Hydrate Or Production Thereof Patents (Class 585/15)
  • Patent number: 6359047
    Abstract: A gas hydrate inhibitor includes, by weight, a copolymer including about 80 to about 95% of polyvinyl caprolactam (VCL) and about 5 to about 20% of N,N-dialkylaminoethyl(meth)acrylate or N-(3-dimethylaminopropyl) methacrylamide.
    Type: Grant
    Filed: March 20, 2001
    Date of Patent: March 19, 2002
    Assignee: ISP Investments Inc.
    Inventors: Vu Thieu, Kirill N. Bakeev, Jenn S. Shih
  • Patent number: 6350928
    Abstract: A process is provided for converting a multi-phase fluid stream having an initial gas phase and an initial liquid phase to a gas hydrate slurry. The initial liquid phase includes an initial water and the initial gas phase includes a hydrocarbon gas. An inert solid particle medium is entrained in the multi-phase fluid stream to form a fluidizable mixture which is conveyed through the interior of a heat transfer tube enclosed within a shell. A heat transfer medium resides within the shell, but is external to the heat transfer tube in fluid isolation from the fluidizable mixture. The wall of the heat transfer tube provides a heat transfer surface for heat exchange between the multi-phase fluid stream and the heat transfer medium, cooling the multi-phase fluid stream on contact to a temperature below the gas hydrate formation temperature and converting at least a portion of the hydrocarbon gas and initial water to a plurality of solid gas hydrate particles.
    Type: Grant
    Filed: December 30, 1999
    Date of Patent: February 26, 2002
    Assignee: Marathon Oil Company
    Inventors: John J. Waycuilis, Stephen D. York
  • Patent number: 6331508
    Abstract: A method for controlling the formation of gas hydrate crystals in a fluid mixture by admixing with said fluid mixture a polyoxyalkylenediamine in an amount effective to prevent and/or inhibit crystal growth.
    Type: Grant
    Filed: February 2, 1998
    Date of Patent: December 18, 2001
    Assignee: BJ Service Company, U.S.A.
    Inventor: Marek K. Pakulski
  • Patent number: 6331652
    Abstract: There are disclosed a sulfonaldehyde derivative of formula (2): a phosphonium salt of formula (3): processes for producing the same and a sulfone derivative of formula (4): a process for producing the same and a process for producing lycopene therefrom.
    Type: Grant
    Filed: July 24, 2000
    Date of Patent: December 18, 2001
    Assignee: Sumitomo Chemical Company, Limited
    Inventors: Naoto Konya, Shinzo Seko
  • Patent number: 6281274
    Abstract: A composition for preventing or retarding the formation of gas hydrates during the transport of a fluid comprising water and a hydrocarbon through a conduit. The composition is a copolymer of vinyl caprolactam and vinyl pyridine, and terpolymers thereof, with vinyl pyrrolidone, preferably including 70-97% by weight vinyl caprolactam. Suitably such polymers have a molecular weight in the range of 500 to 2500, and are made in a polymerization solvent, preferably a glycol ether, most preferably, 2-butoxyethanol; and also including a carrier solvent, preferably monoethylene glycol.
    Type: Grant
    Filed: October 12, 1999
    Date of Patent: August 28, 2001
    Assignee: ISP Investments Inc.
    Inventors: Kirill N. Bakeev, Jui-Chang Chuang, Thomas Winkler, Michael A. Drzewinski, David E. Graham
  • Patent number: 6251836
    Abstract: A hydrate inhibitor comprising a blend of an additive (i) and at least one of an additive (ii) and an additive (iii) wherein additive (i) is a polymer of an ethylenically unsaturated N-heterocyclic carbonyl compound, with 6-8 ring atoms in the heterocyclic ring, additive (ii) is a corrosion inhibitor and additive (iii) is a salt of formula (I):[R1(R2)XR3]+Y− 1/v, I wherein each of R1, R2 and R3 is bonded directly to X, each of R1 and R2, which may be the same or different is an alkyl group of at least 4 carbons, X is S, NR4 or PR4, wherein each of R3 and R4 which may be the same or different represents hydrogen or an organic group, with the proviso that at least one of R3 and R4 is an organic group of at least 4 carbons, especially at least 5 carbons, and Y is an anion of valency v, wherein v is an integer of 1-4.
    Type: Grant
    Filed: November 18, 1997
    Date of Patent: June 26, 2001
    Assignee: BP Exploration Operating Company Limited
    Inventors: Simon Neil Duncum, Antony Roland Edwards, Keith James, Christopher George Osborne
  • Patent number: 6245955
    Abstract: There is provided a method to separate sub-sea and/or liquid hydrocarbons from the commingled stream of gas, water, oil, and or hydrocarbon condensate produced from subterranean wells comprising collecting a subterranean well product from at least one subterranean well, wherein said subterranean well product comprises hydrocarbon liquid, gas and water; forcing the water and gas to form hydrates; and separating the hydrates from the hydrocarbon liquid.
    Type: Grant
    Filed: August 31, 1999
    Date of Patent: June 12, 2001
    Assignee: Shell Oil Company
    Inventor: David Randolph Smith
  • Patent number: 6235091
    Abstract: Systems are provided for the selective removal of CO2 from a multicomponent gaseous stream to provide a CO2 depleted gaseous stream having at least a reduction in the concentration of CO2 relative to the untreated multicomponent gaseous stream. In the subject systems, the multicomponent gaseous stream is contacted with CO2 nucleated water under conditions of selective CO2 clathrate formation, where the CO2 nucleated water serves as a liquid absorbent or adsorbent to produce a CO2 clathrate slurry and CO2 depleted gaseous stream. In a preferred embodiment, the CO2 clathrate slurry is then decomposed to produce CO2 gas and nucleated water. The subject systems find use in a variety of applications where it is desired to selectively remove CO2 from a multicomponent gaseous stream, including chemical feedstock processing applications and air emissions control applications.
