WO1997048639A1 - Synthesis gas production system and method - Google Patents

Synthesis gas production system and method Download PDF

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Publication number
WO1997048639A1
WO1997048639A1 PCT/US1997/010733 US9710733W WO9748639A1 WO 1997048639 A1 WO1997048639 A1 WO 1997048639A1 US 9710733 W US9710733 W US 9710733W WO 9748639 A1 WO9748639 A1 WO 9748639A1
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WO
WIPO (PCT)
Prior art keywords
gas
compressor
autothermal reformer
air
conduit
Prior art date
Application number
PCT/US1997/010733
Other languages
French (fr)
Inventor
Kenneth L. Agee
Mark A. Agee
Larry J. Weick
Elliot L. Trepper
Original Assignee
Syntroleum Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syntroleum Corporation filed Critical Syntroleum Corporation
Priority to EP97931292A priority Critical patent/EP0909258A1/en
Priority to EA199900039A priority patent/EA001466B1/en
Priority to AU34960/97A priority patent/AU740616B2/en
Priority to BR9709857-4A priority patent/BR9709857A/en
Publication of WO1997048639A1 publication Critical patent/WO1997048639A1/en
Priority to NO985973A priority patent/NO985973L/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32Production 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
    • C01B3/34Production 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
    • C01B3/38Production 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
    • C01B3/382Multi-step processes
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0485Set-up of reactors or accessories; Multi-step processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2/00Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02CGAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C3/00Gas-turbine plants characterised by the use of combustion products as the working fluid
    • F02C3/20Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products
    • F02C3/26Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension
    • F02C3/28Gas-turbine plants characterised by the use of combustion products as the working fluid using a special fuel, oxidant, or dilution fluid to generate the combustion products the fuel or oxidant being solid or pulverulent, e.g. in slurry or suspension using a separate gas producer for gasifying the fuel before combustion
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02CGAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C9/00Controlling gas-turbine plants; Controlling fuel supply in air- breathing jet-propulsion plants
    • F02C9/16Control of working fluid flow
    • F02C9/18Control of working fluid flow by bleeding, bypassing or acting on variable working fluid interconnections between turbines or compressors or their stages
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/146At least two purification steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/148Details of the flowsheet involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus

