Plural Zones Each Having A Fischer-tropsch Reaction Patents (Class 518/706)
  • Patent number: 6444712
    Abstract: An improved method for the production of methanol and hydrocarbons from a methane-containing gas, such as natural gas. The improved method integrates a hydrocarbon synthesis unit with a methanol synthesis unit without the need to recycle unreacted syngas exiting the methanol synthesis reactor. The invention combines a syngas stream and additional carbon dioxide from the hydrocarbon synthesis unit to form an optimal syngas composition for methanol and hydrocarbon synthesis. The invention also integrates other process parameters and process components of a methanol and hydrocarbon synthesis process plant to effectively convert most of the carbon in the natural gas to commercial-value products. The invention is also directed to a method of making olefin from the methanol produced by the process of the invention.
    Type: Grant
    Filed: September 28, 2000
    Date of Patent: September 3, 2002
    Assignee: ExxonMobil Chemical Patents, Inc.
    Inventor: Gary F. Janda
  • Patent number: 6433029
    Abstract: Methanol is synthesised in a synthesis loop wherein recycled unreacted gas, optionally together with part of the make-up gas, is passed through a bed of synthesis catalyst under methanol synthesis conditions, make-up gas is then added and the mixture passed through at least one further bed of synthesis catalyst under methanol synthesis conditions prior to separation of the synthesised methanol. Preferably the further bed of synthesis catalyst is located in a heat exchange reactor producing pressurised hot water which is employed to saturate a hydrocarbon feedstock from which the make-up gas is produced by steam reforming.
    Type: Grant
    Filed: November 17, 2000
    Date of Patent: August 13, 2002
    Assignee: Imperial Chemical Industries PLC
    Inventor: Terence James Fitzpatrick
  • Patent number: 6387963
    Abstract: Methanol is synthesised in a synthesis loop wherein recycled unreacted gas, optionally together with part of the make-up gas, is passed through a bed of synthesis catalyst under methanol synthesis conditions, make-up gas is then added and the mixture passed through at least one further bed of synthesis catalyst under methanol synthesis conditions prior to separation of the synthesised methanol. Preferably the further bed of synthesis catalyst is located in a heat exchange reactor producing pressurised hot water which is employed to saturate a hydrocarbon feedstock from which the make-up gas is produced by steam reforming.
    Type: Grant
    Filed: November 17, 2000
    Date of Patent: May 14, 2002
    Assignee: Imperial Chemical Industries PLC
    Inventor: Terence James Fitzpatrick
  • Patent number: 6359018
    Abstract: An integrated process for producing a liquid hydrocarbon stream from Fischer-Tropsch hydrocarbon product without having to remove particulate contaminants such as catalyst fines from hot Fischer-Tropsch wax is disclosed. The process involves performing Fischer-Tropsch synthesis, preferably under conditions which favor formation of wax and heavy products (i.e., using a catalyst with high chain growth probabilities), and obtaining a waxy heavy fraction including particulate contaminants. The fraction is subjected to hydroprocessing conditions, preferably upflow hydroprocessing conditions, using a catalyst bed which, through judicious selection of hydroprocessing catalysts and/or flow conditions, permits passage of the particulate contaminants. The particulates are then removed from the upgraded liquid product, for example by filtration, distillation and/or centrifugation.
    Type: Grant
    Filed: October 27, 2000
    Date of Patent: March 19, 2002
    Assignee: Chevron U.S.A. Inc
    Inventors: Dennis J. O'Rear, Krishniah Parimi, Richard O. Moore, Jr.
  • Patent number: 6331573
    Abstract: An integrated process for producing liquid fuels from syngas via a two-stage Fischer-Tropsch reaction is disclosed. The first stage of the Fischer-Tropsch chemistry is performed using conditions in which chain growth probabilities are relatively low to moderate, and the product of the reaction includes a relatively high proportion of low molecular (C2-8) weight olefins and a relatively low proportion of high molecular weight (C30+) waxes. The product from the first stage is fed into the second stage where the chain growth probabilities are relatively high. The wax and other paraffins produced in the first reaction are largely inert under these conditions. The light olefins compete with heavier olefins for chain initiation, and fewer chains will be initiated at C20+. With most chains initiated at C2-8, moderate chain growth probability will produce a relatively larger fraction in the C5-12 range. In this manner, wax yield is minimized.
    Type: Grant
    Filed: February 29, 2000
    Date of Patent: December 18, 2001
    Assignee: Chevron U.S.A. Inc.
    Inventor: Charles L. Kibby
  • Patent number: 6265452
    Abstract: A process for producing liquid and gaseous products from gaseous reactants. The process includes a) feeding a synthesis gas stream of mainly carbon monoxide and hydrogen, as gaseous reactants, into a slurry bed of solid Fischer-Tropsch catalyst particles suspended in a suspension liquid, with the slurry bed being provided in a reaction zone, b) allowing the gaseous reactants to react, by means of Fischer-Tropsch synthesis, as they pass upwardly through the slurry bed; c) withdrawing liquid phase from the slurry bed, to maintain the slurry bed at a desired level; d) allowing gaseous products and unreacted gaseous reactants to disengage from the slurry bed and to pass upwardly as a gas phase into a freeboard zone of a head space above the reaction zone; e) subjecting the gas phase to distillation; f) returning separated catalyst particles and liquid phase from the distillation zone and g) withdrawing treated gas phase from the head space.
