrocarbons in the C5 to C-9 range, together with naphthenics as well as minor amounts of aromatics and sulfur compounds. The liquid stream it is vaporized and preheated in heater 2, to form naphtha vapor stream 3. Vapor stream 3 may be produced at any suitable temperature, ranging from the boiling point of naphtha up to about 1000 F. Above this temperature level the naphtha vapor may become unstable, and certain portions or components will readily crack to smaller molecules with concomitant carbon deposition. Stream 3 thus is preferably produced at a temperature ranging from 400 F. to 800 F.
Stream 4 consists of highly superheated steam, preheated usually to a temperature above l500 F. and preferably to the range of 1500 F. to 1700 F. Although lower ratios are feasible, it has been found that a range of molar steam/ carbon ratios between 3 and 6 is desirable in proportioning the relative flow rates of streams 4 and 3, in order to assure the avoidance of formation or accumulated deposition of carbon under normal operating conditions.
Stream 5 consists of air, preheated usually to a temperature above 800 F. and preferably to the range of 800 F. to 1200 F. The proportion of air employed in the process is quite small, thus only enough air is used to provide the desired thermal effects of temperature elevation due to naphtha combustion. The streams and 5 are preferably combined, to form a mixed steam-air stream 6 at a temperature of at least 1100 F. Stream 6 is now combined with naphtha vapor stream 3, and the mixed stream 7 is immediately passed into residence or gasification chamber 8. It will be appreciated that streams 3, 4 and 5 may be separately passed into chamber however premixing of the air and steam to form stream 6 is a preferable procedure since this results in better and more rapid mixing of the several streams. Thus, stream 3 is more rapidly dispersed and diluted due to the mixing with stream 6, prior to entry of the naphtha vapor into residence chamber 8. Consequently, the possibility of transient carbon formation or deposition due to cracking of the naphtha is reduced by the pre-mixing step.
In chamber 8, simultaneous reactions take place between and among the several reactants and intermediate components. The temperature of the process stream immediately rises, due to exothermic combustion of a portion of the naphtha with the oxygen content of the air. In addition, a portion of the naphtha is non-catalytically steam reformed due to the high temperature and high steam concentration in chamber 3. This endothermic reaction serves to produce free hydrogen, and also moderates the temperature rise due to combustion. A further portion of the naphtha is thermally cracked to lower hydrocarbons, due also to the high temperature level. However, simultaneous deposition and accumulation of free carbon does not instantaneously occur. Instead, the unstable lower hydrocarbons are selectively hydrogenated to a certain extent due to the in situ formation of hydrogen, which may possibly be formed in the nascent state. Thus, the resultant gaseous stream 9 contains significant proportions of steam, nitrogen, hydrogen, carbon dioxide, carbon monoxide unsaturated hydrocarbons (mostly ethylene), methane and possibly ethane. It should be understood, however, that some of these components are present on a transient or instantaneous basis. If stream is allowed to reach stable equilibrium under these process conditions, significant formation and accumulated deposition of free carbon will take place.
Under some conditions, the temperature in unit 8 may be in the range of 1450 F. to 1500 F. However, with such low reaction temperatures, the formation of free carbon may readily occur, especially after all the residual free oxygen is consumed, unless the residence time is kept I) oxide and hydrogen.
in the range of 0.05 to 0.33 second. In general, the residence time in chamber 8 must be kept below 1.0 sec- 0nd, and preferably in the range of 0.05 to 0.33 second, in order to achieve the desired reactions without carbon formation. In addition, the instantaneous mix temperature of stream '7 must be kept above 1000 F. since it has been found in practice that the various competing reactions will tend to form free carbon if the initial mix temperature is below 1000" F. This initial or instantaneous mixture temperature should preferably be in the range of 1400" F. to 1700 F. in order to preclude carbon formation due to process upsets. It will be evident that chamber 8 may actually, in terms of apparatus design, consist merely of an insulated pipe section extending between the point of mixing of the reactant streams and the entry of the gasified process stream into the following quench.