Definitions

  • the present invention relates to a synthesis gas production unit and more particularly to a combined autothermal reformer and turbine for a synthesis gas production system.
  • Synthesis gas is a mixture of gases prepared as feedstock for a chemical reaction; for example, carbon monoxide and hydrogen to make hydrocarbons or organic chemicals, or hydrogen and nitrogen to make ammonia. Syngas may be produced for use with a Fischer- Tropsch process, which is described further below and which is used as an example throughout.
  • the synthetic production of hydrocarbons by the catalytic reaction of carbon monoxide and hydrogen is known and is generally referred to as the Fischer-Tropsch reaction.
  • Numerous catalysts have been used in carrying out the reaction, and at relatively low to medium pressure (near atmospheric to 600 psig) and temperatures in the range of from about 300° F. to 600° F., both saturated and unsaturated hydrocarbons can be produced.
  • the synthesis reaction is very exothermic and temperature sensitive whereby temperature control is required to maintain a desired hydrocarbon product selectivity.
  • the Fischer-Tropsch reaction can be characterized by the following general reaction:
  • Two basic methods have been employed for producing the synthesis gas utilized as feedstock in the Fischer-Tropsch reaction.
  • the two methods are steam reforming, wherein one or more light hydrocarbons such as methane are reacted with steam over a catalyst to form carbon monoxide and hydrogen, and partial oxidation, wherein one or more light hydrocarbons are combusted or reacted sub-stoichiometrically to produce synthesis gas.
  • the steam reforming reaction is endothermic and a catalyst containing nickel is often utilized.
  • the hydrogen to carbon monoxide ratio of the synthesis gas produced by steam reforming of methane is approximately 3:1.
  • Partial oxidation is the non-catalytic, sub-stoichiometric combustion of light hydrocarbons such as methane to produce the synthesis gas.
  • the basic reaction is represented as follows: CHstay + l A 0 ? ⁇ CO + 2H 2
  • the partial oxidation reaction is typically carried out using high purity oxygen.
  • High purity oxygen can be quite expensive.
  • the hydrogen to carbon monoxide ratio of synthesis gas produced by the partial oxidation of methane is approximately 2:1.
  • a combination of partial oxidation and steam reforming known as autothermal reforming, wherein air is used as a source of oxygen for the partial oxidation reaction has also been used for producing synthesis gas heretofore.
  • autothermal reforming is a combination of partial oxidation and steam reforming where the exothermic heat of the partial oxidation supplies the necessary heat for the endothermic steam reforming reaction.
  • the autothermal reforming process can be carried out in a relatively inexpensive refractory lined carbon steel vessel whereby low cost is typically involved.
  • the autothermal process results in a lower hydrogen to carbon monoxide ratio in the synthesis gas than does steam reforming alone. That is, as stated above, the steam reforming reaction with methane results in a ratio of about 3:1 while the partial oxidation of methane results in a ratio of about 2:1.
  • the optimum ratio for the hydrocarbon synthesis reaction carried out at low or medium pressure over a cobalt catalyst is 2:1.
  • the feed to the autothermal reforming process is a mixture of light hydrocarbons such as a natural gas stream, some form of additional control is desired to maintain the ratio of hydrogen to carbon monoxide in the synthesis gas at the optimum ratio of about 2:1.
  • a residue gas is frequently produced.
  • a synthesis gas production system includes a gas turbine with an autothermal reformer (ATR) interposed between the compressor and expander and wherein the ATR produces syngas and serves as the combustor for the gas turbine .
  • ATR autothermal reformer
  • a system for converting lighter hydrocarbons to heavier hydrocarbons includes: a synthesis gas production unit having a compressor, an autothermal reformer fluidly coupled to the compressor for producing synthesis gas and reacting at least a portion the gas therein, and an expansion turbine fluidly coupled to the autothermal reformer for developing energy with the gas from the autothermal reformer; and a synthesis unit fluidly coupled to the expansion turbine for receiving the synthesis gas therefrom and producing heavier hydrocarbons.
  • a method of manufacturing synthesis gas production system includes providing a compressor, fluidly coupling an autothermal reformer to the compressor for producing synthesis gas and reacting at least a portion of the gas therein, and fluidly coupling an expansion turbine to the autothermal reformer for developing energy with the gas from the autothermal reformer.
  • a technical advantage of the present invention is that the system may obtain higher production of synthesis gas by running all or substantially all of the compressed air from the gas turbine through the autothermal reformer.
  • FIGURE 1 is a schematic representation of a process flow in which the present invention is well suited
  • FIGURE 2 is a schematic representation of a process flow showing a separate syngas reactor and turbine
  • FIGURE 3 is a schematic representation of a process flow showing an embodiment of the present invention with a combined syngas reactor and turbine;
  • FIGURE 4 is a schematic representation of a process flow showing a second embodiment of the present invention with a combined syngas reactor and turbine;
  • FIGURE 5 is a schematic representation of a process flow showing a third embodiment of the present invention with a combined syngas reactor and turbine .
  • FIGURES 1-5 of the drawings like numerals being used for like and corresponding parts of the various drawings.
  • the present invention involves the production of a synthesis gas, which may be used with synthesizing to produce methanol, DME, gasoline, or numerous other substances.
  • a synthesis gas which may be used with synthesizing to produce methanol, DME, gasoline, or numerous other substances.
  • the invention is suitable for use to produce syngas for a Fischer-Tropsch reactor, methanol reactor, ammonia reactor, or reactors requiring synthesis gas.
  • the invention is presented, however, in context of the Fischer-Tropsch process although it is to be understood that the application is much broader.
  • a process flow in which the invention may be incorporated including the use of a turbine is first presented in connection with FIGURES 1 and 2, and then a couple of specific embodiments of the present invention are described in connection with FIGURES 3-5.
  • the present invention may be used in the conversion of lighter hydrocarbons to heavier hydrocarbons.
  • FIGURE 1 one illustrative system for the conversion of heavier hydrocarbons from gaseous light hydrocarbons is shown.
  • a continuous stream of gaseous light hydrocarbons e.g., a natural gas stream, is conducted to a heat exchanger 10 of a conduit 12. While flowing through the heat exchanger 10, the stream of light hydrocarbons is heated by exchange of heat with a process stream of generated synthesis gas which as will be described below, comes from reactor 28.
  • the feed stream of light hydrocarbons is at a pressure in the range of from near atmospheric pressure to 600 psig and is preheated in the heat exchanger 10 to a temperature in the range of from about 500° F. to about 1000° F.
  • the preheated feed stream is conducted by a conduit 14 to a synthesis gas generator, generally designated by the numeral 16.
  • Air is drawn to an air compressor 18 by way of an inlet conduit 20, and from the compressor 18, a stream of air is conducted to a heat exchanger 22 by a conduit 21.
  • the stream of air is preheated in the heat exchanger 22 to a temperature in the range of from about 500° F. to about 1000° F. by exchange of heat with the synthesis gas stream exiting the heat exchanger 10. From the heat exchanger 22, the preheated air is conducted to the synthesis gas generator 16 by a conduit 24.
  • the synthesis gas generator 16 can take various forms, it generally includes a burner 26 connected to one end of a reactor vessel 28.
  • the reactor 28 is a refractory lined carbon steel vessel. Steam or water, which instantly converts to steam, is introduced into the reactor 28 by way of a conduit 32 connected thereto, and optionally carbon dioxide may be introduced into the reactor 28 by way of a conduit 34 connected thereto.
  • the preheated feed stream of gaseous light hydrocarbons from conduit 14 is intimately mixed with a preheated stream of air from conduit 24 in the burner 26 and ignited whereby the reaction takes place within the reactor 28.
  • the combustion reaction is carried out at a temperature in the range of from about 1500° F. to about 2500° F. under sub-stoichiometric conditions whereby the light hydrocarbons are partially oxidized.
  • a gas stream including nitrogen, unreacted light hydrocarbons, hydrogen and carbon monoxide is produced.
  • the unreacted light hydrocarbons in the combustion gas stream react with steam introduced into the reactor 28 in the presence of the reforming catalyst whereby additional hydrogen and carbon monoxide are produced therefrom.
  • carbon dioxide may be introduced into the reactor 28 to react with unreacted light hydrocarbons to produce additional carbon monoxide and hydrogen.
  • the resulting synthesis gas stream generated within the generator 16 includes hydrogen, carbon monoxide, carbon dioxide, nitrogen and unreacted light hydrocarbons, synthesis gas exits the reactor 28 by way of a conduit 36.
  • the combustion and reforming reactions preferably occur as coexisting reactions that reach equilibrium in generator 16.
  • the rates of water introduced into the reactor 28 by way of the conduit 32 and carbon dioxide introduced by way of the conduit 34 are varied. That is, the ratio of hydrogen to carbon monoxide in the produced synthesis gas stream, or the composition of the feed light hydrocarbon stream, or both, are monitored and used as the basis for changing the flow rates of steam and carbon dioxide to the reactor 28 whereby a constant ratio of hydrogen to carbon monoxide at about 2:1 is maintained in the existing synthesis gas.
  • the synthesis gas product stream produced in the generator 16 is conducted by the conduit 36 through the heat exchanger 10, then through the heat exchanger 22 and then to the inlet connection of a first hydrocarbon synthesis reactor 38.
  • the synthesis gas is at a temperature in the range of from about 1000° F. to about 2000° F.
  • the light hydrocarbon stream in conduit 14 is preheated to a temperature in the range of from about 500° F. to about 1000° F.
  • the synthesis gas stream flows through the heat exchanger 22 on conduit 36, it gives up heat to the air flowing to the generator 16 through conduit 24 whereby the air is also preheated to a temperature in the range of from about 500° F. to about 1000° F.
  • Additional cooling of the synthesis gas stream is provided by a cooler or heat exchanger 23 disposed in the conduit 36 whereby the temperature of the synthesis gas entering the reactor 38 is then in the range of from about 350° F. to about 550° F.
  • reactor 38 can take various forms, but in the embodiment shown is a tubular reactor containing a fixed bed 37 of hydrocarbon synthesis catalyst.
  • the catalyst of bed 37 may be of cobalt supported on silica, alumina or silica-alumina material in an amount in the range of from about 5 to about 50 parts by weight of cobalt per 100 parts by weight of the support material.
  • the catalyst may also contain in the range of from about 0.05 to about 1 parts by weight of ruthenium per 100 parts by weight of support material as a promoter.
  • the synthesis gas stream flows into and through the reactor 38.
  • the gas is delivered by conduit 36 and carried on its way by conduit 40.
  • the temperature within the reactor 38 is in the range of from about 350° F. to about 550° F., and upon contact with the catalyst, hydrogen and carbon monoxide in the synthesis gas stream react to form heavier hydrocarbons and water.
  • Conduit 40 leads the stream to a condenser 42. While flowing through the condenser 42, the heavier hydrocarbons and water contained in the stream are condensed. From the condenser 42, a conduit 44 conducts the stream containing condensed components to a separator 46 wherein the condensed heavier hydrocarbons and water are separated and separately withdrawn. That is, the condensed water is withdrawn from the separator 46 by way of a conduit 48 connected thereto, and the condensed heavier hydrocarbons are withdrawn from the separator 46 by way of a conduit 50 connected thereto.
  • a residue gas stream from the separator 46 includes nitrogen and unreacted hydrogen, carbon monoxide, light hydrocarbons and carbon dioxide .
  • a conduit 52 connected to the separator 46 leads the residue gas stream from the separator 46 to a second hydrocarbon synthesis reactor 54 containing a fixed bed 56 of a hydrocarbon synthesis catalyst, such as the one described above.
  • the pressure and temperature of the gas stream flowing through the reactor 54 are maintained at approximately the same levels as the pressure and temperature within the reactor 38 by means of a heater or heat exchanger 58 disposed in the conduit 52 between the separator 46 and reactor 54. While flowing through the reactor 54, additional heavier hydrocarbons are formed from hydrogen and carbon monoxide in the residue gas stream and the resulting product stream exits the reactor 54 by way of a conduit 60 connected thereto.
  • the conduit 60 leads the stream to a condenser 62 wherein heavier hydrocarbons and water contained therein are condensed.
  • a condenser 62 From the condenser 62, the stream containing condensed components is conducted to a chiller 66 of a refrigeration unit by a conduit 64 wherein additional hydrocarbons and water are condensed.
  • the resulting stream is conducted from the chiller 66 to a separator 70 by a conduit 68 connected therebetween. Separator 70 will have water, heavier hydrocarbons, and residue gas exit through three conduits. Water is withdrawn from the separator 70 by a conduit
  • conduit 72 connected thereto.
  • the conduit 72 is in turn connected by way of conventional valves and controls (not shown) to the conduit 48, to a drain conduit 31 and to the conduit 32 previously described whereby all or part of the condensed water separated in the separators 46 and 70 is selectively conducted to the synthesis gas generator 16.
  • the condensed heavier hydrocarbons separated within the separator 70 are withdrawn therefrom by a conduit 74 which connects to the conduit 50 from the separator 46.
  • the conduit 50 leads the heavier hydrocarbons from both the separators 46 and 70 to a conventional fractionation unit 76.
  • a hydrocarbon product stream containing selected components is withdrawn from the fractionation unit 76 by way of a conduit 78 which conducts the product stream to storage or other location.
  • Undesirable light and heavy hydrocarbon fractions produced in the fractionation unit 76 are withdrawn therefrom by conduits 80 and 82, respectively.
  • the conduits 80 and 82 connect to a conduit 84 which conducts the undesirable hydrocarbons to the inlet conduit 12 where they mix with the feed stream of gaseous light hydrocarbons and are recycled.
  • the residue gas stream produced in the separator 70 which may include nitrogen and unreacted hydrogen, carbon monoxide, light hydrocarbons and carbon dioxide, is withdrawn therefrom by a conduit 86 which leads the residue gas stream to a catalytic combustor 88.
  • the catalytic combustor 88 may include a burner 90 into which the residue gas stream is conducted.
  • a stream of air is conducted to the burner 90 by a conduit 92 connected to the discharge of an air blower 94.
  • the residue gas stream from the separator 70 and the air conducted to the burner 90 are intimately mixed therein, ignited and discharged into a reactor 96 connected to the burner 90.
  • the reactor 96 contains a fixed bed of suitable nobel metal containing catalyst 98, e.g., platinum or palladium, for promoting and catalyzing the oxidation of the oxidizable components in the residue gas stream.
  • suitable nobel metal containing catalyst 98 e.g., platinum or palladium
  • an oxidation product stream including carbon dioxide, water vapor and nitrogen is produced and withdrawn from the combustor 88 by a conduit 100 connected thereto.
  • the conduit 100 optionally leads the product stream to a conventional carbon dioxide removal unit 102. Carbon dioxide and water are removed from the stream by the carbon dioxide removal unit 102 thereby producing a relatively pure nitrogen product stream which is conducted from the unit 102 by a conduit 104 to a location of sale, storage or further processing.
  • the carbon dioxide removed by the unit 102 is withdrawn therefrom by a conduit 106 which leads the carbon dioxide to a compressor 108.
  • the discharge of the compressor 108 is connected by way of conventional valves and controls (not shown) to a vent 35 and to the conduit 34 previously described whereby all or part of the carbon dioxide is selectively introduced into the synthesis gas generator 16.
  • the flow rates of the water conducted to the synthesis gas generator 16 by way of the conduit 32 and carbon dioxide conducted thereto by way of the conduit 34 are varied as is necessary to control the ratio of hydrogen to carbon monoxide in the synthesis gas stream produced to as close to 2:1 as possible. This in turn improves the efficiency of the hydrocarbon synthesis reactions carried out in the reactors 38 and 54.
  • the use of air, delivered by conduit 24, in the synthesis gas generator 16 as the source of oxygen for the partial oxidation reaction carried out therein produces nitrogen in the synthesis gas stream. Such nitrogen acts as a diluent in the hydrocarbon synthesis reactors 38 and 54 and prevents hot spots on the catalyst and further increases the efficiency of the hydrocarbon synthesis reactions.
  • the recycling of all or part of the optional carbon dioxide, which is transported in conduit 106 provides additional carbon for producing heavier hydrocarbons and increases overall process efficiency.
  • the system of FIGURE 1 can include a gas turbine as will be further described below in connection with FIGURE 2.
  • a gas turbine As an example of one way the system of FIGURE 1 can be configured, catalytic combustor 88, the burner 90, the blower 94, and air compressor 18 may be removed and replaced with a gas turbine.
  • the gas turbine could include a combustor to burn the gas and the compressor section of the gas turbine could provide combustion air as blower 94 previously did and compressed air as compressor 18 previously did. Other examples will be given further below.
  • System 200 combines a synthesis gas unit 202 with a synthesis unit 204 and a gas turbine 206.
  • System 200 uses gas turbine 206 to provide power for the process at a minimum, but is preferably designed to provide at least some additional power.
  • Gas turbine 206 has a compressor section 208 and an expansion turbine section 210.
  • the power generated by the expansion turbine section 210 drives the compressor section 208 by means of linkage 212, which may be a shaft, and any excess power beyond the requirements of compressor section 208 may be used to generate electricity or drive other equipment as figuratively shown by output 214.
  • Compressor section 208 has inlet or conduit 216, where in the embodiment shown compressor 208 receives air. Compressor section 208 also has an outlet or conduit 218 for releasing compressed air. Expansion turbine 210 has inlet or conduit 220 and outlet or conduit 222. Outlet 218 of compressor section 208 provides compressed air to synthesis gas unit 202 through conduit 260.
  • Synthesis gas unit 202 may take a number of configurations, but in the specific embodiment shown, includes syngas reactor 224, which as shown here may be an autothermal reforming reactor.
  • a stream of gaseous light hydrocarbons e.g., a natural gas stream, is delivered to syngas reactor 224 by inlet or conduit 225.
  • natural gas containing elevated levels of components e.g., N 2 , CO, He, etc. that reduce the BTU value of the gas in conduit 225.
  • the synthesis gas unit 202 may also include one or more heat exchangers 226, which in the embodiment shown is a cooler for reducing the temperature of the synthesis gas exiting outlet 228 of syngas reactor 224.
  • Heat exchanger 226 delivers its output to inlet 230 of separator 232. Separator 232 removes moisture which is delivered to outlet 234. It may be desirable in some instances to introduce the water in conduit 234 as steam to expansion turbine 210. Synthesis gas exits separator 232 through outlet or conduit 236. The synthesis gas exiting through outlet 236 is delivered to synthesis unit 204.
  • Synthesis unit 204 may be used to synthesize a number of materials as previously mentioned, but in the specific example here is used to synthesize heavier hydrocarbons as referenced in connection with FIGURE 1.
  • Synthesis unit 204 includes Fischer-Tropsch reactor 238, which contains an appropriate catalyst.
  • the output of Fischer-Tropsch reactor 238 is delivered to outlet 240 from which it travels to heat exchanger 242 and on to separator 244.
  • the product entering separator 244 is first delivered to inlet 246.
  • Separator 244 distributes the heavier hydrocarbons separated therein to storage tank or container 248 through outlet or conduit 250.
  • Conduit 250 may include additional components such as a conventional fractionation unit as shown in FIGURE 1. Water withdrawn from separator 244 is delivered to outlet or conduit 252.
  • System 200 includes a combustor 256.
  • Combustor 256 receives air from compression section 208 delivered through conduit 258 which is fluidly connected to conduit 260 connecting outlet 218 with syngas reactor 224.
  • the conduit 260 beyond the juncture with conduit 258 delivers bleed air to the autothermal reformer 224.
  • residue gas delivered by separator 244 into conduit 254 is connected to combustor 256. Residue gas within conduit 254 is delivered to conduit 258 and then to combustor 256.
  • Intermediate conduit 260 and the connection of conduit 254 with conduit 258 may be a valve (not explicitly shown) for dropping the pressure delivered from compressor section 208 to combustor 256 in order to match the pressure in conduit 254 as necessary.
  • the output of combustor 256 is delivered to expansion turbine 210.
  • combustor 256 may be incorporated as part of gas turbine 206 itself.
  • the pressure in conduits 260 and 254 may be increased by a compressor to match or exceed the pressure requirements of combustor 256.
  • a synthesis gas production system 300 has an autothermal-reformer-turbine unit 302.
  • Synthesis gas production system 300 may be included as part of system 304 for converting lighter hydrocarbons that further includes a synthesis unit 306.
  • Autothermal-reformer-turbine unit 302 includes an autothermal reformer (ATR) 308 and gas turbine 310.
  • Gas turbine 310 includes a compressor section 312 and an expansion turbine section 314.
  • the power generated by the expansion turbine section 314 drives the compressor section 312 by means of linkage 316, which may be a shaft.
  • linkage 316 which may be a shaft.
  • This embodiment preferably has an exact energy balance, but if excess energy is developed, it may be removed from gas turbine 310 with an additional shaft extending from expansion section 314 as shown in FIGURE 4.
  • Compressor section 312 has inlet or conduit 318, where compressor 312 receives air.
  • Compressor 312 also has an outlet or conduit 320 for releasing compressed air.
  • the expansion turbine section 314 has inlet or conduit 322 and outlet or conduit 324. Outlet 324 of compressor section 314 provides compressed synthesis gas into conduit 336.
  • Autothermal reformer 308 produces synthesis gas, but also serves as the combustor of gas turbine 310.
  • Compressor section 312 develops compressed air that is delivered to outlet 320, which is delivered to first separator 326, which will be described further below. After traveling through separator 326, compressed air is delivered by way of conduit 328 to ATR 308.
  • gaseous light hydrocarbons such as natural gas, are delivered to conduit 328 from conduit 330 and the residue gas is also delivered through conduit 332 into a portion of conduit 330 and then to conduit 328 and ATR 308.
  • the present invention may realize the most efficient results by the inclusion of thrust bearings in gas turbine 310 that allow for a substantial imbalance between compressor section 312 and expansion section 314.
  • unit 302 may provide for balancing of the loads within the turbine manufacturer's specifications. This may be accomplished with first separator 326 or by bleeding air as will be described.
  • the balancing may be thought of as balancing the mass that is received in the compressor section with the mass received by the turbine section or some percentage thereof.
  • unit 302 receives additional mass from conduits 330 and 332 between compressor section 312 and expansion section 314 that would cause an imbalance without provisions being made.
  • separator 326 may remove mass by separating out nitrogen or bleeding off a portion of the compressed air as suggested by FIGURE 3.
  • Separator 326 may include separation technology such as a membrane or carbon absorption or any other technique suitable for the removal of nitrogen or other substances not needed by ATR 308. In embodiments with sufficiently strong thrust bearings in compressor 312 and turbine 314, no separator 326 or device for bleeding air is required.
  • ATR 308 will receive air and/or enriched air from conduit 328 along with the gaseous light hydrocarbons and residual gasses from conduits 330 and 332, respectively.
  • ATR 308 will then autothermally reform the gas before delivering synthesis gas to conduit 334.
  • the amount of gas delivered and produced by ATR 308 may be notably higher than that which would normally be expected from a normal gas-turbine combustor.
  • ATR 308 does not fully combust or react the gas, but because of the larger volumes of gas delivered to ATR 308, an adequate amount of energy may be produced by expansion section 314.
  • the ATR 308 will have an exit temperature in conduit 304 within an acceptable range for input into expansion section 314.
  • the gas delivered to ATR 308 may further be controlled to establish the proper ratios for ATR 308 such that the oxygen disappears and everything substantially goes to CO or C0 2.
  • one or more control valves which are represented by control valve 331, may be used to control the ratio of gaseous light hydrocarbons to air entering ATR 308.
  • Outlet 324 of expansion section 314 delivers its products to conduit 336 which fluidly connects with heat exchanger or cooler 338. Then, the process continues from cooler 338 to conduit 340 and second separator 342.
  • the synthesis gas which will contain some combustion products and/or a nitrogen diluted gas, is delivered to expansion section 314 and expanded before exiting outlet 324.
  • Cooler 338 further cools the gas which will condense at least some water from the gas.
  • a Fischer-Tropsch process is presented, and the separator 342 will be desirable.
  • the water condensed by the gas as it travels through the expansion section 314 and cooler 338, should be removed prior to delivering the product to second compressor 348.
  • separator 342 includes drain 344 for the removal of water.
  • the gaseous product leaving separator 342 is delivered by conduit 346 to compressor 348.
  • the syngas exiting expansion section 314 of gas turbine 310 may need to be pressurized before entering the Fischer-Tropsch reactor 350, and thus, compressor 348 may be added. Separator 342 removed the liquids that may have condensed prior to the compressor 348. Compressor 348 may be driven in a number of different ways. If the thrust bearings of gas turbine 310 allow for a sufficient imbalance for gas turbine 310 to create excess energy, a direct linkage 400 between expansion section 314 and compressor 348 may be utilized as shown in FIGURE 4. If excess energy is not available from gas turbine 310 in adequate quantities, the excess energy may be used along with a supplement.
  • Compression and compressor 348 should adequately heat the gas existing to conduit 352 sufficiently for entry into Fischer-Tropsch reactor 350.
  • the input to reactor 350 is preferably in the general range of 350° F. to 500° F. In some situations, it may be desirable to add a heat exchanger between compressor 348 and Fischer-Tropsch reactor 350 to further heat the gas therein.
  • Conduit 352 fluidly connects compressor 348 with reactor 350.
  • Reactor 350 may be a Fischer-Tropsch reactor which contains an appropriate catalyst. Other reactors may be used with other processes as previously noted.
  • the output of Fischer-Tropsch' s reactor 350 is delivered to outlet 354 of conduit 356 connecting with heat exchanger 358. After heat exchanger 358, the product is delivered via conduit 360 to third separator 362.
  • the heavier hydrocarbons separated in separator 362 are then delivered to storage tank or container 364 by conduit 368.
  • the residual gas is delivered to conduit 370. Separator 362 will also remove water which is delivered to conduit 372 for the case of a Fischer-Tropsch process.
  • Conduit 370 delivers the residual gas to separator
  • Fischer-Tropsch system 500 includes synthesis gas production system 501 and a Fischer-Tropsch reactor 550.
  • compressed air is delivered through conduit 518 to compressor 512.
  • Compressor 512 delivers compressed air to conduit 520.
  • Conduit 520 delivers compressed air to autothermal reformer 508.
  • Gaseous light hydrocarbons are delivered to conduit 520 and ultimately to ATR 508 by conduit 530.
  • the thrust bearings associated with link 516 between compressor 512 and turbine 514 must be adequate to handle the imbalance, or a sufficient amount of mass will need to be removed to allow the thrust bearings to be within their specifications for an imbalance force.
  • a separator removing nitrogen or a mechanism for bleeding a portion of the compressed air may be installed on conduit 520 as shown by reference numeral 526.
  • the synthesis gas exiting ATR 508 is delivered to turbine 514 by conduit 534.
  • the gas exiting turbine 514 enters conduit 536, which delivers it to Fischer-Tropsch' s reactor 550.
  • the turbine may decrease the pressure of a synthesis gas entering turbine 514 down to a lesser, non- zero number as it exits into conduit 536. For example, it may exit at 50 psi before being delivered to reactor 550. While a higher pressure may be desired for reactor 550, sufficiently active catalysts may be utilized in reactor 550 such that the performance of reactor 550 is adequate at the lower pressure. This system will obviate the need for a second compressor. Thus, while reactor 550 may not perform at optimum output, the reduced capital cost of removing a compressor may make operation in this mode desirable.