    Type: Grant
    Filed: March 22, 2000
    Date of Patent: May 22, 2001
    Inventor: Dwain F. Spencer
  • Patent number: 6235092
    Abstract: Systems are provided for the selective removal of CO2 from a multicomponent gaseous stream to provide a CO2 depleted gaseous stream having at least a reduction in the concentration of CO2 relative to the untreated multicomponent gaseous stream. In the subject systems, the multicomponent gaseous stream is contacted with CO2 nucleated water under conditions of selective CO2 clathrate formation, where the CO2 nucleated water serves as liquid solvent to produce a CO2 clathrate slurry and CO2 depleted gaseous stream. In a preferred embodiment, the CO2 clathrate slurry is then decomposed to produce CO2 gas and nucleated water. The subject systems find use in a variety of applications where it is desired to selectively remove CO2 from a multicomponent gaseous stream, including chemical feedstock processing applications and air emissions control applications.
    Type: Grant
    Filed: March 22, 2000
    Date of Patent: May 22, 2001
    Inventor: Dwain F. Spencer
  • Patent number: 6232273
    Abstract: Disclosed herein are clathrate hydrate inhibitors and the method of inhibiting the formation, agglomeration, and deposition of clathrate hydrate using the inhibitors. The clathrate hydrate inhibitor comprises a macromolecular compound in which 3-15 membered ring pendant is connected to the polymer main chain via a specific spacer group such as homo- or co-polymer of (meth)acryloyl pyrrolidine, pyrrolidinocarbonylethyl (meth)acrylate, 2-oxo-pyrrolidino-ethyl (meth)acrylate, glyoxyloyl pyrrolidine, pyrrolidinocarbonyl aspartate.
    Type: Grant
    Filed: May 7, 1998
    Date of Patent: May 15, 2001
    Assignee: Nippon Shokubai Co., Ltd.
    Inventors: Takashi Namba, Yoshikazu Fujii, Takuya Saeki, Hiyora Kobayashi
  • Patent number: 6222083
    Abstract: A method for inhibiting the formation of gas hydrates in a petroleum fluid having hydrate-forming constituents is claimed. More specifically, the method can be used to treat a petroleum fluid, such as natural gas conveyed in a pipe, to inhibit the formation of a hydrate flow restriction in the pipe. The hydrate inhibitors used for practicing the method comprise substantially water soluble homopolymers and copolymers of N-acyldehydroalanine derivatives which are esters or amides of N-acyldehydroalanine.
    Type: Grant
    Filed: October 1, 1999
    Date of Patent: April 24, 2001
    Assignee: ExxonMobil Upstream Research Company
    Inventor: Karla Schall Colle
  • Patent number: 6214091
    Abstract: A method is disclosed for inhibiting the plugging of a conduit for the transport of hydrocarbon fluids by gas hydrates.
    Type: Grant
    Filed: April 12, 2000
    Date of Patent: April 10, 2001
    Assignee: Shell Oil Company
    Inventor: Ulfert C. Klomp
  • Patent number: 6194622
    Abstract: A method for inhibiting the formation of gas hydrates in a petroleum fluid having hydrate-forming constituents is claimed. More specifically, the method can be used to treat a petroleum fluid, such as natural gas conveyed in a pipe, to inhibit the formation of a hydrate flow restriction in the pipe. The hydrate inhibitors used for practicing the method comprise substantially water soluble homopolymers and copolymers of surfactant monomers, wherein the surfactant monomer unit may be represented by the formula: where R1 and R2 independently are hydrogen or a methyl group, M is a metal cation, n is a number sufficient to produce a number average molecular weight between 1000 and 6,000,000, and o is a number from 1 to 5.
    Type: Grant
    Filed: March 11, 1999
    Date of Patent: February 27, 2001
    Assignee: ExxonMobil Upstream Research Company
    Inventors: Dennis G. Peiffer, Christine A. Costello, Lawrence D. Talley, Pamela J. Wright
  • Patent number: 6180843
    Abstract: An apparatus for producing gas hydrates includes a reactor vessel having a fluidized or expanded bed reaction zone. The reactor vessel has an upper portion and a lower portion, wherein a cross-sectional area of the upper portion is larger than a cross-sectional area of the lower portion. Water is introduced into the reactor vessel, and hydrate-forming gas is introduced, under an elevated pressure, into the lower portion of the reactor vessel. Preferably, the water and gas flow in a countercurrent manner through the reactor and into the fluidized or expanded bed reaction zone. The apparatus can include a mechanism for withdrawing unreacted hydrate-forming gas from the upper portion of the reactor vessel and recycling it back into the fluidized or expanded reaction bed. A defrosting device can be included with the reactor so that at least a portion of at least one wall of the reactor vessel can be defrosted.
