Solvent Utilized Patents (Class 518/710)
  • Patent number: 8431081
    Abstract: Solvent extraction is used to remove wax and contaminants from an iron-based Fischer-Tropsch catalyst in a natural circulation continuous-flow system. The wax-free catalyst is then subjected to controlled oxidation to convert the iron to its initial oxidized state, Fe2O3. Reactivation of the oxide catalyst precursor is carried out by addition of synthesis gas.
    Type: Grant
    Filed: May 10, 2011
    Date of Patent: April 30, 2013
    Assignee: Rentech, Inc.
    Inventors: Belma Demirel, Mark S. Bohn, Charles B. Benham, James E. Siebarth, Mark D. Ibsen
  • Patent number: 8022108
    Abstract: Novel methods of treating a Fischer-Tropsch product stream with an acid are disclosed. Such methods are capable of removing contamination from the Fischer-Tropsch product stream such that plugging of the catalyst beds of a subsequent hydroprocessing step is substantially reduced.
    Type: Grant
    Filed: July 2, 2003
    Date of Patent: September 20, 2011
    Assignee: Chevron U.S.A. Inc.
    Inventors: Lucy M. Bull, Donald L. Kuehne, William L. Schinski, Philippus Rudolf Heydenrich, Richard O. Moore, Jr., Quintin John Beukes, Gianni Guilio Eligio Bacco Rodriquez
  • Patent number: 7964156
    Abstract: Solvent extraction is used to remove wax and contaminants from an iron-based Fischer-Tropsch catalyst in a natural circulation continuous-flow system. The wax-free catalyst is then subjected to controlled oxidation to convert the iron to its initial oxidized state, Fe203. Reactivation of the oxide catalyst precursor is carried out by addition of synthesis gas.
    Type: Grant
    Filed: October 18, 2007
    Date of Patent: June 21, 2011
    Assignee: Rentech, Inc.
    Inventors: Belma Demirel, Mark S. Bohn, Charles B. Benham, James E. Siebarth, Mark D. Ibsen
  • Patent number: 7375143
    Abstract: Embodiments of the invention relate to processes and apparatus for the washing and recovery of metal-containing catalyst solids in a form suitable for reclamation. More specifically, a catalyst recovery process comprises removing an organic residue with a washing medium from a metal-containing catalyst solids, recovering washed solids, and treating the washed solids under oxidative conditions to form non-reactive solids. The treatment oxidative conditions may be effective to convert the metal(s) into an oxide form and/or may facilitate the removal of remaining organic residue from the washed solids. The treatment of the washed solids may comprise calcination. In some embodiments, the metal-containing catalyst solids may be recovered from a slurry stream, and the process further comprises passing the slurry stream though a separation unit to obtain a catalyst-enriched retentate slurry.
    Type: Grant
    Filed: November 22, 2005
    Date of Patent: May 20, 2008
    Assignee: ConocoPhillips Company
    Inventors: Sara I. Kopponen, Ralph T. Goodwin, Kristi A. Fjare, Barbara A. Belt, Brian J. Levitt, Kindra Snow-McGregor, Richard J. Wissbaum, Mariella L. Raven, Frank B. Walter
  • Patent number: 7303731
    Abstract: Solvent extraction is used to remove wax and contaminants from an iron-based Fischer-Tropsch catalyst in a natural circulation continuous-flow system. The wax-free catalyst is then subjected to controlled oxidation to convert the iron to its initial oxidized state, Fe2O3. Reactivation of the oxide catalyst precursor is carried out by addition of synthesis gas.
    Type: Grant
    Filed: December 7, 2004
    Date of Patent: December 4, 2007
    Assignee: Rentech, Inc.
    Inventors: Belma Demirel, Mark S. Bohn, Charles B. Benham, James E. Siebarth, Mark D. Ibsen
  • Patent number: 6974842
    Abstract: In a system and method for recovering a catalyst, a slurry comprising said catalyst and residual hydrocarbons is heated so as to vaporize hydrocarbons. The vaporized hydrocarbons are separated from the catalyst. The separated catalyst is preferably further contacted with a stripping medium so as to further remove remaining hydrocarbons. In an embodiment, the catalyst is a Fischer-Tropsch catalyst contained in a reactor, preferably a slurry bubble reactor. In some embodiments, the slurry is diluted with additional hydrocarbons, and the residual hydrocarbons comprise waxy hydrocarbons. In an embodiment, substantially all of the hydrocarbons in the slurry are vaporized. In an embodiment, the catalyst is separated from the vaporized hydrocarbons via centrifugation. In an embodiment, substantially all of the hydrocarbons are removed from the catalyst.