In summary, the competing reactions of naphtha combustion, cracking and non-catalytic thermal steam reform are carried out in the first stage of the process of the present invention. It has been determined that, by maintenance of reaction conditions within certain critical ranges, these competing reactionsmay be carried out without carbon accumulation. In addition, the resulting unstable process stream, when passed to the following quench step before further reaction ensues, is successfully stabilized to yield a crude combustible gas mixture without carbon accumulation. The present invention essentially accomplishes the gasification of naphtha by a process using preheated air and steam. It has been determined that the resulting mixed gas stream may be successfully maintained as a stable crude combustible gas, if the mixed gas stream is quenched before final process equilibrium is reached. Thus, the critical features of the present invention essentially involve the maintenance of several inter-related process variables within operating limits in which the new result of the present invention is achieved, namely the continuous gasification of naphtha.
Stream 9 now passes into the quench unit 10, in which the gas stream is quenched to a temperature below 800 F, so as to terminate the reaction before final equilibrium is attained, and thereby prevent carbon formation. Quench liquid stream 11 is any suitable coolant liquid and may consist of a stable heavy hydrocarbon oil, however stream 11 will preferably consist of water. Warmed quench liquid is removed via 12. The cooled process gas stream is removed via 13 at a temperature below 800 F., and consists of a crude combustible gas typically containing hydrogen, carbon monoxide, ethylene, methane, carbon dioxide and nitrogen. Stream i3 is directly usable as a gaseous fuel in certain applications, however stream 13 is preferably further processed to saturate any unsaturated hydrocarbons such as, ethylene, which act as illuminants and thus are undesirable in town gas. In addition, it is generally desirable to subject the gas stream to the water gas shift reaction in which carbon monoxide is converted to carbon dioxide by reaction with steam, in order to increase the hydrogen content of the gas stream. Carbon dioxide is also usually removed from the gas stream, in order to increase the Btu. content by decreasing the ballast or inerts content.
Stream 13 is first passed into water gas shift converter 14-, together with further steam which is supplied via 15 when required, to react with the carbon monoxide; content of stream 13. In some cases stream'i5 may be omitted, if sufficient steam is already present in stream 13. Converter, 14- is provided with at least one bed to" of catalyst, usually consisting of active iron oxide plus alkali oxide promoter, deposited on a suitable carrier. Unit 14 may consist of the apparatus described in US. Patent No. 3,010,807, or other suitable apparatus. When the gas stream passes through converter 14, contact with catalyst bed 16 results in the water gas shift reaction be tween carbon monoxide and steam, yielding carbon di- The resulting gas stream removed via 17 has low or negligible carbon monoxide content, and is relatively high in content of free hydrogen.
Stream 17 is now passed through catalytic hydrogenation unit 18, which is provided with gauze layers 19 consisting of a platinum group metal such as platinum or palladium. As an alternative, unit 18 may be provided with a catalyst bed consisting of platinum deposited on a suitable carrier. In any case, catalytic hydrogenation ofunsaturates in the gas stream is carried out in unit 18. Thus in the case of ethylene, addition of hydrogen to the unsaturated double bond produces ethane.
The resulting process stream 20 withdrawn from unit 18 has a negligible content of unsaturates. Stream .20 is now passed through scrubber 21, Where the gas stream is contacted with a liquid scrubbing agent such as hot aqueous potassium carbonate solution or aqueous monoethanolamine solution, for removal of carbon dioxide. The scrubbing unit 21 is provided with a packed section 22 for gas-liquid contact, alternatively bubble cap trays or grid trays may be provided for this purpose. The scrubbing liquid solution is admitted via 23, and liquid solution containing absorbed carbon dioxide is removed via 24 for external regeneration.
The final gas stream of reduced carbon dioxide content is removed from unit 21 via 25, and may be subsequently cooled or otherwise treated by means not shown for the removal of Water vapor. In any case, a finished town gas is produced, containing principally ethane, methane, hydrogen and nitrogen. .Nitrogen is a desirable component in finished town gas, since it serves as ballast in diluting the gas stream to provide the proper B.t.u. value. Due to thehydrogenation in unit 18, the finished town gas is low in unsaturates, which are undesirable since these compounds act as illuminants during combustion and also have gum-forming tendencies.