    Type: Grant
    Filed: October 14, 1997
    Date of Patent: January 30, 2001
    Assignee: Mobil Oil Corporation
    Inventors: Robert Frederick Heinemann, David Da-Teh Huang, Jinping Long, Roland Bernard Saeger
  • Patent number: 6177497
    Abstract: The invention relates to an additive for inhibiting gas hydrate formation, containing a) from 5 to 90% by weight of 2-isobutoxyethanol, b) from 5 to 60% by weight of a copolymer which has structural units which are derived from maleic acid, maleic anhydride or derivatives of maleic acid or of maleic anhydride, and c) at least 10% by weight of water or a monohydric or polyhydric alcohol, except the 2-isobutoxyethanol, or mixtures of the stated substances, based on the total weight of the additive, the sum of the contents of compounds a) and b) being from 10 to 90% by weight, and a process for inhibiting gas hydrate formation using 2-isobutoxyethanol.
    Type: Grant
    Filed: January 29, 1999
    Date of Patent: January 23, 2001
    Assignee: Clariant GmbH
    Inventors: Peter Klug, Frank Holtrup
  • Patent number: 6152993
    Abstract: A method is disclosed for inhibiting the plugging of a conduit for the transport of hydrocarbon fluids by gas hydrates, wherein use is made of a hydrate formation inhibitor component of formula(R.sub.1) (R.sub.2) (R.sub.3) (R.sub.4)A.sup.+ Y.sup.- (I)wherein two of R.sub.1 -R.sub.4 are independently normal or branched alkyls having 4 or 5 carbon atoms, two of R.sub.1 -R.sub.4 are independently representing organic moieties having at least 8 carbon atoms, A represents a nitrogen or a phosphorus atom, Y represents an anion and wherein at least one of R.sub.1 -R.sub.4 represents a --(CH.sub.2 --CHR.sub.5 --O).sub.p --(CH.sub.2).sub.q --(CHR.sub.6 --CH.sub.2).sub.r --(CH.sub.2 --CHR.sub.7).sub.s --(CHR.sub.8).sub.t --O--C(O)--R.sub.9 moiety with the meaning as defined in the description.
    Type: Grant
    Filed: November 16, 1998
    Date of Patent: November 28, 2000
    Assignee: Shell Oil Company
    Inventor: Ulfert C. Klomp
  • Patent number: 6117929
    Abstract: A composition is provided herein for preventing or retarding the formation of gas hydrates or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit. The composition is a homopolymer of vinyl caprolactam having the low molecular weight in the range of 500 to 2500, or copolymers thereof, in a defined solvent. Such homopolymers and copolymers preferably are made and applied in the defined solvent, which, most preferably, is a glycol ether such as 2-butoxyethanol.
    Type: Grant
    Filed: December 3, 1998
    Date of Patent: September 12, 2000
    Assignee: ISP Investments Inc.
    Inventors: Kirill N. Bakeev, Jui-Chang Chuang, Michael A. Drzewinski, David E. Graham
  • Patent number: 6111155
    Abstract: A process for producing natural gas hydrate comprises three states (i), (ii), and (iii). State (i) comprises three pressure vessels (A1, A2, and A3), stage (ii) two pressure vessels (A4 and A5), and stage (iii) the pressure vessel (A6). The conditions of temperature and pressure in the pressure vessels are such that the gas hydrate is formed in the vessels. The formed hydrate is taken off through pipes (e1, e2, e3, e4, e5, and e6) from the pressure vessels to a manifold (34). Chilled water which is both the reactant water and coolant for the process is provided by cooling means (20) and supplied simultaneously to the lower part of each pressure vessel via pipe (22), manifold (32) and pipes (b1, b2, b4, b5, and b6). Natural gas from supply (26) is fed via pipe (30), manifold (32) and pipes (c1, c2, and c3) to nozzles in the lower part of each vessel (A1, A2, and A3) from which nozzles the gas bubbles upwards through the columns of water in vessels (A1, A2, and A3).
    Type: Grant
    Filed: October 7, 1997
    Date of Patent: August 29, 2000
    Assignee: BG PLC
    Inventors: Andrew Richard Williams, Trevor Smith
  • Patent number: 6107531
    Abstract: A method for inhibiting the formation of clathrate hydrates in a fluid having hydrate-forming constituents involves treating the fluid with an inhibitor comprising a substantially water soluble polymer having a polymer backbone .with a pendant C.sub.1 --C.sub.3 alkyl group; the polymer having an average molecular weight between about 1,000 and about 6,000,000. Preferably, the pendant alkyl group is a methyl group. The rate of nucleation, growth, and/or agglomeration of gas hydrate crystals in a petroleum fluid stream Is reduced using the alkylated polymer backbone inhibitor, thereby inhibiting the formation of a hydrate blockage in the pipe conveying the petroleum fluid stream. Test results are disclosed which unexpectedly show that alkylating the polymer backbone with a methyl group will produce a subcooling for the alkylated polymer that is at least about 2.degree. F. (about 1.1.degree. C.) greater than its nonalkylated counterpart.
    Type: Grant
    Filed: January 6, 1998
    Date of Patent: August 22, 2000
    Assignee: ExxonMobil Upstream Research Company
    Inventors: Karla S. Colle, Christine A. Costello, Larry D. Talley, Russell H. Oelfke, Enock Berluche
  • Patent number: 6106595
    Abstract: Methods are provided for the selective removal of CO.sub.2 from a multicomponent gaseous stream to provide a CO.sub.2 depleted gaseous stream having at least a reduction in the concentration of CO.sub.2 relative to the untreated multicomponent gaseous stream. In the subject methods, the multicomponent gaseous stream is contacted with CO.sub.2 nucleated water under conditions of selective CO.sub.2 clathrate formation, where the CO.sub.2 nucleated water serves as a liquid absorbent or adsorbent to produce a CO.sub.2 clathrate slurry and CO.sub.2 depleted gaseous stream. In a preferred embodiment, the CO.sub.2 clathrate slurry is then decomposed to produce CO.sub.2 gas and nucleated water. The subject methods find use in a variety of applications where it is desired to selectively remove CO.sub.2 from a multicomponent gaseous stream, including chemical feedstock processing applications and air emissions control applications.