Abstract

A synthesis gas production system (302) includes a gas turbine (310) having a compressor (312) with an autothermal reformer (308) between the compressor (312) and the turbine (314). The system (302) may include a separator (326) for removing a portion of the mass exiting the compressor (312) prior to its delivery to the autothermal reformer (308). Gaseous light hydrocarbons are delivered to the autothermal reformer (308) through conduit (330) and may be selectively controlled with a valve (331). Synthesis gas production system (302) may be used with a methanol process, ammonia process, a Fischer-Tropsch process (304), or other process involving synthesis gas.

Description

SYNTHESIS GAS PRODUCTION SYSTEM AND METHOD
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a synthesis gas production unit and more particularly to a combined autothermal reformer and turbine for a synthesis gas production system.
BACKGROUND OF THE INVENTION
Synthesis gas, or "syngas," is a mixture of gases prepared as feedstock for a chemical reaction; for example, carbon monoxide and hydrogen to make hydrocarbons or organic chemicals, or hydrogen and nitrogen to make ammonia. Syngas may be produced for use with a Fischer- Tropsch process, which is described further below and which is used as an example throughout. The synthetic production of hydrocarbons by the catalytic reaction of carbon monoxide and hydrogen is known and is generally referred to as the Fischer-Tropsch reaction. Numerous catalysts have been used in carrying out the reaction, and at relatively low to medium pressure (near atmospheric to 600 psig) and temperatures in the range of from about 300° F. to 600° F., both saturated and unsaturated hydrocarbons can be produced. The synthesis reaction is very exothermic and temperature sensitive whereby temperature control is required to maintain a desired hydrocarbon product selectivity. The Fischer-Tropsch reaction can be characterized by the following general reaction:
2H, + CO — Ca►talyst — CH 2 ~ + H?0 Two basic methods have been employed for producing the synthesis gas utilized as feedstock in the Fischer-Tropsch reaction. The two methods are steam reforming, wherein one or more light hydrocarbons such as methane are reacted with steam over a catalyst to form carbon monoxide and hydrogen, and partial oxidation, wherein one or more light hydrocarbons are combusted or reacted sub-stoichiometrically to produce synthesis gas.
The basic steam reforming reaction of methane is represented by the following formula: CH4 + H20 r , → CO + 3H2
The steam reforming reaction is endothermic and a catalyst containing nickel is often utilized. The hydrogen to carbon monoxide ratio of the synthesis gas produced by steam reforming of methane is approximately 3:1.
Partial oxidation is the non-catalytic, sub-stoichiometric combustion of light hydrocarbons such as methane to produce the synthesis gas. The basic reaction is represented as follows: CH„ + lA 0? CO + 2H2
The partial oxidation reaction is typically carried out using high purity oxygen. High purity oxygen can be quite expensive. The hydrogen to carbon monoxide ratio of synthesis gas produced by the partial oxidation of methane is approximately 2:1.
In some situations these approaches may be combined. A combination of partial oxidation and steam reforming, known as autothermal reforming, wherein air is used as a source of oxygen for the partial oxidation reaction has also been used for producing synthesis gas heretofore. For example, U.S. Pat. Nos. 2,552,308 and 2,686,195 disclose low pressure hydrocarbon synthesis processes wherein autothermal reforming with air is utilized to produce synthesis gas for the Fischer-Tropsch reaction. Autothermal reforming is a combination of partial oxidation and steam reforming where the exothermic heat of the partial oxidation supplies the necessary heat for the endothermic steam reforming reaction. The autothermal reforming process can be carried out in a relatively inexpensive refractory lined carbon steel vessel whereby low cost is typically involved.
The autothermal process results in a lower hydrogen to carbon monoxide ratio in the synthesis gas than does steam reforming alone. That is, as stated above, the steam reforming reaction with methane results in a ratio of about 3:1 while the partial oxidation of methane results in a ratio of about 2:1. The optimum ratio for the hydrocarbon synthesis reaction carried out at low or medium pressure over a cobalt catalyst is 2:1. When the feed to the autothermal reforming process is a mixture of light hydrocarbons such as a natural gas stream, some form of additional control is desired to maintain the ratio of hydrogen to carbon monoxide in the synthesis gas at the optimum ratio of about 2:1. In producing a product from the synthesis unit, a residue gas is frequently produced. For some processes, the use of this gas to create energy has been suggested. Systems that have utilized the residue gas have required numerous additional components and steps to do so. In producing a synthesis gas for the Fischer-Tropsch process or any other process, it is desirable to produce the synthesis gas as efficiently as possible. The ability to develop a process with low capital expense may be an imperative to development of large-scale systems.
SUMMARY OF THF, INVENTION
Therefore, a need has arisen for a synthesis gas production system that addresses the shortcomings of the prior art . According to an aspect of the present invention, a synthesis gas production system includes a gas turbine with an autothermal reformer (ATR) interposed between the compressor and expander and wherein the ATR produces syngas and serves as the combustor for the gas turbine .
According to another aspect of the present invention, a system for converting lighter hydrocarbons to heavier hydrocarbons includes: a synthesis gas production unit having a compressor, an autothermal reformer fluidly coupled to the compressor for producing synthesis gas and reacting at least a portion the gas therein, and an expansion turbine fluidly coupled to the autothermal reformer for developing energy with the gas from the autothermal reformer; and a synthesis unit fluidly coupled to the expansion turbine for receiving the synthesis gas therefrom and producing heavier hydrocarbons. According to another aspect of the present invention, a method of manufacturing synthesis gas production system includes providing a compressor, fluidly coupling an autothermal reformer to the compressor for producing synthesis gas and reacting at least a portion of the gas therein, and fluidly coupling an expansion turbine to the autothermal reformer for developing energy with the gas from the autothermal reformer.
A technical advantage of the present invention is that the system may obtain higher production of synthesis gas by running all or substantially all of the compressed air from the gas turbine through the autothermal reformer.
BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present invention and advantages thereof, reference is now made to the following description taken in conjunction with the accompanying drawings in which like reference numbers indicate like features, and wherein:
FIGURE 1 is a schematic representation of a process flow in which the present invention is well suited; FIGURE 2 is a schematic representation of a process flow showing a separate syngas reactor and turbine; and
FIGURE 3 is a schematic representation of a process flow showing an embodiment of the present invention with a combined syngas reactor and turbine;
FIGURE 4 is a schematic representation of a process flow showing a second embodiment of the present invention with a combined syngas reactor and turbine; and
FIGURE 5 is a schematic representation of a process flow showing a third embodiment of the present invention with a combined syngas reactor and turbine .
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the present invention and its advantages are best understood by referring to FIGURES 1-5 of the drawings, like numerals being used for like and corresponding parts of the various drawings.
A. INTRODUCTION The present invention involves the production of a synthesis gas, which may be used with synthesizing to produce methanol, DME, gasoline, or numerous other substances. As noted in the background, the invention is suitable for use to produce syngas for a Fischer-Tropsch reactor, methanol reactor, ammonia reactor, or reactors requiring synthesis gas. The invention is presented, however, in context of the Fischer-Tropsch process although it is to be understood that the application is much broader. A process flow in which the invention may be incorporated including the use of a turbine is first presented in connection with FIGURES 1 and 2, and then a couple of specific embodiments of the present invention are described in connection with FIGURES 3-5.
B. THE CONVERSION OF HEAVIER HYDROCARBONS FROM GASEOUS LIGHT HYDROCARBONS The present invention may be used in the conversion of lighter hydrocarbons to heavier hydrocarbons. Referring to FIGURE 1, one illustrative system for the conversion of heavier hydrocarbons from gaseous light hydrocarbons is shown. A continuous stream of gaseous light hydrocarbons, e.g., a natural gas stream, is conducted to a heat exchanger 10 of a conduit 12. While flowing through the heat exchanger 10, the stream of light hydrocarbons is heated by exchange of heat with a process stream of generated synthesis gas which as will be described below, comes from reactor 28. Typically, the feed stream of light hydrocarbons is at a pressure in the range of from near atmospheric pressure to 600 psig and is preheated in the heat exchanger 10 to a temperature in the range of from about 500° F. to about 1000° F. From the heat exchanger 10, the preheated feed stream is conducted by a conduit 14 to a synthesis gas generator, generally designated by the numeral 16.
Air is drawn to an air compressor 18 by way of an inlet conduit 20, and from the compressor 18, a stream of air is conducted to a heat exchanger 22 by a conduit 21. The stream of air is preheated in the heat exchanger 22 to a temperature in the range of from about 500° F. to about 1000° F. by exchange of heat with the synthesis gas stream exiting the heat exchanger 10. From the heat exchanger 22, the preheated air is conducted to the synthesis gas generator 16 by a conduit 24.
While the synthesis gas generator 16 can take various forms, it generally includes a burner 26 connected to one end of a reactor vessel 28. A bed of steam reforming catalyst 30, which typically contains nickel, is disposed within the reactor 28 at the end opposite the burner 26.
In this embodiment, the reactor 28 is a refractory lined carbon steel vessel. Steam or water, which instantly converts to steam, is introduced into the reactor 28 by way of a conduit 32 connected thereto, and optionally carbon dioxide may be introduced into the reactor 28 by way of a conduit 34 connected thereto.
In the operation of the synthesis gas generator 16, the preheated feed stream of gaseous light hydrocarbons from conduit 14 is intimately mixed with a preheated stream of air from conduit 24 in the burner 26 and ignited whereby the reaction takes place within the reactor 28. The combustion reaction is carried out at a temperature in the range of from about 1500° F. to about 2500° F. under sub-stoichiometric conditions whereby the light hydrocarbons are partially oxidized. A gas stream including nitrogen, unreacted light hydrocarbons, hydrogen and carbon monoxide is produced.
The unreacted light hydrocarbons in the combustion gas stream react with steam introduced into the reactor 28 in the presence of the reforming catalyst whereby additional hydrogen and carbon monoxide are produced therefrom. Simultaneously, carbon dioxide may be introduced into the reactor 28 to react with unreacted light hydrocarbons to produce additional carbon monoxide and hydrogen. The resulting synthesis gas stream generated within the generator 16 includes hydrogen, carbon monoxide, carbon dioxide, nitrogen and unreacted light hydrocarbons, synthesis gas exits the reactor 28 by way of a conduit 36. The combustion and reforming reactions preferably occur as coexisting reactions that reach equilibrium in generator 16.
In order to control the ratio of hydrogen to carbon monoxide in the synthesis gas stream produced in the synthesis gas generator 16 at a ratio as close to 2:1 as possible, the rates of water introduced into the reactor 28 by way of the conduit 32 and carbon dioxide introduced by way of the conduit 34 are varied. That is, the ratio of hydrogen to carbon monoxide in the produced synthesis gas stream, or the composition of the feed light hydrocarbon stream, or both, are monitored and used as the basis for changing the flow rates of steam and carbon dioxide to the reactor 28 whereby a constant ratio of hydrogen to carbon monoxide at about 2:1 is maintained in the existing synthesis gas. The synthesis gas product stream produced in the generator 16 is conducted by the conduit 36 through the heat exchanger 10, then through the heat exchanger 22 and then to the inlet connection of a first hydrocarbon synthesis reactor 38. Upon exiting the generator 16, the synthesis gas is at a temperature in the range of from about 1000° F. to about 2000° F. As the synthesis gas stream flows through the heat exchanger 10 on conduit 36 it gives up heat to the feed light hydrocarbon stream. The light hydrocarbon stream in conduit 14 is preheated to a temperature in the range of from about 500° F. to about 1000° F. In a like manner, as the synthesis gas stream flows through the heat exchanger 22 on conduit 36, it gives up heat to the air flowing to the generator 16 through conduit 24 whereby the air is also preheated to a temperature in the range of from about 500° F. to about 1000° F. Additional cooling of the synthesis gas stream is provided by a cooler or heat exchanger 23 disposed in the conduit 36 whereby the temperature of the synthesis gas entering the reactor 38 is then in the range of from about 350° F. to about 550° F.
In the hydrocarbon synthesis case, reactor 38 can take various forms, but in the embodiment shown is a tubular reactor containing a fixed bed 37 of hydrocarbon synthesis catalyst. The catalyst of bed 37 may be of cobalt supported on silica, alumina or silica-alumina material in an amount in the range of from about 5 to about 50 parts by weight of cobalt per 100 parts by weight of the support material. The catalyst may also contain in the range of from about 0.05 to about 1 parts by weight of ruthenium per 100 parts by weight of support material as a promoter. The synthesis gas stream flows into and through the reactor 38. The gas is delivered by conduit 36 and carried on its way by conduit 40. As mentioned above, the temperature within the reactor 38 is in the range of from about 350° F. to about 550° F., and upon contact with the catalyst, hydrogen and carbon monoxide in the synthesis gas stream react to form heavier hydrocarbons and water.
The product stream produced in the reactor 38 exits the reactor by way of a conduit 40 connected thereto. Conduit 40 leads the stream to a condenser 42. While flowing through the condenser 42, the heavier hydrocarbons and water contained in the stream are condensed. From the condenser 42, a conduit 44 conducts the stream containing condensed components to a separator 46 wherein the condensed heavier hydrocarbons and water are separated and separately withdrawn. That is, the condensed water is withdrawn from the separator 46 by way of a conduit 48 connected thereto, and the condensed heavier hydrocarbons are withdrawn from the separator 46 by way of a conduit 50 connected thereto.
A residue gas stream from the separator 46 includes nitrogen and unreacted hydrogen, carbon monoxide, light hydrocarbons and carbon dioxide . A conduit 52 connected to the separator 46 leads the residue gas stream from the separator 46 to a second hydrocarbon synthesis reactor 54 containing a fixed bed 56 of a hydrocarbon synthesis catalyst, such as the one described above. The pressure and temperature of the gas stream flowing through the reactor 54 are maintained at approximately the same levels as the pressure and temperature within the reactor 38 by means of a heater or heat exchanger 58 disposed in the conduit 52 between the separator 46 and reactor 54. While flowing through the reactor 54, additional heavier hydrocarbons are formed from hydrogen and carbon monoxide in the residue gas stream and the resulting product stream exits the reactor 54 by way of a conduit 60 connected thereto. The conduit 60 leads the stream to a condenser 62 wherein heavier hydrocarbons and water contained therein are condensed. From the condenser 62, the stream containing condensed components is conducted to a chiller 66 of a refrigeration unit by a conduit 64 wherein additional hydrocarbons and water are condensed. The resulting stream is conducted from the chiller 66 to a separator 70 by a conduit 68 connected therebetween. Separator 70 will have water, heavier hydrocarbons, and residue gas exit through three conduits. Water is withdrawn from the separator 70 by a conduit
72 connected thereto. The conduit 72 is in turn connected by way of conventional valves and controls (not shown) to the conduit 48, to a drain conduit 31 and to the conduit 32 previously described whereby all or part of the condensed water separated in the separators 46 and 70 is selectively conducted to the synthesis gas generator 16.
The condensed heavier hydrocarbons separated within the separator 70 are withdrawn therefrom by a conduit 74 which connects to the conduit 50 from the separator 46. The conduit 50 leads the heavier hydrocarbons from both the separators 46 and 70 to a conventional fractionation unit 76. A hydrocarbon product stream containing selected components is withdrawn from the fractionation unit 76 by way of a conduit 78 which conducts the product stream to storage or other location. Undesirable light and heavy hydrocarbon fractions produced in the fractionation unit 76 are withdrawn therefrom by conduits 80 and 82, respectively. The conduits 80 and 82 connect to a conduit 84 which conducts the undesirable hydrocarbons to the inlet conduit 12 where they mix with the feed stream of gaseous light hydrocarbons and are recycled.