As an alternative embodiment of the present invention, a suitable catalyst such as metallic nickel rings may be provided in unit 8, in order to promote the formation of hydrogen by catalytic steam reform, thus yieldinga final gas product of higher B.t.u. value.
It has been found that operating pressure does not appear to be a significant variable in the process of the present invention. Although pressure is notcritical, an operating pressure in the range of 1 to 22 atmospheres is preferable since reform plant equipment size is reduced, and also become subsequent compression costs are reduced. In addition, gasification at elevated pressure yields a high pressure process gas which thus may range of 1450 F. to 1500 F. However, of a longer residence interval up to 1.0 second is required, then the initial streams 3, 4 and 5 must be preheated to higher levels so as to provide a temperature range of 1650 F. to 1690 F. in chamber 8, in order to prevent accumulated deposition of free carbon in actual operation of the process.
Similarly, it will be recognized that a minimum steam/carbon ratio of 1.5 is generally required,in order to satisfy material balance considerations by providing snflicient steam for complete reaction with the naphtha. However, a steam/carbon ratio in the range of 3 to 6 has been found to be optimum in providing complete reaction, satisfactory reaction rate, and minimum tendency for carbon formation due to process upsets. Higher proportions of process air will generally berequired if minimum steam/carbon ratios are adopted, in order to prevent carbon deposition. In general, the molar air/ carbon ratio Will range between 0.1 and 1.0.
Following are examples of industrial application of the process of the present invention in the production of a stable combustible gas from naphtha.
TABLE I Production of crude combustible gas Run No 1 2 3 Steam/Carbon Ratio 3. 6 4. 4 3. 6 Air/Carbon Ratio 0. 58 i 0.59 0.59 Reaction Time, sec.-- 0. 48 .0. 37 0. 30 Pressure, p.s.i.g 240 150 100 Gasification Temp Carbon Dioxide 9. 9 11.0 9. 6 Carbon M0noxid" 8. 5 7. 4 12. 5 Ethylene. 5.8 7. 8, 7. 2 Methane 20. 5 16. 6 16. 0 Hydroge 27. 8 27. 6 31. 1 N itrogen 27. 5 29. 6 23. 6
Runs 1 and 2 were non-catalytic, while in run 3 a nickel type catalyst was provided in the gasification step. It is evident that a highercontent of free liydrogen was present in the exit gas from run 3, thus the B.t.u. value was somewhat greater due to the catalytic effect.
Production of finished town gas be directly treated for carbon dioxide removal by hot potassium carbonate scrubbing.
It will be evident to those skilled in the art that the a significant process variables in the gasification of naphtha according to the present invention are closely interrelated. T bus, the required minimum preheat temperature of the reactant streams piror to chamber 8 will depend principally on the residence time in 8 prior to entry of the mixed stream via 9 into quench unit 10. With lower residence times in the range of 0.05 to 0.10 second, it has been found that the process may be successfully carried out with a residence chamber temperature in the The final town gas product had a net heating value of 437 Btu/ft. and a specific gravity of 0.502.
Following is an analysis of the commercial naphtha employed in the above runs. It is evident that naphthas of varying compositions and analysesmay be successfully reformed by suitable selection of process variables within the scope of the present invention.
TABLE HI Specification of tested naphtha Initial boiling point F.) End point F.) 250 Specific gravity 60 F -Q. 0.70 Composition (wt. percent):
Parafiins 57.4 Naphthenes 32.5 Aromatics 9.4 Olefins 0.7 Sulfur content (p.p.rn.) -10 From the above analyses of the gas stream in Table I, certain conclusions may be reached with respect to probable reaction mechanism. Thus, since no oxygen is present, combustion of naphtha has already taken place to completion. Since some unsaturates as well as methane are present, it is evident that some thermal cracking of naphtha also took place, probably together with some hydrogenation of unstable free radicals and unsaturated carbon linkages. This thermal cracking thus was accomplished without carbon accumulation. Finally some free hydrogen is also present hence non-catalytic (thermal) steam reform of naphtha also took place.