    Type: Grant
    Filed: June 10, 1999
    Date of Patent: August 22, 2000
    Inventor: Dwain F. Spencer
  • Patent number: 6102986
    Abstract: The present application relates to a method for inhibiting gas hydrate formation, which involves the addition to the aqueous phase, in the case of multiphase mixtures comprising water, gas and possibly condensate, of an amine oxide or salts thereof.
    Type: Grant
    Filed: January 20, 1999
    Date of Patent: August 15, 2000
    Assignee: CLARIANT GmbH
    Inventor: Peter Klug
  • Patent number: 6093863
    Abstract: A composition for preventing or retarding the formation of gas hydrates or for reducing the tendency of gas hydrates to agglomerate, during the transport of a fluid comprising water and a hydrocarbon, through a conduit, comprising, (a) a polymer or copolymer selected from a terpolymer of vinyl pyrrolidone, vinyl caprolactam and an ammonium derivative monomer having from 6 to 12 carbon atoms, selected from the group consisting of dialkyl aminoalkyl methacrylamide, dialkyl dialkenyl ammonium halide and a dialkylamino alkyl acrylate or methacrylate, a copolymer of vinyl pyrrolidone and vinyl caprolactam, and a homopolymer of vinyl caprolactam, and (b) an alcohol containing three to five carbon atoms and one hydroxy group.
    Type: Grant
    Filed: December 1, 1999
    Date of Patent: July 25, 2000
    Assignee: ISP Investments Inc.
    Inventors: Jeffrey M. Cohen, William D. Young
  • Patent number: 6093862
    Abstract: A process for slowing the growth and/or agglomeration of hydrates in a fluid comprising water and gases by adding at least one essentially water-soluble polyoxyalkylene glycol macromer or at least one essentially water-soluble polymer containing a single macromer or a plurality of different macromer units of polyoxyalkylene glycol or a mixture of essentially water-soluble macromers and/or polymacromers. It is also possible to both retard the formation of hydrates and to substantially slow their growth and limit their agglomeration during crystallization by combining polyoxyalkylene glycol macromer type structures with kinetic additive type structures which are known to inhibit hydrate formation.
    Type: Grant
    Filed: August 5, 1998
    Date of Patent: July 25, 2000
    Assignee: Institut Francais du Petrole
    Inventors: Anne Sinquin, Marie Velly, Patrick Gateau, Jean-Pierre Durand
  • Patent number: 6090186
    Abstract: Methods are provided for the selective removal of CO.sub.2 from a multicomponent gaseous stream to provide a CO.sub.2 depleted gaseous stream having at least a reduction in the concentration of CO.sub.2 relative to the untreated multicomponent gaseous stream. In the subject methods, the multicomponent gaseous stream is contacted with CO.sub.2 nucleated water under conditions of selective CO.sub.2 clathrate formation, where the CO.sub.2 nucleated water serves as liquid solvent to produce a CO.sub.2 clathrate slurry and CO.sub.2 depleted gaseous stream. In a preferred embodiment, the CO.sub.2 clathrate slurry is then decomposed to produce CO.sub.2 gas and nucleated water. The subject methods find use in a variety of applications where it is desired to selectively remove CO.sub.2 from a multicomponent gaseous stream, including chemical feedstock processing applications and air emissions control applications.
    Type: Grant
    Filed: April 28, 1998
    Date of Patent: July 18, 2000
    Inventor: Dwain F. Spencer
  • Patent number: 6082118
    Abstract: A suitable slurry composition allows gas hydrates to be stored or transported under metastable conditions. The slurry includes gas hydrate particles and a carrier liquid for the gas hydrate particles. Suitable carrier liquids have a specific gravity in the range from about 0.6 to about 2, a pour point below about -20.degree. C. a viscosity of about 10 centipoise or less, and a thermal conductivity lower than that of the gas hydrate particles. The slurry can be stored or transported in a system that includes a container for holding the slurry; a device for agitating the slurry while in the container (e.g., a mixing blade, a rotating screw, a reciprocating box beam, or an ultrasound generator); a device for removing excess carrier liquid from the container while it is loaded or being loaded with gas hydrates and/or carrier liquid (e.g., a skimming device or a drain); and a device for reslurrifying the gas hydrates with carrier liquid before or during unloading of the gas hydrates from the container (e.g.
    Type: Grant
    Filed: July 7, 1998
    Date of Patent: July 4, 2000
    Assignee: Mobil Oil Corporation
    Inventors: Fred P. Endrizzi, Robert F. Heinemann, David Da-Teh Huang, Jinping Long, Roland B. Saeger, Anthony A. Urbanelli
  • Patent number: 6080704
    Abstract: The present invention provides a method for suppressing the formation of hydrates during drilling operations under conditions that are conducive to hydrate formation comprising using a water based fluid selected from the group consisting of a drilling, a drill-in, and a completion fluid, wherein said water based fluid comprises as an integral component a hydrate suppressing amount of a water-soluble organic compound having a molecular weight below about 800 and said fluid has effective rheology and fluid loss control properties.