    Type: Grant
    Filed: March 27, 2000
    Date of Patent: July 24, 2001
    Assignee: Sasol Technology (Proprietary) Limited
    Inventors: André Peter Steynberg, David H. Jones, Roy W. Silverman
  • Patent number: 6262131
    Abstract: A Fischer-Tropsch catalyst for the conversion of synthesis gas into Fischer-Tropsch products includes a stationary Fischer-Tropsch catalyst having a voidage ratio greater than approximately 0.45 or 0.6 and may further have a catalyst concentration for a given reactor volume of at least 10 percent. A Fischer-Tropsch catalyst has a structured shape promoting non-Taylor flow and/or producing a productivity in the range of 200-4000 vol CO/vol. Catalyst/hour or greater over at least a 600 hour run of a Fischer-Tropsch reactor with the catalyst therein. A system for converting synthesis gas into longer-chain hydrocarbon products through the Fisher-Tropsch reaction has a reactor for receiving synthesis gas directly or as a saturated hydrocarbon liquid or a combination, and a stationary, structured Fischer-Tropsch catalyst disposed within the reactor for converting at least a portion of the synthesis gas into longer-chain hydrocarbons through Fischer-Tropsch reaction.
    Type: Grant
    Filed: December 6, 1999
    Date of Patent: July 17, 2001
    Assignee: Syntroleum Corporation
    Inventors: Kym B Arcuri, Kenneth L. Agee, Mark A. Agee
  • Patent number: 6258860
    Abstract: The invention provides a process for the production of methanol from synthesis gas derived from a carbonaceous feedstock which comprises the following steps: (1) part of the unreacted gas stream from a first methanol synthesis zone is recycled to the first methanol zone; (2) another part of the unreacted gas stream from the first methanol synthesis zone is supplied to a second methanol synthesis zone; (3) part of the unreacted gas stream from the second methanol synthesis zone is recycled to the second methanol synthesis zone; (4) hydrogen is recovered from another part of the unreacted gas from the second methanol synthesis zone to give a hydrogen enriched gas stream and a hydrogen depleted gas stream; and (5) recycling the hydrogen depleted gas stream to the second methanol synthesis zone.
    Type: Grant
    Filed: January 14, 1998
    Date of Patent: July 10, 2001
    Inventors: Geoffrey Gerald Weedon, James Bernard Duhan
  • Patent number: 6225359
    Abstract: Salable hydrocarbon products prepared by reacting a light hydrocarbon gaseous stream with a gaseous oxidant to produce carbon oxides and hydrogen, which is contacted in a hydrocarbon synthesis zone to produce a product stream comprising salable hydrocarbon products. That product stream is separated into a gaseous fraction and at least one fraction of salable hydrocarbon products. The light hydrocarbon gaseous stream is formed by separating a light hydrocarbon gaseous feed comprising alkanes into a lighter fraction and a heavier fraction and contacting that heavier fraction in a disproportionation zone to convert a significant portion of the alkanes in the heavier fraction by disproportionation into both higher and lower alkanes, then at least part of the lighter fraction and the lower alkanes form the light hydrocarbon gaseous stream.
    Type: Grant
    Filed: December 21, 1999
    Date of Patent: May 1, 2001
    Assignee: Chevron U.S.A. Inc.
    Inventors: Dennis John O'Rear, Charles L. Kibby, Russell R. Krug
  • Patent number: 6201030
    Abstract: A method of regenerating a finely-divided particulate catalyst involves the use of an external regeneration system comprising first and second regeneration stations. The method is particularly adapted to regenerating supported catalysts used in Fischer-Tropsch slurry reactors. A slurry-containing partially spent catalyst is flowed from the reactor and alternately regenerated in one of the first and second regeneration stations. The alternate use of the stations for catalyst regeneration permits one station to receive partially deactivated slurry from the reactor while the other station returns regenerated slurry to the reactor. The operation of the reactor thus may be continuous.
    Type: Grant
    Filed: September 22, 1999
    Date of Patent: March 13, 2001
    Assignee: Syntroleum Corporation
    Inventor: Gary L. Beer
  • Patent number: 6169120
    Abstract: An extended catalyst life two-stage hydrocarbon synthesis process wherein a first synthesis gas stream is reacted in a first stage reactor in the presence of a suitable catalyst to produce liquid hydrocarbon products and a gaseous stream; the gaseous stream is cooled and water and liquid hydrocarbons are separated from the gaseous stream to produce a second synthesis gas stream which is then passed to a second stage reactor for the production of additional liquid hydrocarbons.