We claim:
1. A process for the gasification of naphtha to produce a combustible gas which comprises vaporizing and preheating naphtha to a temperature in the range of 122 F. to 1000" F., 'superheating steam, and preheating air;
combining said streams of naphtha, steam and air .to
form a mixed gaseous stream at an initial temperature of at least 1000 F., said mixed gaseous stream having a steam to carbon molar ratio of at least 1.5 and an air to carbon molar ratio of at least 0.1, reacting said mixture for an interval less than 1.0 second whereby the process stream temperature rises to a minimum of at least 1400 F. and said naphtha is simultaneously oxidized, cracked and partially reformed without accumulated deposition of free carbon, and quenching the process gas stream to a temperature below 800 F. by contact with a liquid quench agent, whereby a stable crude combustible gas mixture is produced comprising carbon dioxide, carbon monoxide, ethylene, methane, hydrogen and nitrogen,
without accumulated deposition of free carbon.
2. The process of claim 1, in which said liquid quench agent is water.
3. A process forthe gasification of naphtha to produce a combustible gas which comprises vaporizing and preheating naphtha to a temperature of 400 F. to 800 F., preheating air to a temperature above 800 F. and supereating steam to a temperature above 1500 F.; combining said streams of naphtha, steam and air to form a mixed gaseous stream at a temperature of 1400 F. to 1700 F. and a total pressure in the range or" 1 to 22 atmospheres, said mixed gaseous stream having a steam to carbon molar ratio in the range of 1.5 to 6.0 and an air .to carbon molar ratio in the range of 0.1 to 1.0,
reacting said mixture for a time interval between 0.05 to .0.33 second, whereby said naphtha is simultaneously oxidized, cracked and partially reformed Without accumulated deposition of free carbon, and quenching the process gas stream to a temperature below 800 F. by contact with liquid water, whereby a stable crude combustible gas mixture is produced comprising carbon dioxide, carbon monoxide, ethylene, methane, hydrogen 'ahd nitrogen,
without accumulated deposition of free carbon.
combining said streams of naphtha, steam and air to form a mixed gaseous stream at an initial temperature of at least 1000 F, said mixed gaseous stream having a steam to carbon molar ratio of at least 1.5 and an air to carbon molar ratio of at least 0.1, reacting said mixture for an interval less than 1.0 second whereby the process stream temperature rises to a minimum of at least 1400 F. and said naphtha is simultaneously oxidized, cracked and partially reformed Without accumulated deposition of free carbon, quenching the process gas stream to a temperature below 800 F. by contact with liquid water, whereby a crude combustible gas mixture is produced comprising carbon dioxide, carbon monoxide, ethylene, methane, hydrogen and nitrogen, without accumulated deposition of free carbon, catalytically reacting the carbon monoxide content of the gas mixture with water vapor to form further hydrogen and carbon dioxide by contacting the gas mixture with a water gas shift catalyst comprising promoted iron oxide, catalytically hydrlogenating the ethylone content of the gas mixture to ethane, and scrubbing the gas mixture with a liquid absorbent to remove carbon dioxide, whereby a stable combustible town gas is produced comprising ethane, methane, hydrogen and nirogen.
6. The process of claim 5, in which said reaction of vaporized naphtha with steam and air is carried out in the presence of a nickel catalyst.