    Type: Grant
    Filed: March 11, 1997
    Date of Patent: June 27, 2000
    Inventors: William S. Halliday, Dennis K. Clapper, Mark R. Smalling
  • Patent number: 6076278
    Abstract: The present invention provides improved methods of drying pipelines containing water which are to transport hydrate forming gaseous fluids. The methods basically comprise flowing a liquid which forms an azeotrope mixture with water into contact with water in a pipeline, the amount of the azeotropic liquid being sufficient to form an azeotrope mixture with the water whereby as the mixture is evaporated in the pipeline, the water concentration in the remaining mixture does not reach that concentration which will form hydrates with the hydrate forming gaseous fluid.
    Type: Grant
    Filed: December 18, 1997
    Date of Patent: June 20, 2000
    Assignee: Halliburton Energy Services, Inc.
    Inventor: Gary W. Bradley
  • Patent number: 6063972
    Abstract: A method of inhibiting or retarding formation of hydrates from water and a lower alkane, such as methane or ethane, involves adding additives which comprise (i) a corrosion inhibitor and (ii) a salt which is of formula [R.sup.1 (R.sup.2)XR.sup.3 ].sup.+ Y.sup.-, wherein each of R.sup.1, R.sup.2 and R.sup.3 is bonded directly to X, each of R.sup.1 and R.sup.2, which may be the same or different is an alkyl group of at least 4 carbons, X is S, NR.sup.4 or PR.sup.4, wherein each of R.sup.3 and R.sup.4 which may be the same or different represents hydrogen or an organic group, with the proviso that at least one of R.sup.3 and R.sup.4 is an organic group of at least 4 carbons, and Y is an anion, the additives being added in an amount effective to inhibit or retard hydrate formation, to a medium susceptible to hydrate formation.
    Type: Grant
    Filed: August 17, 1998
    Date of Patent: May 16, 2000
    Assignee: BP Exploration Operating Company Limited
    Inventors: Simon Neil Duncum, Antony Roland Edwards, Christopher George Osborne
  • Patent number: 6028234
    Abstract: The present invention provides a process for continuously producing clathrate hydrate. This process includes comprising the steps of:(a) pressurizing a hydrate-forming gas to an elevated pressure and cooling the hydrate-forming gas below the gas-water-hydrate equilibrium point at the elevated pressure;(b) cooling liquid water below the gas-water-hydrate equilibrium temperature for the elevated pressure;(c) charging hydrate-forming gas at the elevated pressure into a reaction zone which contains a movable surface;(d) atomizing water in the reaction zone in contact with the hydrate-forming gas to form gas hydrates in the reaction;(e) depositing the gas hydrates on the movable surface; and(f) collecting the gas hydrates from the movable surface.
    Type: Grant
    Filed: December 17, 1996
    Date of Patent: February 22, 2000
    Assignee: Mobil Oil Corporation
    Inventors: Robert Frederick Heinemann, David Da-Teh Huang, Jinping Long, Roland Bernard Saeger
  • Patent number: 6028235
    Abstract: A method and apparatus for safely, conveniently, and inexpensively liberating gas from gas hydrates includes the use of a device, provided adjacent to or in the bulk gas hydrates, for exposing the gas hydrates to heat from a gas or liquid (preferably steam). The gas hydrates can be directly exposed to the gas or liquid or indirectly exposed through a thermally conductive coil or channel. The heat from the gas or liquid dissociates the gas hydrates into the corresponding gas component and water component. After liberation, the gas component can be collected for further storage, transport, or use. The apparatus further includes a mechanism for moving at least a portion of the gas or liquid through the device for exposing the gas hydrates to heat. The device for exposing the gas hydrates to heat also can be movable, so it can be maintained in close proximity to or in contact with the gas hydrates for continued efficient gasification of the hydrates.
    Type: Grant
    Filed: October 14, 1997
    Date of Patent: February 22, 2000
    Assignee: Mobil Oil Corporation
    Inventors: Robert Frederick Heinemann, David Da-Teh Huang, Jinping Long, Roland Bernard Saeger
  • Patent number: 6028233
    Abstract: A method for inhibiting the formation of clathrate hydrates in a fluid having hydrate forming constituents is claimed. More specifically, the method can be used in treating a petroleum fluid stream such as natural gas conveyed in a pipe to inhibit the formation of a hydrate restriction in the pipe. The hydrate inhibitors used for practicing the method comprise substantially water soluble polymers having N-vinyl amide or N-allyl amide units. Specific examples of such copolymers include, N-vinyl-N-methylacetamide (VIMA) copolymerized with acryloylpyrrolidine (APYD) or acryloylpiperidine (APID), and more preferably, VIMA copolymerized with N-substituted methacrylamides, such as N-isopropylmethacrylamide (iPMAM) and methacryloylpyrrolidine (MAPYD) to produce inhibitors for practicing the claimed method.
    Type: Grant
    Filed: March 28, 1996
    Date of Patent: February 22, 2000
    Assignee: Exxon Production Research Company
    Inventors: Karla Schall Colle, Christine Ann Costello, Enock Berluche, Russell Harlan Oelfke, Larry Dalton Talley
  • Patent number: 6028236
    Abstract: The process for slowing the growth and/or agglomeration of hydrates in a fluid comprising water and gases comprises adding gas hydrate growth and/or agglomeration inhibitors comprising an essentially water soluble polymer, characterized by a total number of rotational degrees of freedom per statistical repeat unit RDFTm of over 9, preferably over 10, and a degree of polymerization DP of a statistical repeat unit in the range 18/RDFTm to 200,000, preferably in the range 20/RDFTm to 100,000. The growth and/or agglomeration inhibitor(s) is/are generally incorporated into the fluid to be treated in a concentration of 0.05% to 5% by weight with respect to the amount of water in the medium.
