US3351563A - Production of hydrogen-rich synthesis gas - Google Patents

Production of hydrogen-rich synthesis gas Download PDF

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US3351563A
US3351563A US285672A US28567263A US3351563A US 3351563 A US3351563 A US 3351563A US 285672 A US285672 A US 285672A US 28567263 A US28567263 A US 28567263A US 3351563 A US3351563 A US 3351563A
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steam
carbon
naphtha
carbon dioxide
hydrogen
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US285672A
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John S Negra
Barclay Kenneth Mac
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Chemical Construction Corp
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Chemical Construction Corp
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Priority to US285672A priority Critical patent/US3351563A/en
Priority to GB21989/64A priority patent/GB1006745A/en
Priority to ES300406A priority patent/ES300406A1/es
Priority to FR976603A priority patent/FR1400701A/fr
Priority to DE19641467004 priority patent/DE1467004A1/de
Priority to BE648834D priority patent/BE648834A/xx
Priority to NL6406292A priority patent/NL6406292A/xx
Priority to JP39031735A priority patent/JPS4822597B1/ja
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    • 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
    • C01B3/388—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 heat being generated by superheated steam
    • 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
    • C01B3/384—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
    • 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

  • a process has been developed which features the cracking and partial thermal reforming of naphtha vapor, by reaction with superheated steam under controlled conditions of temperature and reaction time.
  • the formation and accumulation of free carbon is avoided by limiting the reaction time prior to catalysis to prevent attainment of reaction equilibrium, while the formation of lower hydrocarbons by thermal cracking is also controlled and becomes a transient phenomenon.
  • the final process gas stream contains only a negligible proportion of unreacted lower hydrocarbons.
  • Nap'htha 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 U.S. Bureau of Mines routine analysis at a vapor temperature of 392 F.
  • a more detailed definition of naphtha appears in Petroleum Refining With Chemical by Kalichevsky & Kobe (1956).
  • a discussion of naphtha on pp. 21-23 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 or 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 the C- to C-9 range, however, up to about 30% naphthenics together with up to 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.
  • crude naphtha may be further refined and upgraded to yield a variety of finished petroleum solvents.
  • naphtha is reformed in the petroleum sense of the term.
  • the crude naphtha is cracked, and hydrocarbon molecules are re-assembled in the presence of platinum-or other suitable catalyst, so as to yield a substantial proportion of branched chain or aromatics molecules.
  • This material is then blended with other refinery cuts for gasoline usage.
  • the word reforming has an entirely different meaning, as will appear infra.
  • naphtha may also be utilized as a hydrocarbon raw material for the manufacture of hydrogen or synthesis gas which is employed in the catalytic synthesis of ammonia or methanol.
  • synthesis gas There are two general approaches to the conversion of the various types of hydrocarbons to synthesis gas, namely, steam reforming and partial oxidation.
  • steam reforming a normally gaseous hydrocarbon such as methane is mixed with steam, and the mixture is then passed through an externally heated bed of nickel-c0ntaining reform catalyst. An endothermic reaction takes place between the hydrocarbon and steam, resulting in the formation of a synthesis gas product stream containing principally hydrogen, carbon monoxide and carbon dioxide.
  • a hydrocarbon raw material is reacted with oxygen or oxygen-enriched air at a highly elevated temperature.
  • the product stream is then quenched, to yield a crude synthesis gas stream.
  • a catalyst is not employed in conventional partial oxidation practice, since essentially complete reaction of the hydrocarbon is readily accomplished at the high temperature levels generated in this process.
  • a variety of hydrocarbons may be employed in partial oxidation, including liquid or even powdered solid hydrocarbons as well as gases.
  • a partial oxidation effect is obtained in a catalytic process by adding oxygen to a stream of hydrocarbon vapor or partially reformed gas, immediately before the stream is passed through a catalyst bed.
  • the bed is not externally heated, instead the process is carried out in a refractory-lined chamber as in conventional partial oxidation. It will be evident that this procedure is subject to the principal economic drawback of all partial oxidation processes, namely, that an air separation plant is required.
  • naphtha is catalytically steam reformed to produce a hydrogen-rich synthesis gas.
  • carbon dioxide is employed together with process steam, to yield a synthesis gas having the proper ratio of hydrogen to carbon oxides for usage of the product gas stream in methanol synthesis.