    Type: Grant
    Filed: November 22, 2004
    Date of Patent: December 13, 2005
    Assignee: ConocoPhillips Company
    Inventors: Michael D. Spena, Doug S. Jack, Dan Fraenkel
  • Patent number: 6838487
    Abstract: Solvent extraction is used to remove wax and contaminants from an iron-based Fischer-Tropsch catalyst in a natural circulation continuous-flow system. The wax-free catalyst is then subjected to controlled oxidation to convert the iron to its initial oxidized state, Fe2O3. Reactivation of the oxide catalyst precursor is carried out by addition of synthesis gas.
    Type: Grant
    Filed: December 4, 2003
    Date of Patent: January 4, 2005
    Assignee: Rentech, Inc.
    Inventors: Belma Demirel, Mark S. Bohn, Charles B. Benham, James E. Siebarth, Mark D. Ibsen
  • Patent number: 6835756
    Abstract: Process for the conversion of synthesis gas to liquid hydrocarbon products by contacting, in a slurry reactor, synthesis gas at an elevated temperature and pressure with a suspension of catalyst in a liquid medium, introducing a low boiling solvent into the slurry reactor, vaporising at least a portion of the low boiling solvent in the slurry reactor, withdrawing from the slurry reactor, a gaseous stream comprising unreacted synthesis gas and vaporised low boiling solvent, cooling at least a portion of the gaseous stream to a temperature at which liquid condenses out so as to form a two phase mixture of gas and condensed liquid, and recycling at least a portion of the gas and at least a portion of the condensed liquid to the slurry reactor.
    Type: Grant
    Filed: June 17, 2003
    Date of Patent: December 28, 2004
    Assignees: BP Exploration Operating Company Ltd., Davy Process Technology Limited
    Inventors: Josephus Johannes Helena Maria Font Freide, Stephen Fortune, Barry Nay, David Newton
  • Patent number: 6800579
    Abstract: There is provided a process for regenerating the activity of used metal catalysts for the hydrogenation of carbon monoxide comprising decreasing the hydrocarbon content thereof, calcining under an oxidant-containing atmosphere, impregnating with a solution of at least one of a metal compound, calcining under an oxidant-containing atmosphere and activating by contacting with a hydrogen-contacting gas at elevated temperatures to form an active catalyst. The process regenerates and enhances both supported and dispersed active metal (DAM) catalysts. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operation thereof. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.
    Type: Grant
    Filed: January 29, 2002
    Date of Patent: October 5, 2004
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Michel Daage, Russell John Koveal, Min Chang
  • Patent number: 6777451
    Abstract: A process for enhancing metal catalysts for carbon monoxide hydrogenation comprising reducing the catalyst so that at least a portion is in the metallic state, impregnating under a non-oxidative atmosphere with a solution of a salt of at least one metal, optionally in combination with at least one of an ammonium salt, an alkyl ammonium salt, a weak organic acid and ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, and reducing to form an active catalyst. Used catalysts enhanced by the process are initially treated to decrease their hydrocarbon content. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst may be withdrawn from a reactor and returned to at least one reactor, both preferably during operations. Up to all steps may be effected in a subsequent reactor, or in specialized apparatus.
    Type: Grant
    Filed: January 29, 2002
    Date of Patent: August 17, 2004
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Russell John Koveal, Michel Daage, Charles Harrison Mauldin, Janet Renee Clark
  • Patent number: 6753354
    Abstract: There is provided a process for hydrocarbon synthesis wherein a supported metal catalyst for hydrogenating carbon monoxide to form a mixture of hydrocarbons is regenerated by decreasing its hydrocarbon content, impregnating under a non-oxidative atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally including ammonia, oxidizing with a gaseous oxidant in the presence of the impregnating solution, activating the catalyst by reduction with hydrogen at elevated temperatures and reusing the catalyst. The treatment may be carried out in a single reactor, or by carrying out up to all steps after catalyst has been withdrawn therefrom and returned to at least one reactor. Up to all steps subsequent to decreasing the hydrocarbon content may be effected in a subsequent reactor, or in specialized apparatus.