The residue gas stream produced in the separator 70, which may include nitrogen and unreacted hydrogen, carbon monoxide, light hydrocarbons and carbon dioxide, is withdrawn therefrom by a conduit 86 which leads the residue gas stream to a catalytic combustor 88. The catalytic combustor 88 may include a burner 90 into which the residue gas stream is conducted.
A stream of air is conducted to the burner 90 by a conduit 92 connected to the discharge of an air blower 94. The residue gas stream from the separator 70 and the air conducted to the burner 90 are intimately mixed therein, ignited and discharged into a reactor 96 connected to the burner 90.
The reactor 96 contains a fixed bed of suitable nobel metal containing catalyst 98, e.g., platinum or palladium, for promoting and catalyzing the oxidation of the oxidizable components in the residue gas stream. As a result of such oxidation an oxidation product stream including carbon dioxide, water vapor and nitrogen is produced and withdrawn from the combustor 88 by a conduit 100 connected thereto. The conduit 100 optionally leads the product stream to a conventional carbon dioxide removal unit 102. Carbon dioxide and water are removed from the stream by the carbon dioxide removal unit 102 thereby producing a relatively pure nitrogen product stream which is conducted from the unit 102 by a conduit 104 to a location of sale, storage or further processing.
The carbon dioxide removed by the unit 102 is withdrawn therefrom by a conduit 106 which leads the carbon dioxide to a compressor 108. The discharge of the compressor 108 is connected by way of conventional valves and controls (not shown) to a vent 35 and to the conduit 34 previously described whereby all or part of the carbon dioxide is selectively introduced into the synthesis gas generator 16.
As previously described, the flow rates of the water conducted to the synthesis gas generator 16 by way of the conduit 32 and carbon dioxide conducted thereto by way of the conduit 34 are varied as is necessary to control the ratio of hydrogen to carbon monoxide in the synthesis gas stream produced to as close to 2:1 as possible. This in turn improves the efficiency of the hydrocarbon synthesis reactions carried out in the reactors 38 and 54. Further, the use of air, delivered by conduit 24, in the synthesis gas generator 16 as the source of oxygen for the partial oxidation reaction carried out therein produces nitrogen in the synthesis gas stream. Such nitrogen acts as a diluent in the hydrocarbon synthesis reactors 38 and 54 and prevents hot spots on the catalyst and further increases the efficiency of the hydrocarbon synthesis reactions. The nitrogen together with the additional nitrogen produced in the catalytic combustor 88, after carbon dioxide removal, form a relatively pure nitrogen product stream. In addition, the recycling of all or part of the optional carbon dioxide, which is transported in conduit 106 provides additional carbon for producing heavier hydrocarbons and increases overall process efficiency.
The system of FIGURE 1 can include a gas turbine as will be further described below in connection with FIGURE 2. As an example of one way the system of FIGURE 1 can be configured, catalytic combustor 88, the burner 90, the blower 94, and air compressor 18 may be removed and replaced with a gas turbine. The gas turbine could include a combustor to burn the gas and the compressor section of the gas turbine could provide combustion air as blower 94 previously did and compressed air as compressor 18 previously did. Other examples will be given further below.
Referring now to FIGURE 2, another illustrative system 200 for the conversion of lighter hydrocarbons to heavier hydrocarbons is shown. System 200 combines a synthesis gas unit 202 with a synthesis unit 204 and a gas turbine 206. System 200 uses gas turbine 206 to provide power for the process at a minimum, but is preferably designed to provide at least some additional power. Gas turbine 206 has a compressor section 208 and an expansion turbine section 210. The power generated by the expansion turbine section 210 drives the compressor section 208 by means of linkage 212, which may be a shaft, and any excess power beyond the requirements of compressor section 208 may be used to generate electricity or drive other equipment as figuratively shown by output 214. Compressor section 208 has inlet or conduit 216, where in the embodiment shown compressor 208 receives air. Compressor section 208 also has an outlet or conduit 218 for releasing compressed air. Expansion turbine 210 has inlet or conduit 220 and outlet or conduit 222. Outlet 218 of compressor section 208 provides compressed air to synthesis gas unit 202 through conduit 260.
Synthesis gas unit 202 may take a number of configurations, but in the specific embodiment shown, includes syngas reactor 224, which as shown here may be an autothermal reforming reactor. A stream of gaseous light hydrocarbons, e.g., a natural gas stream, is delivered to syngas reactor 224 by inlet or conduit 225. In some instances it may be desirable to use natural gas containing elevated levels of components, e.g., N2, CO, He, etc. that reduce the BTU value of the gas in conduit 225. The synthesis gas unit 202 may also include one or more heat exchangers 226, which in the embodiment shown is a cooler for reducing the temperature of the synthesis gas exiting outlet 228 of syngas reactor 224. Heat exchanger 226 delivers its output to inlet 230 of separator 232. Separator 232 removes moisture which is delivered to outlet 234. It may be desirable in some instances to introduce the water in conduit 234 as steam to expansion turbine 210. Synthesis gas exits separator 232 through outlet or conduit 236. The synthesis gas exiting through outlet 236 is delivered to synthesis unit 204.
Synthesis unit 204 may be used to synthesize a number of materials as previously mentioned, but in the specific example here is used to synthesize heavier hydrocarbons as referenced in connection with FIGURE 1. Synthesis unit 204 includes Fischer-Tropsch reactor 238, which contains an appropriate catalyst. The output of Fischer-Tropsch reactor 238 is delivered to outlet 240 from which it travels to heat exchanger 242 and on to separator 244. The product entering separator 244 is first delivered to inlet 246. Separator 244 distributes the heavier hydrocarbons separated therein to storage tank or container 248 through outlet or conduit 250. Conduit 250 may include additional components such as a conventional fractionation unit as shown in FIGURE 1. Water withdrawn from separator 244 is delivered to outlet or conduit 252. It may be desirable in some instances to deliver the water in conduit 252 as steam into expansion turbine 210. The residue gas from separator 244 exits through outlet or conduit 254. System 200 includes a combustor 256. Combustor 256 receives air from compression section 208 delivered through conduit 258 which is fluidly connected to conduit 260 connecting outlet 218 with syngas reactor 224. The conduit 260 beyond the juncture with conduit 258 delivers bleed air to the autothermal reformer 224. Also, residue gas delivered by separator 244 into conduit 254 is connected to combustor 256. Residue gas within conduit 254 is delivered to conduit 258 and then to combustor 256. Intermediate conduit 260 and the connection of conduit 254 with conduit 258 may be a valve (not explicitly shown) for dropping the pressure delivered from compressor section 208 to combustor 256 in order to match the pressure in conduit 254 as necessary. The output of combustor 256 is delivered to expansion turbine 210. In some embodiments, combustor 256 may be incorporated as part of gas turbine 206 itself. Alternatively, the pressure in conduits 260 and 254 may be increased by a compressor to match or exceed the pressure requirements of combustor 256. C. COMBINATION AUTOTHERMAL REFORMER AND TURBINE
Referring now to FIGURE 3, there is shown a synthesis gas production system 300 according to an aspect of the present invention has an autothermal-reformer-turbine unit 302. Synthesis gas production system 300 may be included as part of system 304 for converting lighter hydrocarbons that further includes a synthesis unit 306.
Autothermal-reformer-turbine unit 302 includes an autothermal reformer (ATR) 308 and gas turbine 310. Gas turbine 310 includes a compressor section 312 and an expansion turbine section 314. The power generated by the expansion turbine section 314 drives the compressor section 312 by means of linkage 316, which may be a shaft. This embodiment preferably has an exact energy balance, but if excess energy is developed, it may be removed from gas turbine 310 with an additional shaft extending from expansion section 314 as shown in FIGURE 4. Compressor section 312 has inlet or conduit 318, where compressor 312 receives air. Compressor 312 also has an outlet or conduit 320 for releasing compressed air. The expansion turbine section 314 has inlet or conduit 322 and outlet or conduit 324. Outlet 324 of compressor section 314 provides compressed synthesis gas into conduit 336.
Autothermal reformer 308 produces synthesis gas, but also serves as the combustor of gas turbine 310. Compressor section 312 develops compressed air that is delivered to outlet 320, which is delivered to first separator 326, which will be described further below. After traveling through separator 326, compressed air is delivered by way of conduit 328 to ATR 308. In addition, gaseous light hydrocarbons, such as natural gas, are delivered to conduit 328 from conduit 330 and the residue gas is also delivered through conduit 332 into a portion of conduit 330 and then to conduit 328 and ATR 308. An issue in the performance of gas turbines is the balancing of the axial loads on the shaft between the compressor section and the expansion section. The present invention may realize the most efficient results by the inclusion of thrust bearings in gas turbine 310 that allow for a substantial imbalance between compressor section 312 and expansion section 314. In order to use a preexisting turbine, however, unit 302 may provide for balancing of the loads within the turbine manufacturer's specifications. This may be accomplished with first separator 326 or by bleeding air as will be described. The balancing, may be thought of as balancing the mass that is received in the compressor section with the mass received by the turbine section or some percentage thereof.
In the present invention, unit 302 receives additional mass from conduits 330 and 332 between compressor section 312 and expansion section 314 that would cause an imbalance without provisions being made. To address this, separator 326 may remove mass by separating out nitrogen or bleeding off a portion of the compressed air as suggested by FIGURE 3. Separator 326 may include separation technology such as a membrane or carbon absorption or any other technique suitable for the removal of nitrogen or other substances not needed by ATR 308. In embodiments with sufficiently strong thrust bearings in compressor 312 and turbine 314, no separator 326 or device for bleeding air is required. ATR 308 will receive air and/or enriched air from conduit 328 along with the gaseous light hydrocarbons and residual gasses from conduits 330 and 332, respectively. ATR 308 will then autothermally reform the gas before delivering synthesis gas to conduit 334. The amount of gas delivered and produced by ATR 308 may be notably higher than that which would normally be expected from a normal gas-turbine combustor. ATR 308 does not fully combust or react the gas, but because of the larger volumes of gas delivered to ATR 308, an adequate amount of energy may be produced by expansion section 314. The ATR 308 will have an exit temperature in conduit 304 within an acceptable range for input into expansion section 314.
The gas delivered to ATR 308 may further be controlled to establish the proper ratios for ATR 308 such that the oxygen disappears and everything substantially goes to CO or C02. To control the gas that is delivered to ATR 308, one or more control valves, which are represented by control valve 331, may be used to control the ratio of gaseous light hydrocarbons to air entering ATR 308. Outlet 324 of expansion section 314 delivers its products to conduit 336 which fluidly connects with heat exchanger or cooler 338. Then, the process continues from cooler 338 to conduit 340 and second separator 342. The synthesis gas, which will contain some combustion products and/or a nitrogen diluted gas, is delivered to expansion section 314 and expanded before exiting outlet 324. Cooler 338 further cools the gas which will condense at least some water from the gas. In this example, a Fischer-Tropsch process is presented, and the separator 342 will be desirable. The water condensed by the gas as it travels through the expansion section 314 and cooler 338, should be removed prior to delivering the product to second compressor 348. Thus, separator 342 includes drain 344 for the removal of water. The gaseous product leaving separator 342 is delivered by conduit 346 to compressor 348.
The syngas exiting expansion section 314 of gas turbine 310 may need to be pressurized before entering the Fischer-Tropsch reactor 350, and thus, compressor 348 may be added. Separator 342 removed the liquids that may have condensed prior to the compressor 348. Compressor 348 may be driven in a number of different ways. If the thrust bearings of gas turbine 310 allow for a sufficient imbalance for gas turbine 310 to create excess energy, a direct linkage 400 between expansion section 314 and compressor 348 may be utilized as shown in FIGURE 4. If excess energy is not available from gas turbine 310 in adequate quantities, the excess energy may be used along with a supplement.
Compression and compressor 348 should adequately heat the gas existing to conduit 352 sufficiently for entry into Fischer-Tropsch reactor 350. The input to reactor 350 is preferably in the general range of 350° F. to 500° F. In some situations, it may be desirable to add a heat exchanger between compressor 348 and Fischer-Tropsch reactor 350 to further heat the gas therein.
Conduit 352 fluidly connects compressor 348 with reactor 350. Reactor 350, for this example, may be a Fischer-Tropsch reactor which contains an appropriate catalyst. Other reactors may be used with other processes as previously noted. The output of Fischer-Tropsch' s reactor 350 is delivered to outlet 354 of conduit 356 connecting with heat exchanger 358. After heat exchanger 358, the product is delivered via conduit 360 to third separator 362. The heavier hydrocarbons separated in separator 362 are then delivered to storage tank or container 364 by conduit 368. The residual gas is delivered to conduit 370. Separator 362 will also remove water which is delivered to conduit 372 for the case of a Fischer-Tropsch process. Conduit 370 delivers the residual gas to separator
374, which utilizes a separation process such as a membrane or carbon absorption or centrifugal process or other separation devices. For the instance of the Fischer Tropsch example, nitrogen may be removed from the methane. The output of separator 374 is delivered into conduit 332, which as previously noted delivers to ATR 308. In the preferred embodiment, the residual gas is completely consumed back into ATR 308 since the energy balance of the system is zero, or even a slight amount of additional energy is needed for a second compressor 348. Referring now to FIGURE 5, there is shown another embodiment of the present invention. Fischer-Tropsch system 500 includes synthesis gas production system 501 and a Fischer-Tropsch reactor 550. In this embodiment, compressed air is delivered through conduit 518 to compressor 512. Compressor 512 delivers compressed air to conduit 520. Conduit 520 delivers compressed air to autothermal reformer 508. Gaseous light hydrocarbons are delivered to conduit 520 and ultimately to ATR 508 by conduit 530. Because the addition of mass to the flow between compressor 512 and turbine 514, the thrust bearings associated with link 516 between compressor 512 and turbine 514 must be adequate to handle the imbalance, or a sufficient amount of mass will need to be removed to allow the thrust bearings to be within their specifications for an imbalance force. To remove the mass, if required, a separator removing nitrogen or a mechanism for bleeding a portion of the compressed air may be installed on conduit 520 as shown by reference numeral 526. The synthesis gas exiting ATR 508 is delivered to turbine 514 by conduit 534. The gas exiting turbine 514 enters conduit 536, which delivers it to Fischer-Tropsch' s reactor 550. In this embodiment, the turbine may decrease the pressure of a synthesis gas entering turbine 514 down to a lesser, non- zero number as it exits into conduit 536. For example, it may exit at 50 psi before being delivered to reactor 550. While a higher pressure may be desired for reactor 550, sufficiently active catalysts may be utilized in reactor 550 such that the performance of reactor 550 is adequate at the lower pressure. This system will obviate the need for a second compressor. Thus, while reactor 550 may not perform at optimum output, the reduced capital cost of removing a compressor may make operation in this mode desirable. Although the present invention has been described in detail with respect to alternative embodiments, various changes and modifications may be suggested to one skilled in the art, and it should be understood that various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