  • the process of the present invention depends on a unique balance of reaction conditions to achieve the catalytic steam reforming of naphtha, since this is accomplished without accumulated deposition of free carbon. Inaddition, no significant amount of unreacted hydrocarbon is present in the final synthesis gas. The process is carried out in two stages, a gasification-conditioning stage and a cata lytic steam reform stage.
  • process streams of naphtha and steam are preheated and mixed.
  • a partial reaction ensues, and the mixed process stream, now containing a variety of intermediate components but not in final reaction equilibrium, is passed through an externally heated bed of reform catalyst.
  • a final process stream is produced by steam reforming of residual naphtha and intermediate lower hydrocarbons.
  • This final process stream consists of a synthesis gas containing principally hydrogen, carbon monoxide, carbon dioxide and steam. The stream is essentially free of unreacted hydrocarbons or solid particulate carbon.
  • a primary advantage is that naphtha is catalytically steam reformed to a hydrogen-rich synthesis gas, without the concomitant accumulation of free carbon or tars, and without the production of lower hydrocarbons as a significant component of the final process stream. Thus, no recycle or side stream disposal 1s required.
  • the process is continuous rather than cyclic or intermittent.
  • one major economic cost in partial oxidation processes namely an air separation plant or other source of free oxygen, is not required in the process of the present invention.
  • conventional steam reformer apparatus rather than a special or costly apparatus design may be employed in the catalytic reforming stage of the present invention.
  • Another object is to reform naphtha in a continuous process, without accumulated deposition of tars or free carbon.
  • a further object is to reform naphtha by catalytic reaction with steam.
  • An additional object is to react naphtha with steam by a two-stage mixing and catalytic reform process, whereby naphtha is completely reformed and a gas stream principally containing hydrogen, carbon monoxide, carbon dioxide and steam is produced.
  • Still another object is to gasify and reform naphtha to a hydrogen-rich synthesis gas suitable for methanol synthesis using steam and carbon dioxide as process reactants.
  • stream 1 is a liquid naphtha, derived from petroleum refining or other types of crude oil processing.
  • stream 1 consists principally of paraffinic hydrocarbons in the C to C9 range, together with naphthentics as well as minor amounts of aromatics and sulfur compounds.
  • the liquid stream 1 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 to a temperature above 1000 F., and preferably to the range of 1500 F. to 1800 F. Although lower ratios are feasible, it has been found that a range of molar steam/carbon ratios between 5 to 1 and 6 to 1 is desirable in proportioning the relative flow rates of streams 4 and 3, in order to prevent accumulated deposition of carbon under normal operating conditions.
  • Optional stream 5 consists of carbon dioxide, preheated usually to a temperature above 1000 F.
  • the proportion of carbon dioxide employed in the process is quite small, thus carbon dioxide is used only to provide a suitable molar ratio of hydrogen to carbon oxides in the final synthesis gas stream when methanol synthesis gas is the desired product.
  • the molar ratio of carbon dioxide to naphtha carbon will generally be in the range of 0.1 to 1.0.
  • the streams 4 and 5 are preferably combined, to form a mixed steam-carbon dioxide stream 6 at a temperature of at least 1500 F. Stream 6 is now combined with naphtha vapor stream 3, and the mixed stream 7 is immediately passed into residence or gas conditioning chamber 8.
  • streams 3, 4 and 5 may be separately passed into chamber 8, however premixing of the carbon dioxide 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 resultant gaseous stream 9 contains significant proportions of steam, hydrogen, carbon dioxide, carbon monoxide, unsaturated hydrocarbons (mostly ethylene), methane and ethane. It should be understood, however, that these components are present on a transient or instantaneous basis. If stream 9 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, unless the residence time is kept in the range of 0.05 to 0.33 second. With such short residence times, unreacted naphtha may passing to the following catalytic stage of the process, however, as will appear infra, the formation of free carbon is readily prevented in the catalytic stage by maintenance of a temperature level above 1600 F. In general, the residence time in chamber 8 must be kept below 1.0 second, and preferably in the range of 0.05 to 0.33 second, in order to achieve the desired reactions without carbon formation.
  • 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.
  • chamber 3 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 conditioned gas stream into the catalyst bed section.
  • Reformer 10 may be a unit of conventional design, such as shown in US. Patent 2,660,519.
  • unit 10 is provided with a plurality of reformer tubes such as 11 having a bed or charge of reform catalyst 12, usually consisting of nickel or cobalt deposited on a suitable carrier.