    Type: Grant
    Filed: November 25, 1998
    Date of Patent: February 22, 2000
    Assignee: Institut Francais du Petrole
    Inventors: Herve Toulhoat, Anne Sinquin
  • Patent number: 6025302
    Abstract: New compositions and methods for inhibiting the formation and/or growth of gas hydrates are described. The compositions are generally polyether ammonium compounds of the formula:[R'R'R"N--(CHRCH.sub.2 (OCH.sub.2 CHR).sub.n NR'--).sub.m R'].sup.+ [X].sup.-where R=H or CH.sub.3 ;R'=H or C.sub.a H.sub.2a+1, where a=1 to 4;R"=C.sub.b H.sub.2b+1, where b=4 to 20;m=1 to 4;and n=2 to 6.The anion [X].sup.- may be freely substituted. Methods for inhibiting the formation and/or growth of gas hydrates involve treating fluid mixtures with the polyether ammonium compounds described.
    Type: Grant
    Filed: May 18, 1998
    Date of Patent: February 15, 2000
    Assignee: BJ Services Company
    Inventor: Marek K. Pakulski
  • Patent number: 6015929
    Abstract: This invention is directed toward a method for inhibiting the formation (nucleation, growth and agglomeration) of clathrate hydrates. The method comprises adding into a mixture of hydrate forming substituents and water, an effective amount of a hydrate anti-agglomerate selected from the group consisting of anionic, cationic, non-ionic and zwitterionic hydrate anti-agglomerate. The hydrate anti-agglomerant has a polar head group and a nonpolar tail group said nonpolar tail group not exceeding 11 carbon atoms in the longest carbon chain.
    Type: Grant
    Filed: February 13, 1998
    Date of Patent: January 18, 2000
    Assignee: Exxon Research and Engineering Co.
    Inventors: Manese Rabeony, Dennis George Peiffer, Christine Ann Costello, Karla Schall Colle, Pamela J Wright, Larry Dalton Talley
  • Patent number: 5998681
    Abstract: A process for preventing the formation of a solid phase from hydrocarbons and water in a fluid is disclosed. A physical disturbance is transmitted to the fluid intermittently in time to prevent the formation of crystalline bonds in the fluid.
    Type: Grant
    Filed: November 8, 1995
    Date of Patent: December 7, 1999
    Assignee: Institut Francais du Petrole
    Inventor: Alexandre Rojey
  • Patent number: 5981816
    Abstract: The inhibiting or retarding hydrate formation, growth and/or agglomeration in a fluid comprising water and gases, is accomplished by addition of at least one hydrosoluble homopolymer or copolymer derived from at least one nitrogen-containing monomer selected from cationic monomers, for example those containing at least one quaternary ammonium moiety, amphoteric monomers, for example those containing at least one quaternary ammonium moiety and at least one carboxylate or sulphonate moiety, and various neutral monomers, said hydrosoluble homopolymer or copolymer being neutral or anionic, or consisting of a polyampholyte. The homopolymer, copolymer or mixture of polymers optionally mixed with an alcohol is generally incorporated into the fluid to be treated at a concentration of 0.05% to 5% by weight with respect to the quantity of water in the medium.
    Type: Grant
    Filed: May 15, 1997
    Date of Patent: November 9, 1999
    Assignee: Institut Francais du Petrole
    Inventors: Anne Sinquin, Marie Velly, Jean-Pierre Durand
  • Patent number: 5964093
    Abstract: A gas hydrate storage reservoir includes at least one insulated wall defining an opening and a sunlight permeable top covering the opening. A gas-tight, gas hydrate storage cavity is defined within the top and the wall(s). A cover element is provided to cover at least a portion of the top to prevent sunlight from passing through that portion of the top. The gas storage reservoir also includes devices for removing gas and water from the storage cavity. In use, when gas is desired by the user, the cover element is removed from at least a portion of the sunlight permeable top so that sunlight will pass through the top and into the storage reservoir. Heat energy from the sun warms the exposed gas hydrates, thereby forcing the hydrates to dissociate into gas and water. The gas is removed from the tank and transported to an appropriate location for use. When sunlight is unavailable or when additional gas is needed than that produced by dissociation via the sun, an external, auxiliary heater (e.g.
    Type: Grant
    Filed: October 14, 1997
    Date of Patent: October 12, 1999
    Assignee: Mobil Oil Corporation
    Inventors: Robert Frederick Heinemann, David Da-Teh Huang, Jinping Long, Roland Bernard Saeger
  • Patent number: 5958844
    Abstract: A method of transporting hydrates suspended in a fluid comprising water, a gas and a liquid hydrocarbon is described in which at least one non-ionic amphiphilic composition obtained by reacting at least one polymerized unsaturated vegetable oil with an aminoalcohol is incorporated into the fluid. The non-ionic amphiphilic composition is generally introduced in a concentration of 0.1% to 5% by weight with respect to the water.