    Type: Grant
    Filed: January 29, 2002
    Date of Patent: June 22, 2004
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Russell John Koveal, Michel Daage, Eric Baochun Shen
  • Patent number: 6753351
    Abstract: A process for activating a supported metal catalyst or catalyst precursor useful for the hydrogenation of carbon monoxide to form a mixture of hydrocarbons, comprising reducing with a hydrogen-containing gas at elevated temperature so that at least a portion is in the metallic state, impregnating under a non-oxidizing atmosphere with a solution of at least one member selected from the group consisting of ammonium salts, alkyl ammonium salts and weak organic acids, optionally further including ammonia, to the point where it has absorbed a volume of solution equal to at least about 10% of its calculated pore volume, oxidizing with a gaseous oxidant in the presence of the impregnating solution and reducing with hydrogen-containing gas at elevated temperatures to form an active catalyst. The steps beginning with the impregnation may be repeated. Optionally, the catalyst may be calcined after the oxidation step and/or passivated after activation.
    Type: Grant
    Filed: January 29, 2002
    Date of Patent: June 22, 2004
    Assignee: ExxonMobil Research and Engineering Company
    Inventors: Janet Renee Clark, Michel Daage, Russell John Koveal
  • Patent number: 6476086
    Abstract: Fine iron-based catalyst particles from. Fischer-Tropsch (F-T) synthesis processes are effectively separated from catalyst/liquid/wax slurry by contacting and/or mixing the slurry with a coalescence enhancing treating solution to facilitate gravity separation and settling of such catalyst, and thereby yield a substantially clean hydrocarbon liquid/wax product. The treating solution includes a surface tension reducing agent, an agglutinating agent, and a coalescing agent each in selected proportions in aqueous solution. Useful mixing and settling conditions are 10-250° C. temperature, 0-500 psig pressure and treating solution to slurry volume ratio of 0.5-5:1, with the settling time for at least about 90% and preferably substantially all of the catalyst fines after the mixing step being less than about 15 minutes. The treating solution can be desirably recovered and reused in the F-T synthesis process, and the recovered catalyst either recycled or disposed as desired.
    Type: Grant
    Filed: April 4, 2001
    Date of Patent: November 5, 2002
    Assignee: Hydrocarbon Technologies, Inc.
    Inventor: Peizheng Zhou
  • Publication number: 20020143075
    Abstract: The invention is directed to reactor systems, apparatus, and processes which are useful for conducting chemical reactions that may be effected in a three phase slurry system. One particular application of the invention converts synthesis gas (syngas) into hydrocarbons. Syngas is comprised of carbon monoxide and hydrogen. In general, a low profile bed reactor is capable of conducting an exothermic catalytic conversion. The reactor may also include a catalyst contained in a moving fluid system which ascends in the reactor in one or more stages. A heat exchanger optionally may be used to remove heat, and water may be removed from the reaction as it proceeds from one stage to another. The reactor is designed in a relatively low profile horizontal design, and is usually more efficient and inexpensive to operate (or build) than taller vertically oriented reactors of the same type.
    Type: Application
    Filed: March 27, 2001
    Publication date: October 3, 2002
    Inventors: Kenneth L. Agee, Larry J. Weick
  • Patent number: 6284807
    Abstract: A slurry catalytic hydrocarbon synthesis process which employs a catalyst comprising a supported cobalt component achieves a short term catalyst half life of more than 10 days, by using a syngas feed which contains less than fifty parts per billion of a combined total amount of HCN and NH3.
    Type: Grant
    Filed: August 14, 1998
    Date of Patent: September 4, 2001
    Assignee: Exxon Research and Engineering Company
    Inventors: Stephen C. Leviness, Charles J. Mart, William C. Behrmann, Stephen J. Hsia, Daniel R. Neskora
  • Patent number: 6114399
    Abstract: A method of separating a Fischer-Tropsch catalyst from the output slurry of a Fischer-Tropsch bubble column reactor, where the slurry comprises Fischer-Tropsch catalyst particles and liquid hydrocarbon product is disclosed. The method comprises contacting a compressed hydrocarbon solvent (e.g., a supercritical hydrocarbon solvent, or liquid hydrocarbon solvent which may be at near supercritical conditions) with the output slurry at a temperature and pressure where the liquid hydrocarbon product is soluble in the solvent to form a concentrated slurry phase containing the catalyst particles, and an enriched solvent phase containing liquid hydrocarbon product. This contacting step is then followed by the step of separating the concentrated slurry from the enriched solvent. Apparatus for carrying out the method of the invention is also disclosed.