'7. A process for the gasification of naphtha to produce a combustible town gas which comprises vaporizing and preheating naphtha to a temperature of. 400 F. to 800 F., preheating air to a temperature of 800 F. to 1200 F., and superheating steam to a temperature of 1500 F. to 1700 F; combining said streams of naphtha, steam and air to form a mixed gaseous stream at a temperature of 1400 F. to 1700 F. and a total pressure in the range of 1 to 22 atmospheres, said mixed gaseous stream having a steam to carbon molar ratio in the range of 3.0 to 6.0 and an air to carbon molar ratio in the range of 0.1 to 1.0, reacting said mixture in the presence of a nickel catalyst for a time interval between 0.05 to 0.33 second, whereby said naphtha is simultaneously oxidized, cracked and partially reformed without'accumulated deposition of free carbon, quenching the process gas stream to a temperature below 800 F. by contact with liquid water, whereby a crude combustible gas mixture is produced comprising carbon dioxide, carbon monoxide, ethylene, methane, hydrogen and nitrogen, without accumulated deposition of .tree carbon, catalytically reacting the carbon monoxide content of the gas mixture with water vapor to form further hydrogen and carbon dioxide by contacting the gas mixture with a Water gas shift catalyst comprising promoted iron oxide, catalytically hydrogenating the ethylene content of the gas mixture to ethane, and scrubbing the gas mixture with a liquid absorbent to remove carbon dioxide, whereby a stable combustible town gas is produced comprising ethane, methane, hydrogen and nitrogen.
References Cited by the Examiner UNITED STATES PATENTS ldORRES O. W OLK, Primary Examiner,

Claims (1)

1. A PROCESS FOR THE GASIFICATIN OF NAPHTHA TO PRODUCE A COMBUSTIBLE GAS WHICH COMPRISES VAPORIZING AND PREHEATING NAPHTHA TO A TEMPERATURE IN THE RANGE OF 112*F. TO 1000*F., SUPERHEATING STEAM, AND PREHEATING AIR; COMBINING SAID STREAMS OF NAPHTHA, STEAM AND AIR TO FORM A MIXED GASEOUS STREAM AT AN INITIAL TEMPERATURE OF AT LEAST 1000*F., SAID MIXED GASEOUS STREAM HAVING A STEAM TO CARBON MOLAR RATIO OF AT LEAST 1.5 AND AN AIR TO CARBON MOLAR RATIO OF AT LEAST 0.1, REACTING SAID MIXTURE FOR AN INTERVAL LESS THAN 1.0 SECOND WHEREBY THE PROCESS STREAM TEMPERATURE RISES TO A MINIMUM OF AT LEAST 1400* F. AND SAID NAPHTHA IS SIMULTANEOUSLY OXIDIZED, CRACKED AND PARTIALLY REFORMED WITHOUT ACCUMULATED DEPOSITION
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US9284854B2 (en) 2010-02-01 2016-03-15 SEE—Soluções, Energia e Meio Ambiente Ltda. Method and system for producing a source of thermodynamic energy by CO2 conversion from carbon-containing raw materials
US9327986B2 (en) 2010-02-01 2016-05-03 SEE—Soluções, Energia e Meio Ambiente Ltda. Method for recycling carbon dioxide CO2
US9340735B2 (en) 2010-02-01 2016-05-17 SEE—Soluções, Energia e Meio Ambiente Ltda. Method and system for producing hydrogen from carbon-containing raw materials
US9505997B2 (en) 2010-02-01 2016-11-29 SEE—Soluções, Energia e Meio Ambiente Ltda. Method and system for supplying thermal energy to a thermal processing system from the gasification of dry, carbon-containing raw materials, followed by oxidation, and installation for operating this system
WO2013117854A1 (en) * 2012-02-09 2013-08-15 Cotaver Process, system and installation for treating liquid and/or pasty hydrocarbon materials
FR2986800A1 (en) * 2012-02-09 2013-08-16 Cotaver PROCESS, SYSTEM AND SYSTEM FOR TREATING LIQUID AND / OR PASSIZED HYDROCARBON MATERIALS
US9327971B2 (en) 2012-02-09 2016-05-03 See-Soluções, Energia E Meio Ambiente Ltda Process, system and installation for treating liquid and/or pasty hydrocarbon materials

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DE1274270B (en) 1968-08-01
NL6406228A (en) 1964-12-08
BE648837A (en) 1964-12-04
GB1005935A (en) 1965-09-29

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