    Type: Grant
    Filed: September 25, 1998
    Date of Patent: September 28, 1999
    Assignee: Institut Francais du Petrole
    Inventors: Anne Sinquin, Marie Velly, Gerard Hillion, Jean-Pierre Durand
  • Patent number: 5950732
    Abstract: A system for recovering liquid hydrocarbons from hydrates on an ocean floor includes a vessel, a positioning subsystem coupled to the vessel for holding the vessel in a desired location over a hydrate formation, a hydrate recovery subsystem coupled to the vessel for delivering hydrates from an ocean floor to the vessel and separating gas from hydrates removed from an ocean floor, a gas conversion subsystem coupled to the hydrate recovery subsystem for converting gas to liquids, and a storage and removal subsystem. Excess energy from the gas conversion subsystem is used elsewhere in the system. A method of recovering hydrates from an ocean floor is also provided.
    Type: Grant
    Filed: March 25, 1998
    Date of Patent: September 14, 1999
    Assignee: Syntroleum Corporation
    Inventors: Mark A. Agee, Larry J. Weick, Kenneth L. Agee
  • Patent number: 5900516
    Abstract: A method for inhibiting the formation and/or agglomeration of clathrate hydrates in a petroleum fluid stream containing water is disclosed. The disclosed method uses predetermined inhibitors having a guest group, a polymer backbone, and an anchor group positioned between the guest group and the polymer backbone. The inhibitor predetermination method comprises selection of the polymer backbone, anchor group and guest group using several types of criteria. The polymer backbone should produce a substantially water soluble polymer in combination with the anchor group and the guest group. The anchor group should be a hydrophilic moiety with between one and four hydrogen bonding atoms. The guest group should be either a hydrophobic or amphiphilic moiety with a carbon atom to heteroatom ratio greater than or equal to about two to one and an average van der Waals diameter between about 3.8 angstroms and about 8.6 angstroms.
    Type: Grant
    Filed: October 10, 1997
    Date of Patent: May 4, 1999
    Assignee: Exxon Production Research Company
    Inventors: Larry Dalton Talley, Russell Harlan Oelfke
  • Patent number: 5880319
    Abstract: Discussed is a process for preventing clathrate hydrate masses from detrimentally impeding the possible flow of a fluid susceptible to clathrate hydrate formation. The process is particularly useful in the natural gas and petroleum production, transportation and processing industry where gas hydrate formation can cause serious problems. Additives preferably contain one or more five member, six member and/or seven member cyclic chemical groupings. Additives include polymers having lactam rings. Additives can also contain polyelectrolytes that are believed to improve conformance of polymer additives through steric hinderance and/or charge repulsion. Additional additives include alkoxy compounds, and particularly those comprising ethoxy and or propoxy polymer blocks. Further additives include alcohols and oxazoline polymers which are preferably used in combination with polymers having lactam rings. Additives are useful in controlling clathrate hydrates in highly saline aqueous liquids.
    Type: Grant
    Filed: May 25, 1994
    Date of Patent: March 9, 1999
    Assignee: Colorado School of Mines
    Inventor: Earle Dendy Sloan, Jr.
  • Patent number: 5879561
    Abstract: A method for inhibiting the plugging of a conduit, the conduit containing a flowing mixture comprising an amount of hydrocarbons having from one to eight carbon atoms and an amount of water wherein the amounts of hydrocarbons and water could form hydrates at conduit temperatures and pressures, the method comprising the steps of:adding to the mixture an amount of a hydrate formation inhibitor component of the formula ##STR1## wherein two of R.sub.1 -R.sub.4 are independently normal or branched alkyls having 4 or 5 carbon atoms,two of R.sub.1 -R.sub.4 are independently representing organic moieties having at least 8 carbon atoms,A represents a nitrogen or phosphorus atom, andY represents an anion;the amount of the hydrate formation inhibitor component being effective to inhibit formation of hydrates in the mixture at conduit temperatures and pressures; andflowing the mixture containing the hydrate formation inhibitor component through the conduit.
    Type: Grant
    Filed: April 23, 1996
    Date of Patent: March 9, 1999
    Assignee: Shell Oil Company
    Inventors: Ulfert Cornelis Klomp, Rene Reijnhart
  • Patent number: 5877361
    Abstract: A process for transporting a fluid in a pipe under conditions where hydrates may form. In the process, the pipe fluid contains at least one of a gaseous hydrocarbon or liquid hydrocarbon and water and the water content is less than the liquid hydrocarbon content. The process includes the steps of 1) adding a dispersive additive in a hydrocarbon solution to the fluid to be transported, so as to form an emulsion, 2) transporting the liquid and gaseous hydrocarbons in the presence of water and the hydrates, 3) separating the gas phase, the hydrocarbon liquid in excess and a liquid hydrocarbon phase comprising the hydrates and the dispersing additive, and 4) separating the liquid hydrocarbon phase comprising the hydrates and the dispersing additives.
    Type: Grant
    Filed: June 6, 1996
    Date of Patent: March 2, 1999
    Assignee: Institute Francais du Petrole
    Inventors: Alexandre Rojey, Michel Thomas, Anne-Sophie Delion, Jean-Pierre Durand
  • Patent number: 5877362
    Abstract: A method for producing diphenylmethane from 1,1-diphenylethane with a high yield and selectivity, wherein the 1,1-diphenylethane is reacted with hydrogen and/or water.