    Type: Grant
    Filed: September 17, 1999
    Date of Patent: January 2, 2001
    Assignee: Syntroleum Corporation
    Inventor: Gary L. Beer
  • Patent number: 6162754
    Abstract: Continuous process for the production of prevalently heavy hydrocarbons starting from synthesis gas in the presence of a gas phase, a liquid and a solid catalyst, the above process being carried out using a bubble column, characterized in that the bubble column internally has: (a) at least one draft-tube; (b) at least one device for the inlet of the synthesis gas; (c) at least one device for the inlet of the regenerating gas; (d) at least one device for activating/interrupting the stream of regenerating gas; (e) optional devices suitable for minimizing the mixing of the synthesis gas with the regenerating gas.
    Type: Grant
    Filed: March 18, 1999
    Date of Patent: December 19, 2000
    Assignees: Agip Petroli S.p.A., ENI S.p.A., Institut Francais du Petrole
    Inventors: Cristina Maretto, Vincenzo Piccolo, Dominique Casanave, Pierre Galtier
  • Patent number: 6156809
    Abstract: A Fischer-Tropsch process is provided for synthesizing hydrocarbons, involving multiple Fischer-Tropsch reactor stages (110) arranged in series, and characterized by very low carbon monoxide conversion per Fischer-Tropsch reactor stage (110) and intermediate removal of water between reactor stages (110). In one embodiment, the system utilizes an iron-based catalyst and balances the molar H.sub.2 /CO feed ratio in the synthesis gas (108) with the overall H.sub.2 /CO consumption ratio across all of the Fischer-Tropsch reactor stages (110). In a preferred embodiment, carbon dioxide is recycled from the last in series of the Fischer-Tropsch reactor stages (110) to the synthesis gas generator (106). The system may advantageously utilize a gaseous hydrocarbon feed (102), such as obtained from natural gas, as feed for producing the synthesis gas (108).
    Type: Grant
    Filed: April 21, 1999
    Date of Patent: December 5, 2000
    Assignee: Reema International Corp.
    Inventors: Glen L. Clark, David G. Walker
  • Patent number: 6121333
    Abstract: Process for the production of hydrocarbons from synthesis gas which comprises:a) feeding to a reactor for Fischer-Tropsch reactions, containing a catalyst based on supported cobalt, a synthesis gas in molar ratios H.sub.2 /CO ranging from 1 to 3;b) discharging from the reactor a hydrocarbon liquid phase containing the catalyst, in suspension;c) feeding the suspension to a hydrocracking reactor operating at a temperature ranging from 200 to 500.degree. C.;d) discharging a vapour phase from the head of the hydrocracking reactor and from the bottom a suspension containing heavier products which is recycled to the Fischer-Tropsch reactor;e) cooling and condensing the vapour phase.
    Type: Grant
    Filed: June 18, 1999
    Date of Patent: September 19, 2000
    Assignees: AGIP Petroli S.p.A., Institut Francais du Petrole
    Inventors: Gabriele Carlo Ettore Clerici, Vincenzo Piccolo, Giuseppe Belmonte, Paul Broutin, Fran.cedilla.ois Hugues
  • Patent number: 6096789
    Abstract: Process for the production of hydrocarbons from synthesis gas which comprises: a) feeding to the bottom of a reactor for Fischer-Tropsch reactions a synthesis gas with molar ratios H.sub.2 /CO ranging from 1 to 3;b) discharging from the head of the reactor a hydrocarbon liquid phase containing the catalyst, in suspension;c) feeding the suspension to at least a first hydrocyclone to obtain a partially separated product containing from 0.5 to 15% by volume of solid particles;d) feeding the partially separated product to at least a second hydrocyclone to obtain a stream of liquid substantially without solid particles.
    Type: Grant
    Filed: April 21, 1999
    Date of Patent: August 1, 2000
    Assignees: Agip Petroli S.p.A., Institut Francais du Petrole
    Inventors: Gabriele Clerici, Vincenzo Piccolo, Paul Broutin, Jean-Charles Viltard
  • Patent number: 6075061
    Abstract: The instant invention is directed to an integrated process for producing a hydroisomerate in the presence of sulfur comprising the steps of (a) separating a natural gas into a first stream comprising a C.sub.5 + gas field condensate containing sulfur and a second stream comprising said natural gas having said a C.sub.
    Type: Grant
    Filed: June 30, 1998
    Date of Patent: June 13, 2000
    Assignee: Exxon Research and Engineering Company
    Inventors: Robert Jay Wittenbrink, Bruce Randall Cook, Paul Joseph Berlowitz
  • Patent number: 6060524
    Abstract: The invention concerns a process for optimal operation of a slurry bubble column containing a suspension of solid particles in a liquid, characterized in that a gas phase containing the reactant(s) required for the production of the desired products is injected in the form of bubbles close to the lower extremity of said reactor and at least a portion of the liquid fraction and optionally of the solid fraction of said suspension is recirculated, drawn off from close to one extremity of said reactor and reintroduced close to the other extremity of said reactor, with a liquid flow rate U.sub.1 in the reactor which is at least equal to and preferably greater than the sedimentation rate U.sub.s of the solid particles. The invention also concerns an apparatus for optimal operation of the process. Finally, the invention concerns the use of the process and apparatus in the Fischer-Tropsch synthesis.