WHAT IS CLAIMED IS:
1. A synthesis gas production system comprising: a compressor; an autothermal reformer fluidly coupled to the compressor for producing synthesis gas; and an expansion turbine section fluidly coupled to the autothermal reformer for developing energy with the gas from the autothermal reformer.
2. The system of Claim 1 further comprising a separator fluidly coupled to the compressor and autothermal reformer for selectively removing mass from the gas flow therethrough.
3. The system of Claim 2 wherein the separator comprises an nitrogen separator fluidly coupled to the compressor and autothermal reformer for selectively removing nitrogen from the gas flow therethrough.
4. The system of Claim 1 further comprising a first conduit fluidly coupled to the autothermal reformer for delivering gaseous light hydrocarbons thereto.
5. The system of Claim 4 further comprising a valve on the first conduit for selectively controlling the gaseous light hydrocarbons delivered to the autothermal reformer.
6. The system of Claim 1 wherein the compressor and expansion turbine comprise a single gas turbine.
7. The system of Claim 6 wherein the gas turbine further comprises the autothermal reformer as a combustor for the gas turbine.
8. The system of Claim 1 wherein the autothermal reformer is operable to autothermally reform a gas to produce a synthesis gas and to adiabatically expand a gas to provide to the turbine section.
9. The system of Claim 1 wherein the autothermal reformer is operable to autothermally reform a gas to produce a synthesis gas and to produce a nitrogen diluted gas for powering the turbine section.
10. The system of Claim 1 wherein the compressor is operable to receive air, compress air, and deliver air to the autothermal reformer.
11. The system of Claim 1 wherein the compressor is operable to receive enriched air, compress enriched air, and deliver enriched air to the autothermal reformer.
12. The system of Claim 1 wherein the compressor is operable to receive an air-and-enriched-air gas, compress an air-and-enriched-air gas, and deliver an air-and- enriched-air gas to the autothermal reformer.
13. A system for converting lighter hydrocarbons to heavier hydrocarbons, the system comprising: a synthesis gas production unit including: a first compressor, an autothermal reformer fluidly coupled to the first compressor for producing synthesis gas and combusting at least a portion the gas therein, and an expansion turbine section fluidly coupled to the autothermal reformer for developing energy with the gas from the autothermal reformer; and a synthesis unit fluidly coupled to the expansion turbine section for receiving the synthesis gas therefrom and producing heavier hydrocarbons.
14. The system of Claim 13 further comprising a separator fluidly coupled to the first compressor and autothermal reformer for selectively removing mass from the gas flow therethrough.
15. The system of Claim 14 wherein the separator comprises an nitrogen separator fluidly coupled to the first compressor and autothermal reformer for selectively removing nitrogen from the gas flow therethrough.
16. The system of Claim 13 further comprising a first conduit fluidly coupled to the autothermal reformer for delivering gaseous light hydrocarbons thereto.
17. The system of Claim 16 further comprising a valve on the first conduit for selectively controlling the gaseous light hydrocarbons delivered to the autothermal reformer.
18. The system of Claim 16 wherein the synthesis unit comprises : a second compressor for receiving synthesis gas from the synthesis production unit and elevating a pressure of the synthesis gas, the second compressor coupled to the expansion turbine section to receive power therefrom; and a synthesis reactor coupled to the second compressor for receiving the synthesis gas therefrom and producing heavier hydrocarbons.
19. The system of Claim 13 wherein the compressor and expansion turbine comprise a single gas turbine.
20. The system of Claim 13 wherein the gas turbine further comprises the autothermal reformer that is operable to serve as a combustor for the gas turbine.
21. The system of Claim 13 wherein the autothermal reformer is operable to autothermally reform a gas to produce a synthesis gas and to adiabatically expand a gas to provide to the turbine section.
22. The system of Claim 13 wherein the autothermal reformer is operable to autothermally reform a gas to produce a synthesis gas and to produce a nitrogen diluted gas for powering the turbine section.
23. The system of Claim 13 wherein the compressor is operable to receive air, compress air, and deliver air to the autothermal reformer.
24. The system of Claim 13 wherein the compressor is operable to receive enriched air, compress enriched air, and deliver enriched air to the autothermal reformer.
25. The system of Claim 13 wherein the compressor is operable to receive an air-and-enriched-air gas, compress an air-and-enriched-air gas, and deliver an air-and- enriched-air gas to the autothermal reformer.
26. A method of manufacturing synthesis gas production system comprising the steps of:
Providing a compressor; fluidly coupling an autothermal reformer to the compressor for producing synthesis gas and combusting at least a portion of the gas therein; and fluidly coupling an expansion turbine section to the autothermal reformer for developing energy with the gas from the autothermal reformer.
27. The method of Claim 26 further comprising the step of fluidly coupling a separator to the compressor and autothermal reformer for selectively removing mass from the gas flow therethrough.
28. The method of Claim 26 further comprising the step of fluidly coupling a first conduit to the autothermal reformer for delivering gaseous light hydrocarbons thereto.
29. The method of Claim 28 further comprising attaching a valve on the first conduit for selectively controlling the gaseous light hydrocarbons delivered to the autothermal reformer.
PCT/US1997/010733 1996-06-21 1997-06-20 Synthesis gas production system and method WO1997048639A1 (en)