    Type: Grant
    Filed: September 9, 1997
    Date of Patent: March 2, 1999
    Assignee: Nippon Petrochemicals Company, Limited
    Inventors: Hideyuki Dohi, Kazuo Sakamoto, Tadashi Tayanagi
  • Patent number: 5874660
    Abstract: A method for inhibiting the formation of clathrate hydrates in a fluid having hydrate forming constituents is disclosed. More specifically, the method can be used in treating a petroleum fluid stream such as natural gas conveyed in a pipe to inhibit the formation of a hydrate restriction in the pipe. The hydrate inhibitor used for practicing the method is selected from the family of substantially water soluble copolymers formed from N-methyl-N-vinylacetamide (VIMA) and one of three comonomers, vinylpyrrolidone (VP), vinylpiperidone (VPip), or vinylcaprolactam (VCap). VIMA/VCap is the preferred copolymer. These copolymers may be used alone or in combination with each other or other hydrate inhibitors. Preferably, a solvent, such as water, brine, alcohol, or mixtures thereof, is used to produce an inhibitor solution or mixture to facilitate treatment of the petroleum fluid stream.
    Type: Grant
    Filed: October 4, 1995
    Date of Patent: February 23, 1999
    Assignee: Exxon Production Research Company
    Inventors: Karla Schall Colle, Russell Harlan Oelfke, Malcolm A. Kelland
  • Patent number: 5841010
    Abstract: This invention is directed toward a method for inhibiting the formation (nucleation, growth and agglomeration) of clathrate hydrates. The method comprises adding into a mixture comprising hydrate forming substituents and water, an effective amount of a hydrate inhibitor selected from the group consisting of anionic, cationic, non-ionic and zwitterionic hydrate inhibitors. The hydrate inhibitor has a polar head group and a nonpolar tail group not exceeding 12 carbon atoms in the longest carbon chain.
    Type: Grant
    Filed: June 2, 1995
    Date of Patent: November 24, 1998
    Assignee: Exxon Production Research Company
    Inventors: Manese Rabeony, Dennis George Peiffer, Christine Ann Costello, Pamela Jean Wright, Karla Schall Colle, Larry Dalton Talley
  • Patent number: 5817898
    Abstract: A process is described for retarding or inhibiting the growth and/or aggregation of hydrates in production effluents comprising water and a gas under thermodynamic conditions in which hydrates can form, characterized in that a low concentration (0.05% to 5% by weight with respect to the water) of water-soluble copolymer containing hydrophobic groups is incorporated into the effluent.
    Type: Grant
    Filed: April 25, 1996
    Date of Patent: October 6, 1998
    Assignee: Institut Francais du Petrole
    Inventors: Anne Sophie Delion, Jean Pierre Durand, Patrick Gateau, Marie Velly
  • Patent number: 5789635
    Abstract: The invention concerns a process for inhibiting or retarding hydrate formation, growth and/or agglomeration in a fluid comprising water and gases, by addition of a hydrosoluble copolymer which does not contain a heterocycle but contains at least one sulphonate group.The copolymer is generally introduced at a concentration of 0.05% to 5% by weight with respect to the quantity of water in the medium.The copolymer can also be mixed with an alcohol (monoalcohol or polyol). In this case, the proportions are generally 0.5% to 20% by weight of alcohol with respect to the water content, for 0.05% to 3% by weight of copolymer with respect to the quantity of water content of the medium.
    Type: Grant
    Filed: February 6, 1997
    Date of Patent: August 4, 1998
    Assignee: Institut Francais du Petrole
    Inventors: Jean-Pierre Durand, Anne Sinquin, Marie Velly
  • Patent number: 5744665
    Abstract: Novel maleimide copolymers have at least two monomeric units, a maleimide unit and a vinyl unit having a pendant group, the pendant group having two to twenty-one carbon atoms, at least one nitrogen atom and at least one oxygen atom. The copolymer has an average molecular weight between about 1,000 and about 6,000,000. Preferred maleimide copolymers include acrylamide/maleimide copolymers, N-vinyl amide/maleimide copolymers, vinyl lactam/maleimide copolymers, alkenyl cyclic imino ether/maleimide copolymers, and acryloylamide/maleimide copolymers. The substantially water soluble maleimide copolymers are useful for inhibiting the formation of clathrate hydrates in a fluid having hydrate-forming constituents by reducing the rate of nucleation, growth, and/or agglomeration of gas hydrate crystals in a petroleum fluid stream, thereby inhibiting the formation of a hydrate blockage in the pipe conveying the petroleum fluid stream.
    Type: Grant
    Filed: June 6, 1996
    Date of Patent: April 28, 1998
    Assignee: Exxon Production Research Company
    Inventors: Christine Ann Costello, Enock Berluche, Russell Harlan Oelfke, Larry Dalton Talley
  • Patent number: H1749
    Abstract: A method for inhibiting the formation of clathrate hydrates in a fluid having hydrate forming constituents is disclosed. More specifically, the method can be used in treating a petroleum fluid stream such as natural gas conveyed in a pipe to inhibit the formation of a hydrate restriction in the pipe. The method uses a mixture comprising a first additive and a second additive. The mixture produces a synergistic hydrate inhibition effect. The first additive is selected from the class of substantially water soluble polymers. The second additive is selected from the class of ionic or non-ionic organic compounds which have a polar part and nonpolar part with the nonpolar part having an alkyl, alkenyl, or alkynyl group with 12 or fewer carbon atoms.
    Type: Grant
    Filed: September 15, 1994
    Date of Patent: September 1, 1998
    Assignee: Exxon Production Research Company
    Inventors: Karla Schall Colle, Christine Ann Costello, Russell Harlan Oelfke, Dennis George Peiffer, Manese Rabeony, Larry D. Talley, Pamela Jean Wright