    Type: Grant
    Filed: January 11, 1999
    Date of Patent: May 9, 2000
    Assignees: Institut Francais du Petrole,, Agip S.p.A., Agip Petroli S.p.A.
    Inventors: Dominique Casanave, Pierre Galtier, Jean-Charles Viltard
  • Patent number: 6005011
    Abstract: A plant and process for converting associated gas from crude oil to methanol at or near the wellhead. The process uses partial oxidation of the associated gas, direct quench, liquid phase methanol conversion wherein substoichiometric H.sub.2 :CO is converted to methanol, and a loop purge to a gas turbo generator to provide all of the plant power requirements. This results in avoiding a complex vapor phase, multiple reactor methanol loop and steam-catalytic reforming, and obtains a compact, low-cost, self-sufficient facility suitable for remote locations.
    Type: Grant
    Filed: May 6, 1998
    Date of Patent: December 21, 1999
    Assignee: The M. W. Kellogg Company
    Inventor: Gunnar Henningsen
  • Patent number: 5962537
    Abstract: A downcomer for producing at least two slurries having different solids and gas concentrations from a single three phase slurry of particulate solids and gas bubbles in a slurry liquid has two or more concentric gas and solids disengaging zones, each having an open fluid conduit depending from an orifice in the bottom. The dowwncomer is useful in a slurry hydrocarbon synthesis process for forming a catalyst and gas reduced slurry which is passed to a liquid filter to remove hydrocarbon liquid from the slurry reactor.
    Type: Grant
    Filed: May 6, 1997
    Date of Patent: October 5, 1999
    Assignee: Exxon Research and Engineering Co
    Inventor: Stephen Claude Leviness
  • Patent number: 5866621
    Abstract: Particulate solids and gas are removed from a three phase hydrocarbon synthesis slurry of solid catalyst particles, gas and liquid, by successively passing slurry from a slurry body through solids and gas disengaging zones in fluid communication, with the solids disengaging zone upstream of the gas disengaging zone. This is accomplished using a solids and gas disengaging downcomer immersed in the slurry wherein solids are disengaged in a quiescent zone adjacent the slurry body, from which the solids reduced slurry passes through an enclosed cup in which gas is disengaged and removed. The bottom of the cup terminates in a downwardly depending downcomer which hydraulically feeds the densified, solids and gas reduced slurry to the bottom of the reactor or to filtration.
    Type: Grant
    Filed: May 6, 1997
    Date of Patent: February 2, 1999
    Assignee: Exxon Research and Engineering Company
    Inventors: William C. Behrmann, Charles J. Mart
  • Patent number: 5827902
    Abstract: Process for the optimum operation of a slurry bubble column reactor in the presence of a gas phase and a liquid phase, particularly for the Fischer-Tropsch reaction, characterized in that:1) the process is carried out in a number of stages in series of .gtoreq.2;2) the flow conditions of the gas phase and liquid phase containing the solids are essentially plug flow conditions, with a gas rate of between 3 cm/s and 200 cm/s and a liquid rate of between 0 and 10 cm/s;3) the concentration of solids in each stage is essentially constant and equal for each single stage, and is between 5 and 50% (vol./vol.).
    Type: Grant
    Filed: August 6, 1997
    Date of Patent: October 27, 1998
    Assignees: AGIP Petroli S.p.A., AGIP S.p.A., Institut Francais du Petrole
    Inventors: Cristina Maretto, Vincenzo Piccolo
  • Patent number: 5827901
    Abstract: Methanol is catalytically produced from a synthesis gas containing hydrogen and carbon oxides on copper-containing catalysts at pressures in the range from 20 to 120 bar and temperatures in the range from 130.degree. to 350.degree. C. The synthesis gas is first of all passed through a first synthesis reactor, in which the catalyst is provided in tubes surrounded by water as a coolant which is boiling at an elevated pressure. From the first reactor a first mixture containing gases and methanol vapor is withdrawn and passed through a second synthesis reactor. In the second reactor the catalyst is cooled with synthesis gas.
    Type: Grant
    Filed: January 31, 1997
    Date of Patent: October 27, 1998
    Assignee: Metallgesellschaft Aktiengesellschaft
    Inventors: Peter Konig, Hermann Gohna
  • Patent number: 5770630
    Abstract: An improved process for the manufacture of organic liquids from gases containing hydrogen and carbon monoxide which avoids the build-up of nitrogen content through the use of a se ies of organic liquid reactors.
    Type: Grant
    Filed: February 1, 1995
    Date of Patent: June 23, 1998
    Assignee: Foster Wheeler Energy Limited
    Inventors: Wieslaw Mark Kowal, Geoffrey Frederick Skinner
  • Patent number: 5712313
    Abstract: A process for carrying out a chemical equilibrium reaction is disclosed in which, in a first stage, one or more reactants are contacted with a fixed arrangement of a catalyst under conditions such that the reactants and the products of the reaction are gaseous, the unconverted reactants and products of the first stage being passed to a second stage, in which they are contacted with a fixed arrangement of a catalyst and the reaction allowed to proceed in the presence of an absorbent capable of absorbing a product of the reaction.