  • Tube 11 is externally heated by such means as combustion of fluid hydrocarbon streams 13 with air streams 14, with flue gas removal via 15.
  • the temperature of the catalyst in bed 12 must generally be kept above 1600 F., in order to prevent carbon accumulation.
  • the equivalent linear velocity of the process stream in the bed 12 is maintained above 5 ft./second.
  • Equivalent linear velocity refers to the gas velocity which would exist at normal operating conditions, if the tube was not filled with catalyst. It has been determined that this linear velocity should preferably be in the range of 10 ft./sec. to 30 ft./sec., in order to effectively spread out the reforming reaction through the bed 12 and thereby effectively prevent carbon deposition.
  • stream 16 contains essentially only hydrogen, carbon monoxide, carbon dioxide and steam.
  • a typical analysis of stream 16 is as follows: 72.4% hydrogen, 14.7% carbon dioxide, 11.5% carbon monoxide, 1.0% methane and 0.0% unsaturates. This analysis was on a dry basis, the total product stream generally contained about 50% steam on a total volume basis.
  • stream 16 is now processed by conventional technology, not shown. This will include the usual process steps of CO-oxidation, carbon dioxide removal, etc, if hydrogen gas is the desired final product. It will be understood that the process of the present invention may be carried out wtihout carbon dioxide as process reactant, when hydrogen gas is the desired product.
  • the required minimum preheat temperatures of the reactant streams prior to chamber 8 will depend principally on the residence time in 8 prior to entry of the mixed stream via 9 into bed 12. With lower residence times in the range of 0.05 to 0.10 seconds, it has been found that the process may be successfully carried out with a residence chamber temperature in the range of 1450 F. to 1500 F. However, if a longer residence interval up to 1.0 seconds 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.
  • the reactions of naphtha cracking and 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 reactions may be carried out without carbon accumulation.
  • the resulting unstable process stream when passed to catalytic steam reforming before further reaction ensues, is successfully steam reformed to yield further hydrogen and carbon monoxide in a second stage without carbon accumulation.
  • the present invention essentially accomplishes the steam reforming of naphtha by a process which partially gasifies the naphtha vapor using preheated steam.
  • the resulting mixed gas stream may be successfully converted to a synthesis gas by conventional endothermic catalytic steam reforming without accumulated deposition of carbon, if the mixed gas stream is passed into contact with a catalyst bed. before final process equilibrium is reached.
  • the critical features of the present invention essentially involve the maintenance of the several inter-related process variables within operating limits in which the new result of the present invention is achieved, namely the continuous steam reforming of naphtha.
  • a naphtha feedstock was steam reformed to produce a synthesis gas of high hydrogen content in accordance with the present invention.
  • the data was taken at above normal throughputs for units used in conventional practice. Catalyst bed volume was 1.5 cubic feet.
  • the naphtha was successfully reformed in a continuous manner Without carbon formation. Following are the results obtained.
  • the process of the present invention was also applied to the production of methanol synthesis gas.
  • the final gas stream must have a lower hydrogen to carbon monoxide ratio than shown in Table 1' supra. This is accomplished by lowering the process steam ratio and injecting carbon dioxide into the feed stream. Following are the results obtained.
  • a process for producing a hydrogen-rich synthesis gas suitable for methanol synthesis and containing essentially only hydrogen, carbon monoxide, carbon dioxide and steam, and substantially free of hydrocarbons from naphtha which consists of vaporizing and preheating naphtha to a temperature in the range of 400 F. to 800 F., superheating steam to a temperature in the range of 1500 F. to 1800 F., and preheating carbon dioxide to a temperature above 1000 F., combining said streams of naphtha vapor, carbon dioxide and steam to form a mixed gaseous stream at a temperature in the range of 1400 F. to 1700 F.
  • said mixed stream consisting of a mixture of naphtha vapor, carbon dioxide and steam and having a molar steam to carbon ratio in the range of 5.0 to 6.0 and a molar carbon dioxide to carbon ratio in the range of 0.1 to 1.0, reacting said mixture non-catalytically for an interval in the range of 0.05 to 0.33 second, whereby said naphtha is simultaneously cracked to lower hydrocarbons and partially steam reformed without accumulated deposition of free carbon, and catalytically reform ing the resulting gas mixture in contact with a hydrocarbon reforming catalyst selected from the group consisting of nickel and cobalt deposited on a carrier, at a linear gas velocity in the range of 10 to 30 ft./sec., said catalyst being externally heated to maintain a reaction temperature of at least 1600 F., whereby a final reformed gas mixture is produced substantially free of hydrocarbons and containing essentially only hydrogen, carbon monoxide, carbon dioxide and steam, said reformed gas mixture being produced