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EA199900039A EA001466B1 (en) 1996-06-21 1997-06-20 Synthesis gas production system and method
AU34960/97A AU740616B2 (en) 1996-06-21 1997-06-20 Synthesis gas production system and method
BR9709857-4A BR9709857A (en) 1996-06-21 1997-06-20 Synthesis gas production process and system
NO985973A NO985973L (en) 1996-06-21 1998-12-18 A system and method for producing synthesis gas

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0950636A2 (en) * 1998-04-16 1999-10-20 Haldor Topsoe A/S Process for the combined production of hydrogen rich gas and electrical power
EP0950637A2 (en) * 1998-04-16 1999-10-20 Haldor Topsoe A/S Process and unit for the combined production of ammonia synthesis gas and power
EP0989093A2 (en) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products
FR2796932A1 (en) * 1999-07-29 2001-02-02 Inst Francais Du Petrole Plant for production of synthesis gas from natural gas and air or oxygen diluted with inert gas comprises at least one reactor for preparation of synthesis gas and at least one compressor with power turbine
WO2001021527A1 (en) * 1999-09-23 2001-03-29 Syntroleum Corporation Process for supplying a gaseous mixture to an autothermal reactor
DE10053778A1 (en) * 2000-10-30 2002-05-08 Alstom Switzerland Ltd Production of synthesis gas containing hydrogen and carbon monoxide, especially for methanol production, uses thermodynamic cycle to recover much of enthalpy of gas leaving reformer at high temperature and pressure
WO2003062142A1 (en) * 2002-01-16 2003-07-31 Johnson Matthey Plc Process for the production of hydrocarbons
US9021814B2 (en) 2009-05-22 2015-05-05 Sasol Technology (Proprietary) Limited Process for co-producing synthesis gas and power
US9062260B2 (en) 2008-12-10 2015-06-23 Chevron U.S.A. Inc. Removing unstable sulfur compounds from crude oil
CN110028082A (en) * 2018-01-08 2019-07-19 诺沃皮尼奥内技术股份有限公司 Ammonia production equipment