    Type: Grant
    Filed: February 26, 1996
    Date of Patent: January 27, 1998
    Assignee: Shell Oil Company
    Inventors: Gert Jan Kramer, Jean Paul Lange
  • Patent number: 5631302
    Abstract: From a synthesis gas which contains hydrogen and carbon oxides, methanol is produced on copper-containing catalysts under pressures in the range from 20 to 20 bars and at temperatures in the range from 200 to 350.degree. C. The synthesis gas is passed through a first synthesis reactor, which consists of a shaft reactor and contains a fixed bed of a copper-containing catalyst. The reaction in the shaft reactor is carried out adiabatically and without a recycling of synthesis gas. Together with recycle gas, the gas mixture which has not been reacted in the first synthesis reactor is passed through a second synthesis reactor, which contains a copper-containing catalyst, which is disposed in tubes and is indirectly cooled through boiling water. 10 to 30% of the carbon oxides of the synthesis gas are reacted in the shaft reactor to form methanol.
    Type: Grant
    Filed: May 8, 1995
    Date of Patent: May 20, 1997
    Assignee: Metallgesellschaft Aktiengesellschaft
    Inventors: Peter Konig, Hermann Gohna
  • Patent number: 5498638
    Abstract: High conversion, substantially once-through hydrocarbon synthesis is achieved by reacting H.sub.2 and CO in a first stage(s) in the presence of a non-shifting catalysts, separating liquid products and reacting the remaining gas streams in the presence of hydrocarbon synthesis catalysts having shifting activity.
    Type: Grant
    Filed: April 29, 1994
    Date of Patent: March 12, 1996
    Assignee: Exxon Research & Engineering Co.
    Inventor: David C. Long
  • Patent number: 5455281
    Abstract: Method of direct cooling synthesis gas in a catalytic reactor with one or more catalyst beds of a metal oxide catalyst being loaded on gas permeable partitions with distribution means, which method comprises admixing the synthesis gas during its passage through the reactor with a cooling gas being introduced into a mixing zone beneath each partition, wherein the mixing zones are obtained by passing a reducing gas through the catalyst bed, so that the catalyst volume shrinks during reduction of the catalyst particles, and, thereby, providing necessary cavities for the mixing zones beneath each partition.
    Type: Grant
    Filed: December 7, 1993
    Date of Patent: October 3, 1995
    Assignee: Haldor Topsoe A/S
    Inventor: Haldor F. A. Topsoe
  • Patent number: 5449696
    Abstract: A process for the continuous production of methanol through contacting at least one feed stream containing at least carbon monoxide and hydrogen, and optionally carbon dioxide, with a simulated moving bed acting as a catalyst for methanol synthesis and an adsorbent for the methanol formed has been developed. The carbon monoxide and hydrogen are catalytically reacted to form methanol which is separated from the carbon monoxide and hydrogen by concurrent adsorption. The methanol is desorbed using a carbon dioxide or hydrogen desorbent and collected. A specific embodiment is one where the feed stream is introduced to the simulated moving bed at a temperature from about 210.degree. to about 270.degree. C. and the desorbent is introduced to the simulated moving bed at a temperature of about 150.degree. to about 250.degree. C.
    Type: Grant
    Filed: August 1, 1994
    Date of Patent: September 12, 1995
    Assignee: UOP
    Inventors: Hemant W. Dandekar, Gregory A. Funk
  • Patent number: 5424335
    Abstract: The purge gas from a methanol synthesis loop is subjected to a further step of methanol synthesis, preferably while in indirect heat exchange with the purge gas undergoing heating to the synthesis inlet temperature so that the reacted purge gas, containing synthesized methanol, leaves the synthesis catalyst at a temperature below the maximum temperature achieved by the reacting purge gas during passage over the catalyst.The synthesis loop can be operated less efficiently, eg at a lower pressure or with added carbon dioxide, than is conventional since the additional methanol produced from the purge gas compensates for the loss of loop efficiency.The addition of the purge gas synthesis stage enables existing plants to be uprated by lowering the loop pressure, thus enabling a greater throughput through the synthesis gas compressor to be achieved.
    Type: Grant
    Filed: November 23, 1993
    Date of Patent: June 13, 1995
    Assignee: Imperial Chemical Industries PLC
    Inventor: Peter E. J. Abbott
  • Patent number: 5219891
    Abstract: A process for the production of methanol by reacting a gaseous mixture comprising hydrogen and carbon monoxide in the presence of a catalyst composition in the form of a fluidized bed whilst cooling, characterized in that the catalyst composition is present in a plurality of interconnected fluidized bed sections whereby each section is cooled by at least one heat exchanger and whereby the temperature in the highest section is reduced to below the highest temperature in a lower section.
    Type: Grant
    Filed: October 28, 1991
    Date of Patent: June 15, 1993
    Assignee: Shell Oil Company
    Inventor: Swan T. Sie
  • Patent number: 5216034
    Abstract: A process for the production of methanol by reacting a gaseous mixture comprising hydrogen and carbon monoxide in the presence of a catalyst composition in a fluidized bed while cooling, characterized in that the reaction is carried out in a plurality of fluidized catalyst bed reactors in series with interstage removal of methanol from the reaction mixture.