    Type: Grant
    Filed: February 6, 1997
    Date of Patent: September 5, 2000
    Assignee: North Carolina State University
    Inventors: George W. Roberts, Peter K. Kilpatrick
  • Patent number: 5827903
    Abstract: In a catalytic process for converting synthesis gas including hydrogen and carbon monoxide to hydrocarbons and oxygenates by a slurry Fischer-Tropsch synthesis, the wax product along with dispersed catalyst is removed from the slurry and purified by removing substantially all of the catalyst prior to upgrading the wax and returning a portion to the Fischer-Tropsch reaction. Separation of the catalyst particles from the wax product is accomplished by dense gas and/or liquid extraction in which the organic compounds in the wax are dissolved and carried away from the insoluble inorganic catalyst particles that are primarily inorganic in nature. The purified catalyst free wax product can be subsequently upgraded by various methods such as hydrogenation, isomerization, hydrocracking, conversion to gasoline and other products over ZSM-5 aluminosilicate zeolite, etc.
    Type: Grant
    Filed: January 31, 1996
    Date of Patent: October 27, 1998
    Assignee: The United States of America as represented by the Department of Energy
    Inventors: Curt M. White, Michael S. Quiring, Karen L. Jensen, Richard F. Hickey, Larry D. Gillham
  • Patent number: 5260239
    Abstract: Catalyst which has become deactivated during a hydrocarbon synthesis (HCS) process is reactivated - rejuvenated using an external reactivation - rejuvenation vessel resulting in a multiple HCS reaction - catalyst rejuvenation reactor vessel design. Flow of the catalyst is synthesis product slurry from the reactor vessel to the rejuvenation vessel and the flow of rejuvenated catalyst back to the reactor vessel are driven by gravity only.
    Type: Grant
    Filed: December 18, 1992
    Date of Patent: November 9, 1993
    Assignee: Exxon Research & Engineering Company
    Inventor: Stephen J. Hsia
  • Patent number: 4908341
    Abstract: A method for regenerating a spent porous crystalline catalyst, optionally associated with a metal component such as noble and/or base metal(s), is described. The method comprises contacting the spent catalyst which has become deactivated by accumulation of carbonaceous residue with one or more light aromatic compounds under conditions resulting in reactivation of said catalyst. The light aromatic compounds employed are ones which have the capability of penetrating the catalyst, so as to contact the carbonaceous residue contained therein, undergoing alkylation by alkyl fragments contributed by components of the carbonaceous residue and diffusing from or otherwise escaping the catalyst.
    Type: Grant
    Filed: October 20, 1987
    Date of Patent: March 13, 1990
    Assignee: Mobil Oil Corp.
    Inventors: Ann L. Pruden, Chaya Venkat, Darrell D. Whitehurst
  • Patent number: 4429057
    Abstract: A homogeneous catalytic process wherein a gaseous or vaporized reactant stream is continuously introduced into a liquid phase mixture containing (a) a volatile precious metal catalyst, and (b) methanol and/or ethanol as reactant or reaction product, at least a portion of the volatile precious metal being continuously removed from the liquid phase mixture by the effluent gas and/or vapor stream, and such effluent stream is an integral component of a cyclic process stream and/or a vent stream discharged from the process.
    Type: Grant
    Filed: August 26, 1982
    Date of Patent: January 31, 1984
    Assignee: Union Carbide Corporation
    Inventors: Bernard D. Dombek, George L. O'Connor
  • Patent number: RE37515
    Abstract: A cobalt- or ruthenium-containing hydrocarbon synthesis catalyst, subjected to short term, reversible, partial deactivation in a slurry synthesis process can be rejuvenated, i.e., at least about 80+% catalyst activity recovery, by treating the catalyst in the presence of liquid hydrocarbons, preferably the slurry hydrocarbons, with hydrogen at elevated temperatures and pressures.
    Type: Grant
    Filed: August 13, 1998
    Date of Patent: January 15, 2002
    Assignee: Exxon Research and Engineering Company
    Inventor: Willard N. Mitchell
  • Patent number: RE37649
    Abstract: Catalyst in a slurry phase reactor is rejuvenated and uniformly distributed in said reactor using a substantially vertical draft tube fully immersed in the slurry which utilizes a rejuvenating gas injected substantially near the bottom of the substantially vertical draft tube whereby catalyst near the bottom of the slurry phase reactor is drawn up the draft tube and discharged from the top of the draft tube near the top of the slurry phase in said reactor.
    Type: Grant
    Filed: August 13, 1998
    Date of Patent: April 9, 2002
    Assignee: Exxon Research and Engineering Company
    Inventors: Larry E. Pedrick, Charles H. Mauldin, William C. Behrmann