Families Citing this family (71)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5938975A (en) 1996-12-23 1999-08-17 Ennis; Bernard Method and apparatus for total energy fuel conversion systems
EP1149140A1 (en) * 1998-12-07 2001-10-31 Syntroleum Corporation Structured fischer-tropsch catalyst system and method for its application
US6715546B2 (en) 2000-04-24 2004-04-06 Shell Oil Company In situ production of synthesis gas from a hydrocarbon containing formation through a heat source wellbore
US6715548B2 (en) 2000-04-24 2004-04-06 Shell Oil Company In situ thermal processing of a hydrocarbon containing formation to produce nitrogen containing formation fluids
US6698515B2 (en) 2000-04-24 2004-03-02 Shell Oil Company In situ thermal processing of a coal formation using a relatively slow heating rate
US6588504B2 (en) 2000-04-24 2003-07-08 Shell Oil Company In situ thermal processing of a coal formation to produce nitrogen and/or sulfur containing formation fluids
US6752210B2 (en) 2000-04-24 2004-06-22 Shell Oil Company In situ thermal processing of a coal formation using heat sources positioned within open wellbores
US6921595B2 (en) * 2000-05-31 2005-07-26 Nuvera Fuel Cells, Inc. Joint-cycle high-efficiency fuel cell system with power generating turbine
US6916564B2 (en) * 2000-05-31 2005-07-12 Nuvera Fuel Cells, Inc. High-efficiency fuel cell power system with power generating expander
WO2002028770A1 (en) 2000-10-02 2002-04-11 Chevron U.S.A. Inc. Process for reducing coke formation in hydrocarbon processing by application of radio frequency electromagnetic radiation
US20020077512A1 (en) * 2000-12-20 2002-06-20 Tendick Rex Carl Hydrocarbon conversion system and method with a plurality of sources of compressed oxygen-containing gas
US7051811B2 (en) 2001-04-24 2006-05-30 Shell Oil Company In situ thermal processing through an open wellbore in an oil shale formation
US7100994B2 (en) 2001-10-24 2006-09-05 Shell Oil Company Producing hydrocarbons and non-hydrocarbon containing materials when treating a hydrocarbon containing formation
AU2002359575A1 (en) * 2001-12-05 2003-06-23 Lawrence G. Clawson High efficiency otto cycle engine with power generating expander
AU2003219821A1 (en) * 2002-02-22 2003-09-09 Chevron U.S.A. Inc. Process for reducing metal catalyzed coke formation in hydrocarbon processing
EA009586B1 (en) 2002-10-24 2008-02-28 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Temperature limited heaters for heating subsurface formations or wellbores
US20040157940A1 (en) * 2003-02-07 2004-08-12 Dalton Robert C. Method of transport energy
US8277525B2 (en) * 2003-02-07 2012-10-02 Dalton Robert C High energy transport gas and method to transport same
US6939999B2 (en) * 2003-02-24 2005-09-06 Syntroleum Corporation Integrated Fischer-Tropsch process with improved alcohol processing capability
FR2852358B1 (en) * 2003-03-13 2006-06-09 METHOD AND DEVICE FOR COGENERATION BY GAS TURBINE WITH POSTCOMBUSTION CHAMBER
NZ543753A (en) 2003-04-24 2008-11-28 Shell Int Research Thermal processes for subsurface formations
US20060189702A1 (en) 2003-08-06 2006-08-24 Tomlinson H L Movable gas-to-liquid system and process
US20050106086A1 (en) 2003-08-06 2005-05-19 Tomlinson H. L. Movable gas-to-liquid system and process
US7399329B2 (en) * 2003-08-22 2008-07-15 Syntroleum Corporation Process for production of synthesis gas using an oxygen-containing gas
US6982355B2 (en) * 2003-08-25 2006-01-03 Syntroleum Corporation Integrated Fischer-Tropsch process for production of linear and branched alcohols and olefins
BRPI0506746A (en) * 2004-01-08 2007-05-22 Syntroleum Corp start-up process for autothermal reformer
WO2005097949A1 (en) * 2004-03-30 2005-10-20 Syntroleum Corporation Transportable gas to liquid plant
US20070021513A1 (en) * 2004-03-30 2007-01-25 Kenneth Agee Transportable gas-to-liquid plant
AU2005236490B2 (en) 2004-04-23 2009-01-29 Shell Internationale Research Maatschappij B.V. Subsurface electrical heaters using nitride insulation
US7434547B2 (en) * 2004-06-11 2008-10-14 Nuvera Fuel Cells, Inc. Fuel fired hydrogen generator
DE102004049076A1 (en) * 2004-10-08 2006-04-13 Uhde Gmbh Process for the production of synthesis gas for an ammonia plant
US20060149423A1 (en) * 2004-11-10 2006-07-06 Barnicki Scott D Method for satisfying variable power demand
WO2006058107A1 (en) 2004-11-22 2006-06-01 Syntroleum Corporation Movable gas-to-liquid system and process
GB0502608D0 (en) * 2005-02-09 2005-03-16 Rolls Royce Plc A fuel processor
US7435037B2 (en) 2005-04-22 2008-10-14 Shell Oil Company Low temperature barriers with heat interceptor wells for in situ processes
US20070006566A1 (en) * 2005-07-05 2007-01-11 General Electric Company Syngas turbine
US7266940B2 (en) * 2005-07-08 2007-09-11 General Electric Company Systems and methods for power generation with carbon dioxide isolation
US7591310B2 (en) 2005-10-24 2009-09-22 Shell Oil Company Methods of hydrotreating a liquid stream to remove clogging compounds
CA2649379C (en) 2006-04-21 2016-08-23 Shell Internationale Research Maatschappij B.V. Heating systems and methods using high strength alloys
WO2007127898A2 (en) * 2006-04-27 2007-11-08 Syntroleum Corporation Method of delivery, replacement, and removal of fischer-tropsch catalyst
US20070259973A1 (en) * 2006-05-03 2007-11-08 Syntroleum Corporation Optimized hydrocarbon synthesis process
US20080021118A1 (en) * 2006-07-21 2008-01-24 Syntroleum Corporation Hydrocarbon recovery in the fischer-tropsch process
WO2008051831A2 (en) 2006-10-20 2008-05-02 Shell Oil Company Heating hydrocarbon containing formations in a line drive staged process
US7910629B2 (en) * 2006-10-20 2011-03-22 Exxonmobil Research And Engineering Company Light ends recovery process for a GTL plant
US20080260631A1 (en) 2007-04-18 2008-10-23 H2Gen Innovations, Inc. Hydrogen production process
WO2008131177A1 (en) 2007-04-20 2008-10-30 Shell Oil Company In situ heat treatment of a tar sands formation after drive process treatment
CA2791963C (en) 2007-09-25 2014-01-14 Bogdan Wojak Methods and systems for transporting sulphur as cos
US8536497B2 (en) 2007-10-19 2013-09-17 Shell Oil Company Methods for forming long subsurface heaters
CA2718767C (en) 2008-04-18 2016-09-06 Shell Internationale Research Maatschappij B.V. Using mines and tunnels for treating subsurface hydrocarbon containing formations
US20100155070A1 (en) 2008-10-13 2010-06-24 Augustinus Wilhelmus Maria Roes Organonitrogen compounds used in treating hydrocarbon containing formations
US8327932B2 (en) 2009-04-10 2012-12-11 Shell Oil Company Recovering energy from a subsurface formation
US8875788B2 (en) 2010-04-09 2014-11-04 Shell Oil Company Low temperature inductive heating of subsurface formations
US8701769B2 (en) 2010-04-09 2014-04-22 Shell Oil Company Methods for treating hydrocarbon formations based on geology
US9033042B2 (en) 2010-04-09 2015-05-19 Shell Oil Company Forming bitumen barriers in subsurface hydrocarbon formations
US8631866B2 (en) 2010-04-09 2014-01-21 Shell Oil Company Leak detection in circulated fluid systems for heating subsurface formations
US20120055168A1 (en) 2010-09-08 2012-03-08 General Electric Company System and method for producing hydrogen rich fuel
US8631660B2 (en) * 2011-03-23 2014-01-21 General Electric Company Integrated gasification combined cycle system with vapor absorption chilling
US9016370B2 (en) 2011-04-08 2015-04-28 Shell Oil Company Partial solution mining of hydrocarbon containing layers prior to in situ heat treatment
US20130306573A1 (en) 2011-07-19 2013-11-21 Jacob G. Appelbaum System and method for cleaning hyrocarbon contaminated water
WO2013052561A2 (en) 2011-10-07 2013-04-11 Shell Oil Company Thermal expansion accommodation for circulated fluid systems used to heat subsurface formations
CA2898956A1 (en) 2012-01-23 2013-08-01 Genie Ip B.V. Heater pattern for in situ thermal processing of a subsurface hydrocarbon containing formation
CA2862463A1 (en) 2012-01-23 2013-08-01 Genie Ip B.V. Heater pattern for in situ thermal processing of a subsurface hydrocarbon containing formation
WO2014039095A1 (en) * 2012-09-07 2014-03-13 Afognak Native Corporation Systems and processes for producing liquid transportation fuels
RU2527536C1 (en) * 2013-02-06 2014-09-10 Кирячек Владимир Георгиевич Method of processing hydrocarbon gas into stable liquid synthetic petroleum products and energy complex for its realisation
US9527736B2 (en) * 2013-03-27 2016-12-27 General Electric Company System and method for generating nitrogen from a gas turbine
EA036747B1 (en) 2014-02-28 2020-12-16 Хальдор Топсёэ А/С Process for the production of synthesis gas
DE102014006996A1 (en) * 2014-05-13 2015-11-19 CCP Technology GmbH Process and apparatus for the production of synthetic hydrocarbons
US20160096998A1 (en) * 2014-09-23 2016-04-07 Community Power Corporation Processes and systems for producing liquid transportation fuels
US10836634B1 (en) 2019-03-21 2020-11-17 Emerging Fuels Technology, Inc. Integrated GTL process
EP3715320A1 (en) * 2019-03-27 2020-09-30 Siemens Aktiengesellschaft Method for generating a gas-product
US11220473B1 (en) 2021-02-19 2022-01-11 Emerging Fuels Technology, Inc. Integrated GTL process

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139644A (en) * 1983-04-06 1984-11-14 Ici Plc Synthesis gas
EP0212755A2 (en) * 1985-08-30 1987-03-04 Shell Internationale Researchmaatschappij B.V. Process and apparatus for producing synthesis gas
EP0497425A1 (en) * 1991-01-30 1992-08-05 Shell Internationale Researchmaatschappij B.V. Process for the combined production of organic compounds and power
JPH04364142A (en) * 1991-06-10 1992-12-16 Chiyoda Corp Synthetic process for methanol and its plant
WO1993006041A1 (en) * 1991-09-19 1993-04-01 Starchem, Inc. Process for producing and utilizing an oxygen enriched gas
WO1997033847A1 (en) * 1996-03-11 1997-09-18 Syntroleum Corporation Turbine-powered, synthesis-gas system and method