    Type: Grant
    Filed: October 28, 1991
    Date of Patent: June 1, 1993
    Assignee: Shell Oil Company
    Inventor: Swan T. Sie
  • Patent number: 5179129
    Abstract: Methanol is produced from synthesis gas comprising hydrogen, carbon monoxide, and carbon dioxide in a two-stage liquid phase reactor system. Each reactor is operated in an optimum temperature range to maximize methanol productivity, and once-through product conversion of up to 9.1 moles methanol per 100 moles of synthesis gas can be achieved with reasonable catalyst utilization. Overall catalyst utilization is increased by countercurrent catalyst transfer. In an alternate mode of operation, the liquid phase reactor system is integrated with a coal gasification combined cycle (CGCC) power generation process wherein the unreacted synthesis gas is used as fuel in a gas turbine-driven electric power generator. Operation of each liquid phase reactor in the optimum temperature range maximizes the available heat of reaction which is recovered as steam; the steam is utilized in the gas turbine combustor or the CGCC steam turbine.
    Type: Grant
    Filed: March 1, 1991
    Date of Patent: January 12, 1993
    Assignee: Air Products and Chemicals, Inc.
    Inventor: David W. Studer
  • Patent number: 5177114
    Abstract: This invention comprises a method for converting natural gas to a normally liquid carbon containing compound, such as methanol and/or dimethyl ether and/or to gasoline grade liquid hydrocarbons and/or olefins. The method of this invention eliminates the need for steam reforming and/or adiabatic reforming with essentially pure oxygen of the natural gas to a synthesis gas. In accordance with the process of this invention, a synthesis gas may be produced at an operating pressure suitable for conversion thereof to methanol and/or dimethyl ether without the need for synthesis gas recompression. Further, the vent or bleed gas from the overheads after conversion to the crude product methanol/DME and/or its conversion to gasoline grade liquid hydrocarbons, generally has a BTU capacity required to serve as a fuel gas for supplying the energy needed for operation of a gas turbine which powers the gas compression equipment requirements by which the process of this invention may be practiced.
    Type: Grant
    Filed: March 30, 1992
    Date of Patent: January 5, 1993
    Assignee: Starchem Inc.
    Inventors: Christiaan P. Van Dijk, Lowell D. Fraley
  • Patent number: 5045568
    Abstract: The invention concerns a process and an apparatus for performing chemical reactions under pressure in the presence of a solid catalyst in a multi-stage reaction zone, after external intermediary thermal conditioning. This process may be used for the synthesis of ammonia or methanol or for gasoline reforming. It is characterized in that at least one reaction fluid is introduced into at least one compartment, a first reaction effluent is recovered, a heat exchange takes place, outside the reaction zone, between a first effluent and an external heat exchange medium, then said first effluent is introduced into at least one subsequent compartment and a second reaction effluent is recovered from said subsequent compartment.
    Type: Grant
    Filed: January 21, 1988
    Date of Patent: September 3, 1991
    Assignee: Institut Francais du Petrole
    Inventors: Dang V. Quang, Pierre Ham, Daniel Gelas, Christian Legrand
  • Patent number: 5028634
    Abstract: Hydrocarbon synthesis is carried out in a two stage process wherein the pressure in the first stage is relatively higher and the pressure in the second stage is relatively lower and the second stage catalyst comprises cobalt on alumina.
    Type: Grant
    Filed: August 23, 1989
    Date of Patent: July 2, 1991
    Assignee: Exxon Research & Engineering Company
    Inventor: Rocco A. Fiato
  • Patent number: 4968722
    Abstract: A process for producing methanol by reacting carbon monoxide and hydrogen, wherein said reactants in the gaseous phase are introduced into a reaction zone comprising one or more fixed catalyst beds using a liquid absorbent, selectively absorbing substantially all of the methanol formed, followed by desorption of the methanol. The absorption of methanol is preferably effected in a separate absorption zone.
    Type: Grant
    Filed: February 1, 1989
    Date of Patent: November 6, 1990
    Assignee: Process Engineering Consultants PEC B.V.
    Inventor: Klaas R. Westerterp
  • Patent number: 4908390
    Abstract: A method of preparing methanol consists in that a synthesis-gas containing carbon oxides and hyddrogen is passed through a fixed bed of a copper-containing catalyst under pressure of 3.0-15.0 MPa at a temperature of from 150.degree. to 300.degree. C. The catalyst is divided into two parts either in an equal proportion or in a smaller/greater ratio equal to 0.5-1. The gaseous mixture obtained after passing the first part of the catalyst bed is stirred prior to the supply thereof to the second part of the catalyst bed. As a result, the reaction mixture is formed containing the aim product. Each subsequent direction of passing the synthesis-gas through the catalyst bed and that of removing the reaction mixture are changed to opposite with respect to the previous direction.