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US285672A 1963-06-05 1963-06-05 Production of hydrogen-rich synthesis gas Expired - Lifetime US3351563A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US285672A US3351563A (en) 1963-06-05 1963-06-05 Production of hydrogen-rich synthesis gas
GB21989/64A GB1006745A (en) 1963-06-05 1964-05-27 Process for forming a hydrogen rich synthesis gas
ES300406A ES300406A1 (es) 1963-06-05 1964-05-30 Un procedimiento para formar un gas de síntesis rico en hidrógeno
FR976603A FR1400701A (fr) 1963-06-05 1964-06-01 Procédé pour le reformage catalytique à la vapeur d'eau de naphta, en vue de l'obtention d'un gaz de synthèse riche en hydrogène
DE19641467004 DE1467004A1 (de) 1963-06-05 1964-06-03 Verfahren zur Herstellung eines wasserstoffreichen Synthesegases
BE648834D BE648834A (es) 1963-06-05 1964-06-04
NL6406292A NL6406292A (es) 1963-06-05 1964-06-04
JP39031735A JPS4822597B1 (es) 1963-06-05 1964-06-05

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BE (1) BE648834A (es)
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ES (1) ES300406A1 (es)
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NL (1) NL6406292A (es)

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US3531267A (en) * 1965-06-17 1970-09-29 Chevron Res Process for manufacturing fuel gas and synthesis gas
US4400182A (en) * 1980-03-18 1983-08-23 British Gas Corporation Vaporization and gasification of hydrocarbon feedstocks
WO2011150217A3 (en) * 2010-05-28 2012-05-31 Greatpoint Energy, Inc. Conversion of liquid heavy hydrocarbon feedstocks to gaseous products
US8286901B2 (en) 2008-02-29 2012-10-16 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8297542B2 (en) 2008-02-29 2012-10-30 Greatpoint Energy, Inc. Coal compositions for catalytic gasification
US8328890B2 (en) 2008-09-19 2012-12-11 Greatpoint Energy, Inc. Processes for gasification of a carbonaceous feedstock
US8349039B2 (en) 2008-02-29 2013-01-08 Greatpoint Energy, Inc. Carbonaceous fines recycle
US8361428B2 (en) 2008-02-29 2013-01-29 Greatpoint Energy, Inc. Reduced carbon footprint steam generation processes
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US9034061B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9034058B2 (en) 2012-10-01 2015-05-19 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US20150191352A1 (en) * 2014-01-07 2015-07-09 Advanced Cooling Technologies, Inc. Fuel reforming system and process
US9115324B2 (en) 2011-02-10 2015-08-25 Expander Energy Inc. Enhancement of Fischer-Tropsch process for hydrocarbon fuel formulation
US9127221B2 (en) 2011-06-03 2015-09-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US9156691B2 (en) 2011-04-20 2015-10-13 Expander Energy Inc. Process for co-producing commercially valuable products from byproducts of heavy oil and bitumen upgrading process
US9169443B2 (en) 2011-04-20 2015-10-27 Expander Energy Inc. Process for heavy oil and bitumen upgrading
US9212319B2 (en) 2012-05-09 2015-12-15 Expander Energy Inc. Enhancement of Fischer-Tropsch process for hydrocarbon fuel formulation in a GTL environment
US9234149B2 (en) 2007-12-28 2016-01-12 Greatpoint Energy, Inc. Steam generating slurry gasifier for the catalytic gasification of a carbonaceous feedstock
US9266730B2 (en) 2013-03-13 2016-02-23 Expander Energy Inc. Partial upgrading process for heavy oil and bitumen
US9273260B2 (en) 2012-10-01 2016-03-01 Greatpoint Energy, Inc. Agglomerated particulate low-rank coal feedstock and uses thereof
US9315452B2 (en) 2011-09-08 2016-04-19 Expander Energy Inc. Process for co-producing commercially valuable products from byproducts of fischer-tropsch process for hydrocarbon fuel formulation in a GTL environment
US9328291B2 (en) 2013-05-24 2016-05-03 Expander Energy Inc. Refinery process for heavy oil and bitumen
US9328920B2 (en) 2012-10-01 2016-05-03 Greatpoint Energy, Inc. Use of contaminated low-rank coal for combustion
US9353322B2 (en) 2010-11-01 2016-05-31 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock
US10344231B1 (en) 2018-10-26 2019-07-09 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization
US10435637B1 (en) 2018-12-18 2019-10-08 Greatpoint Energy, Inc. Hydromethanation of a carbonaceous feedstock with improved carbon utilization and power generation
US10464872B1 (en) 2018-07-31 2019-11-05 Greatpoint Energy, Inc. Catalytic gasification to produce methanol
US10557391B1 (en) 2017-05-18 2020-02-11 Advanced Cooling Technologies, Inc. Incineration system and process
US10618818B1 (en) 2019-03-22 2020-04-14 Sure Champion Investment Limited Catalytic gasification to produce ammonia and urea

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DE1467004A1 (de) 1968-12-19
GB1006745A (en) 1965-10-06
BE648834A (es) 1964-12-04

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