Family Cites Families (95)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE414019A (en) *
US1746464A (en) * 1925-07-21 1930-02-11 Fischer Franz Process for the production of paraffin-hydrocarbons with more than one carbon atom
US1798288A (en) * 1926-06-23 1931-03-31 Ig Farbenindustrie Ag Production of hydrocarbons of high-boiling-point range
US2247087A (en) * 1936-11-30 1941-06-24 American Lurgi Corp Process for the production of hydrocarbons
FR871230A (en) * 1938-10-26 1942-04-13 Metallgesellschaft Ag Converter for catalytic reactions
US2468494A (en) * 1944-12-07 1949-04-26 Standard Oil Dev Co Hydrocarbon synthesis
FR922493A (en) 1945-04-13 1947-06-10 Standard Oil Dev Co Gasoline manufacturing process
US2552737A (en) * 1945-05-25 1951-05-15 Texaco Development Corp Process for producing synthesis gas
US2518337A (en) * 1946-04-26 1950-08-08 Standard Oil Dev Co Slurry handling
US2583611A (en) * 1946-07-13 1952-01-29 Hydrocarbon Research Inc Method for the synthesis of hydrocarbons in the presence of a solid adsorbent
US2500533A (en) * 1946-09-06 1950-03-14 Phillips Petroleum Co Preparation of solid hydrocarbons
US2472427A (en) * 1947-02-27 1949-06-07 Standard Oil Co Hydrocarbon synthesis with fluidized catalyst regeneration
US2615911A (en) * 1947-03-21 1952-10-28 Kellogg M W Co Synthesis of organic compounds
US2660032A (en) * 1947-10-04 1953-11-24 Rosenthal Henry Gas turbine cycle employing secondary fuel as a coolant
US2697655A (en) * 1947-12-31 1954-12-21 Kellogg M W Co Manufacture of a hydrogen-rich gas
US2486243A (en) * 1948-01-06 1949-10-25 Texas Co Simultaneous dehydrogenation and hydrocarbon synthesis with fluidized catalysts in a single reactor
US2579828A (en) * 1948-05-12 1951-12-25 Kellogg M W Co Synthesis of organic compounds
US2640843A (en) * 1948-06-15 1953-06-02 Kellogg M W Co Synthesis of organic compounds
US2552308A (en) * 1949-06-16 1951-05-08 Standard Oil Dev Co Low-pressure hydrocarbon synthesis process
US2686195A (en) * 1949-12-10 1954-08-10 Standard Oil Dev Co Hydrocarbon synthesis
US2617709A (en) * 1950-11-10 1952-11-11 Gulf Oil Corp Catalytic process
US3549335A (en) * 1965-10-22 1970-12-22 Braun & Co C F Autothermal reactor
US3450784A (en) 1966-09-22 1969-06-17 Lummus Co Hydrogenation of benzene to cyclohexane
GB1292601A (en) * 1968-10-30 1972-10-11 Fisons Pharmaceuticals Ltd Bis-(2-carboxy-chromone) compounds, their preparation and pharmaceutical compositions containing them
US3765167A (en) * 1972-03-06 1973-10-16 Metallgesellschaft Ag Power plant process
US3868817A (en) * 1973-12-27 1975-03-04 Texaco Inc Gas turbine process utilizing purified fuel gas
US3866411A (en) * 1973-12-27 1975-02-18 Texaco Inc Gas turbine process utilizing purified fuel and recirculated flue gases
US3920579A (en) * 1974-04-24 1975-11-18 Texaco Inc Synthesis gas production by partial oxidation
DE2425939C2 (en) * 1974-05-30 1982-11-18 Metallgesellschaft Ag, 6000 Frankfurt Process for operating a power plant
US4048250A (en) * 1975-04-08 1977-09-13 Mobil Oil Corporation Conversion of natural gas to gasoline and LPG
US3986349A (en) * 1975-09-15 1976-10-19 Chevron Research Company Method of power generation via coal gasification and liquid hydrocarbon synthesis
US4184322A (en) * 1976-06-21 1980-01-22 Texaco Inc. Partial oxidation process
US4075831A (en) * 1976-10-27 1978-02-28 Texaco Inc. Process for production of purified and humidified fuel gas
US4074981A (en) * 1976-12-10 1978-02-21 Texaco Inc. Partial oxidation process
GB1595413A (en) * 1976-12-15 1981-08-12 Ici Ltd Engergy recovery from chemical process off-gas
US4132065A (en) * 1977-03-28 1979-01-02 Texaco Inc. Production of H2 and co-containing gas stream and power
US4121912A (en) * 1977-05-02 1978-10-24 Texaco Inc. Partial oxidation process with production of power
US4147456A (en) * 1978-02-23 1979-04-03 Institute Of Gas Technology Storage of fuel gas
US4423022A (en) * 1979-05-22 1983-12-27 The Lummus Company Processes for carrying out catalytic exothermic and endothermic high-pressure gas reactions
US4372920A (en) * 1979-07-13 1983-02-08 Ammonia Casale S.A. Axial-radial reactor for heterogeneous synthesis
US4549396A (en) * 1979-10-01 1985-10-29 Mobil Oil Corporation Conversion of coal to electricity
US4341069A (en) * 1980-04-02 1982-07-27 Mobil Oil Corporation Method for generating power upon demand
DE3035404C2 (en) * 1980-09-19 1982-09-23 Ruhrchemie Ag, 4200 Oberhausen Process for the production of unsaturated hydrocarbons
US4338292A (en) * 1980-12-08 1982-07-06 Texaco Inc. Production of hydrogen-rich gas
US4315893A (en) * 1980-12-17 1982-02-16 Foster Wheeler Energy Corporation Reformer employing finned heat pipes
DE3121991C2 (en) * 1981-06-03 1985-11-28 Kernforschungsanlage Jülich GmbH, 5170 Jülich Process for generating superheated steam in heat exchange with a synthesis gas to be catalytically methanized and containing carbon monoxide, carbon dioxide and hydrogen, as well as device for carrying out the process
NL8103397A (en) 1981-07-17 1983-02-16 Shell Int Research METHOD FOR PREPARING ORGANIC COMPOUNDS.
US4434613A (en) * 1981-09-02 1984-03-06 General Electric Company Closed cycle gas turbine for gaseous production
US4492085A (en) * 1982-08-09 1985-01-08 General Electric Company Gas turbine power plant
EP0103914B1 (en) * 1982-08-26 1988-01-07 Shell Internationale Researchmaatschappij B.V. Process for the generation of power and the preparation of liquid hydrocarbons
DK147705C (en) * 1982-09-07 1985-05-13 Haldor Topsoe As METHOD FOR MANUFACTURING CARBON HYDRADES FROM SYNTHESE GAS
GB8309359D0 (en) * 1983-04-06 1983-05-11 Ici Plc Synthesis gas
US4522939A (en) * 1983-05-31 1985-06-11 Shell Oil Company Preparation of catalyst for producing middle distillates from syngas
US4528811A (en) * 1983-06-03 1985-07-16 General Electric Co. Closed-cycle gas turbine chemical processor
DE3336024A1 (en) * 1983-10-04 1985-04-18 Boehringer Ingelheim KG, 6507 Ingelheim 4-AMINO-L-BENZYL-PYRROLIDINONE AND ITS ACID ADDITION SALTS, METHOD FOR THEIR PRODUCTION AND MEDICINAL PRODUCTS
CA1240708A (en) * 1983-11-15 1988-08-16 Johannes K. Minderhoud Process for the preparation of hydrocarbons
CA1234158A (en) * 1983-11-15 1988-03-15 Johannes K. Minderhoud Process for the preparation of hydrocarbons
US4524581A (en) * 1984-04-10 1985-06-25 The Halcon Sd Group, Inc. Method for the production of variable amounts of power from syngas
US4579986A (en) * 1984-04-18 1986-04-01 Shell Oil Company Process for the preparation of hydrocarbons
CA1241667A (en) * 1984-04-25 1988-09-06 Martin F.M. Post Process for the preparation of hydrocarbons
US4919909A (en) * 1984-12-03 1990-04-24 Societe Chimique De La Grande Paroisse Reactor for catalytic synthesis and process for using the reactor
US5080872A (en) * 1985-09-26 1992-01-14 Amoco Corporation Temperature regulating reactor apparatus and method
US4778826A (en) * 1985-09-26 1988-10-18 Amoco Corporation Conversion of a lower alkane
US4732092A (en) * 1985-09-30 1988-03-22 G.G.C., Inc. Pyrolysis and combustion apparatus
US4755536A (en) * 1985-12-27 1988-07-05 Exxon Research And Engineering Co. Cobalt catalysts, and use thereof for the conversion of methanol and for Fischer-Tropsch synthesis, to produce hydrocarbons
US5504118A (en) * 1986-05-08 1996-04-02 Rentech, Inc. Process for the production of hydrocarbons
US5543437A (en) * 1986-05-08 1996-08-06 Rentech, Inc. Process for the production of hydrocarbons
US5324335A (en) * 1986-05-08 1994-06-28 Rentech, Inc. Process for the production of hydrocarbons
US5048284A (en) * 1986-05-27 1991-09-17 Imperial Chemical Industries Plc Method of operating gas turbines with reformed fuel
DE3777934D1 (en) * 1986-09-23 1992-05-07 Foster Wheeler Energy Ltd PRODUCTION OF ORGANIC LIQUIDS.
US4678723A (en) * 1986-11-03 1987-07-07 International Fuel Cells Corporation High pressure low heat rate phosphoric acid fuel cell stack
JP2621193B2 (en) * 1987-07-21 1997-06-18 スズキ株式会社 Motorcycle
GB8721964D0 (en) * 1987-09-18 1987-10-28 Shell Int Research Multitube reactor
US4869887A (en) * 1987-10-30 1989-09-26 Dijk Christiaan P Van Integrated ammonia-urea process
US4833170A (en) * 1988-02-05 1989-05-23 Gtg, Inc. Process and apparatus for the production of heavier hydrocarbons from gaseous light hydrocarbons
US4973453A (en) * 1988-02-05 1990-11-27 Gtg, Inc. Apparatus for the production of heavier hydrocarbons from gaseous light hydrocarbons
GB8805351D0 (en) * 1988-03-07 1988-04-07 Ici Plc Desulphurisation
US4946477A (en) * 1988-04-07 1990-08-07 Air Products And Chemicals, Inc. IGCC process with combined methanol synthesis/water gas shift for methanol and electrical power production
DE3902773A1 (en) * 1989-01-31 1990-08-02 Basf Ag METHOD FOR PRODUCING SYNTHESIS GAS BY PARTIAL OXIDATION
US5028634A (en) * 1989-08-23 1991-07-02 Exxon Research & Engineering Company Two stage process for hydrocarbon synthesis
AU638741B2 (en) * 1989-09-11 1993-07-08 Broken Hill Proprietary Company Limited, The Catalyst for conversion of synthesis gas into hydrocarbons
US5122299A (en) * 1989-12-11 1992-06-16 The M. W. Kellogg Company Autothermal steam reforming process
US5026934A (en) * 1990-02-12 1991-06-25 Lyondell Petrochemical Company Method for converting light hydrocarbons to olefins, gasoline and methanol
US5177114A (en) * 1990-04-11 1993-01-05 Starchem Inc. Process for recovering natural gas in the form of a normally liquid carbon containing compound
US5179129A (en) * 1991-03-01 1993-01-12 Air Products And Chemicals, Inc. Staged liquid phase methanol process
NZ242569A (en) * 1991-05-30 1994-07-26 British Petroleum Co Plc Process for the conversion of natural gas into higher hydrocarbons by reforming combined with a fischer-tropsch process
FR2681131A1 (en) * 1991-09-11 1993-03-12 Air Liquide METHOD AND PLANT FOR PRODUCING CARBON MONOXIDE AND HYDROGEN
AU2977792A (en) * 1991-12-06 1993-06-10 Duncan Dr. Seddon A process for producing wax
US5295350A (en) * 1992-06-26 1994-03-22 Texaco Inc. Combined power cycle with liquefied natural gas (LNG) and synthesis or fuel gas
NO934505D0 (en) * 1992-12-10 1993-12-09 Foster Wheeler Ltd Procedure for the preparation of an organic liquid
US5520891A (en) * 1994-02-01 1996-05-28 Lee; Jing M. Cross-flow, fixed-bed catalytic reactor
US5472986A (en) * 1994-11-08 1995-12-05 Starchem, Inc. Methanol production process using a high nitrogen content synthesis gas with a hydrogen recycle
US5477924A (en) * 1994-12-20 1995-12-26 Imodco, Inc. Offshore well gas disposal
US5861441A (en) * 1996-02-13 1999-01-19 Marathon Oil Company Combusting a hydrocarbon gas to produce a reformed gas
US5733941A (en) * 1996-02-13 1998-03-31 Marathon Oil Company Hydrocarbon gas conversion system and process for producing a synthetic hydrocarbon liquid

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139644A (en) * 1983-04-06 1984-11-14 Ici Plc Synthesis gas
EP0212755A2 (en) * 1985-08-30 1987-03-04 Shell Internationale Researchmaatschappij B.V. Process and apparatus for producing synthesis gas
EP0497425A1 (en) * 1991-01-30 1992-08-05 Shell Internationale Researchmaatschappij B.V. Process for the combined production of organic compounds and power
JPH04364142A (en) * 1991-06-10 1992-12-16 Chiyoda Corp Synthetic process for methanol and its plant
WO1993006041A1 (en) * 1991-09-19 1993-04-01 Starchem, Inc. Process for producing and utilizing an oxygen enriched gas
WO1997033847A1 (en) * 1996-03-11 1997-09-18 Syntroleum Corporation Turbine-powered, synthesis-gas system and method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 017, no. 232 (C - 1056) 12 May 1993 (1993-05-12) *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1120127C (en) * 1998-04-16 2003-09-03 赫多特普索化工设备公司 Process and unit for combined production of ammonia synthesis gas and power
EP0950637A2 (en) * 1998-04-16 1999-10-20 Haldor Topsoe A/S Process and unit for the combined production of ammonia synthesis gas and power
EP0950636A3 (en) * 1998-04-16 2000-03-29 Haldor Topsoe A/S Process for the combined production of hydrogen rich gas and electrical power
EP0950637A3 (en) * 1998-04-16 2000-04-05 Haldor Topsoe A/S Process and unit for the combined production of ammonia synthesis gas and power
EP0950636A2 (en) * 1998-04-16 1999-10-20 Haldor Topsoe A/S Process for the combined production of hydrogen rich gas and electrical power
EP0989093A2 (en) * 1998-09-21 2000-03-29 Air Products And Chemicals, Inc. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products
EP0989093A3 (en) * 1998-09-21 2000-11-22 Air Products And Chemicals, Inc. Synthesis gas production by mixed conducting membranes with integrated conversion into liquid products
FR2796932A1 (en) * 1999-07-29 2001-02-02 Inst Francais Du Petrole Plant for production of synthesis gas from natural gas and air or oxygen diluted with inert gas comprises at least one reactor for preparation of synthesis gas and at least one compressor with power turbine
NL1015837C2 (en) * 1999-07-29 2002-08-06 Inst Francais Du Petrole Installation and method for preparing synthesis gas with at least one gas turbine.
WO2001021527A1 (en) * 1999-09-23 2001-03-29 Syntroleum Corporation Process for supplying a gaseous mixture to an autothermal reactor
DE10053778A1 (en) * 2000-10-30 2002-05-08 Alstom Switzerland Ltd Production of synthesis gas containing hydrogen and carbon monoxide, especially for methanol production, uses thermodynamic cycle to recover much of enthalpy of gas leaving reformer at high temperature and pressure
WO2003062142A1 (en) * 2002-01-16 2003-07-31 Johnson Matthey Plc Process for the production of hydrocarbons
US7087652B2 (en) 2002-01-16 2006-08-08 Johnson Matthey Plc Process for the production of hydrocarbons
US9062260B2 (en) 2008-12-10 2015-06-23 Chevron U.S.A. Inc. Removing unstable sulfur compounds from crude oil
US9499749B2 (en) 2008-12-10 2016-11-22 Chevron U.S.A. Inc. Removing unstable sulfur compounds from crude oil
US9021814B2 (en) 2009-05-22 2015-05-05 Sasol Technology (Proprietary) Limited Process for co-producing synthesis gas and power
CN110028082A (en) * 2018-01-08 2019-07-19 诺沃皮尼奥内技术股份有限公司 Ammonia production equipment
CN110028082B (en) * 2018-01-08 2023-07-18 诺沃皮尼奥内技术股份有限公司 Ammonia production equipment

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