    Type: Grant
    Filed: June 7, 1988
    Date of Patent: March 13, 1990
    Assignee: Akademii Institut Katalizsa Sibirskogo Otdelenia Nauk SSSR
    Inventors: Jury S. Matros, Ilya A. Zolotarsky
  • Patent number: 4849206
    Abstract: Process for obtaining an optimal synthesis gas distribution in catalytic beds for heterogeneous reactions in reactors comprising a cylindrical pressure vessel with an internal cartridge containing a catalyst.
    Type: Grant
    Filed: March 13, 1987
    Date of Patent: July 18, 1989
    Assignee: Ammonia Casale S.A.
    Inventor: Umberto Zardi
  • Patent number: 4766154
    Abstract: The present invention is a process for the production of methanol from a syngas feed containing carbon monoxide, carbon dioxide and hydrogen. Basically, the process is the combination of two liquid phase methanol reactors into a staging process, such that each reactor is operated to favor a particular reaction mechanism. In the first reactor, the operation is controlled to favor the hydrogenation of carbon monoxide, and in the second reactor, the operation is controlled so as to favor the hydrogenation of carbon dioxide. This staging process results in substantial increases in methanol yield.
    Type: Grant
    Filed: February 6, 1987
    Date of Patent: August 23, 1988
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Leo W. Bonnell, Alan T. Perka, George W. Roberts
  • Patent number: 4731387
    Abstract: In a process for carrying out a chemical equilibrium reaction by introducing gaseous starting compounds in a reaction zone containing a fixed bed of coarse catalyst particles having interstices between them, fine particles adsorbing substantially all of the product compounds are passed downwardly through the interstices and subsequently withdrawn from the reaction zone.
    Type: Grant
    Filed: September 15, 1986
    Date of Patent: March 15, 1988
    Assignee: Shell Oil Company
    Inventor: Klaas R. Westerterp
  • Patent number: 4670473
    Abstract: Conversion of syn gas to methanol and higher alkanols wherein alkanols are added to a syn gas reactor. Lower alkanols are homologated to higher alkanols. Liquid methanol is added as an interstage quench.
    Type: Grant
    Filed: August 9, 1985
    Date of Patent: June 2, 1987
    Assignee: Amoco Corporation
    Inventors: Robert H. Walker, David A. Palmer, Donna M. Salvatore, Edward J. Bernier
  • Patent number: 4628066
    Abstract: The present invention is a process for increasing the capacity of a gas phase synthesis loop for the production of methanol from a syngas feed. The syngas feed is initially passed to a liquid phase methanol reactor to convert a portion of the syngas to methanol or methanol and higher aliphatic alcohols. The mixture is subsequently cooled to condense and recover the methanol and/or higher alcohols. The unreacted syngas is passed to a gas phase synthesis loop for further conversion and recovery of methanol.
    Type: Grant
    Filed: February 12, 1986
    Date of Patent: December 9, 1986
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Leo W. Bonnell, Joseph M. Pietrantonio
  • Patent number: 4626552
    Abstract: A process for the start-up of a reactor which utilizes a feed comprising hydrogen and carbon monoxide for the synthesis of hydrocarbons. The feed is contacted with a bed of hydrocarbon synthesis catalyst in which perturbations of the temperature profile across the bed can develop, and which, at start-up is particularly acute. In practicing the process the feed is introduced into the reactor at a rate ranging up to about 100 percent of the total flow rate at which the feed is introduced to the reactor at line-out. Hydrogen is introduced into the reactor as a portion of said feed at a molar feed rate generally well below the feed rate in which the hydrogen is employed in the reactor at line-out, the molar ratio of hydrogen:carbon monoxide of the feed generally not exceeding about 90 percent, preferably 75 percent, of the molar ratio of hydrogen:carbon monoxide at line-out.
    Type: Grant
    Filed: January 6, 1986
    Date of Patent: December 2, 1986
    Assignee: Exxon Research and Engineering Company
    Inventor: Kym B. Arcuri
  • Patent number: 4525482
    Abstract: This invention provides an improved, simple and energy saving process for producing a gas containing methane, which process utilizes a reactor having a catalyst bed of a structure wherein a synthesis gas is allowed to pass perpendicularly to the longitudinal directions of a plurality of cooling tubes installed vertically within the catalyst bed. Within the cooling tubes, a liquid coolant at its boiling temperature is flowed upwardly under pressure. A portion of the reaction product gas leaving the catalyst bed is mixed, without cooling, with fresh feed gas and is recirculated to the catalyst bed. The amount of the recycled gas is less than 5 times the amount of fresh feed gas. The foregoing process produces a product gas containing methane from a feed gas containing carbon monoxide and hydrogen.
    Type: Grant
    Filed: March 22, 1984
    Date of Patent: June 25, 1985
    Assignee: Toyo Engineering Corporation
    Inventors: Kozo Ohsaki, Katsutoshi Kikuchi, Yoshitsugu Hirota
  • Patent number: 4496666
    Abstract: Catalysts comprising the mixed oxides of ruthenium, palladium or platinum and alkali metals are provided which are useful in the subject process for the upgrading of synthesis gas, particularly for obtaining alkanes and alcohols having at least two carbon atoms, in addition to methane and methanol. Also provided is a temperature gradient reactor useful in synthesis gas upgrading reactions for increasing selectivity to higher carbon number products.
    Type: Grant
    Filed: December 2, 1983
    Date of Patent: January 29, 1985
    Assignee: The Standard Oil Company
    Inventors: Frederick A. Pesa, Anne M. Graham
  • Patent number: 4443561
    Abstract: In a two-stage process for the conversion of H.sub.2 -poor syngas into hydrocarbons and oxygenates in which uncoverted syngas from the first stage product is converted in a second stage into paraffins over a Ni, Co or Ru catalyst, the H.sub.2 /CO molar ratio of the feed for the second stage is adjusted to the required value of 1.75-2.25 by blending this feed with an H.sub.2 -rich syngas with an H.sub.2 /CO molar ratio of at least above 1.75 which latter gas has been obtained by subjecting a small portion of the feed for the first stage to a high temperature (above 325.degree. C.) CO-shift.
    Type: Grant
    Filed: May 24, 1982
    Date of Patent: April 17, 1984
    Assignee: Shell Oil Company
    Inventors: Sikko J. A. Boelema, Martin F. M. Post, Swan T. Sie
  • Patent number: 4433066
    Abstract: A method for the production of high-caloric content gases is disclosed wherein feed gases containing CO and H.sub.2 are passed through at least two consecutive catalytic fluidized bed stages having cooling elements wherein, the feed gases being introduced to the first stage under pressure and to the subsequent stages under a pressure which is less than the pressure of the next preceding stage, and the gas produced from each preceding stage is fed to the next stage as a diluting gas. As a result of using the method of the present invention, one can avoid the necessity of compression of the feed gases in the subsequent reaction stages, thereby decreasing the cost as well as the technical difficulties encountered in the process.
    Type: Grant
    Filed: January 19, 1982
    Date of Patent: February 21, 1984
    Assignee: Didier Engineering GmbH
    Inventors: Erich Hackler, Claus Flockenhaus, Werner Lommerzheim
  • Patent number: 4431751
    Abstract: Only a part of the synthesis gas supply is passed through a first internally cooled catalytic reactor (1) and the hotter gas coming out of it is reunited with the remaining gas supply for passing through an adiabatic reactor (2) that is followed by a heat exchanger (3) on its way to a second internally cooled reactor (4) in which the methanization reaction is completed. Water is heated up to practically the saturated steam temperature in the cooling system of the last mentioned reactor and is converted to saturated steam in the cooling system of the first internally cooled reactor. The saturated steam is superheated in the above-mentioned heat exchanger. To make the process run more smoothly a steam drum is provided through which the hot water piping between the cooling systems of the two internally cooled reactors runs and the saturated steam is brought into the steam drum and from it to the heat exchanger before it is superheated.
    Type: Grant
    Filed: May 26, 1982
    Date of Patent: February 14, 1984
    Assignee: Kernforschungsanlage Julich GmbH
    Inventors: Bernd Hohlein, Manfred Vorwerk, Udo Boltendahl
  • Patent number: 4407974
    Abstract: A method of catalytic conversion of feed gases, particularly of a low-sulphur gas mixture rich in carbon monoxide and hydrogen, into a product gas mixture containing methane and/or higher hydrocarbons under high pressure includes the step of removing heat of reaction from the catalytic conversion from a reaction zone by feeding both water and steam to form a cooling medium through a pipe coil in the reaction zone. This forms superheated steam in the pipe coil and the superheated steam is then converted into another form of energy, for example in a turbo-generator. Preferably the reaction zone is a fluidized bed. For carrying out this method a reactor is used, which is preferably a fluidized bed reactor and in this reactor the piping system forming the superheater is disposed in the lower part of the reaction zone. The superheater is connected to a feedwater line and to a steam inlet line and a steam turbine is connected to a steam output line leading from the superheater.
    Type: Grant
    Filed: April 23, 1982
    Date of Patent: October 4, 1983
    Assignees: Thyssengas GmbH, Didier Engineering GmbH
    Inventors: Claus Flockenhaus, Erich Hackler, Werner Lommerzheim
  • Patent number: 4383837
    Abstract: This invention concerns an efficient, high recovery, single product, multiple-stage process for producing high BTU methane from a low BTU feed gas containing carbon monoxide, hydrogen, nitrogen and other materials. In the process, impurities like hydrogen sulfide and carbon dioxide are removed at the appropriate point. The carbon monoxide is removed and split into two streams. One stream is reacted with steam to provide additional hydrogen which is mixed with the other carbon monoxide stream and passed to a methanator. The hydrogen in the feed gas is recovered in an especially efficient two stage manner which is suitable for use with standard cooling water and which reduces metallurgical problems, compression requirements and heat requirements. In the first stage, metal hydrides are formed, thereby separating the hydrogen in the feed gas from nitrogen and the nitrogen exits and is removed.
    Type: Grant
    Filed: December 28, 1979
    Date of Patent: May 17, 1983
    Assignee: Atlantic Richfield Company
    Inventor: Robert H. Smith