Patents Represented by Attorney V. A. Mallare
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Patent number: 4495055Abstract: A process for improved catalytic hydrogenation of coal to produce increased yields of low boiling hydrocarbon liquids and gas products, in which a coal-oil slurry is fed directly with only limited preheating into an ebullated bed catalytic reaction zone to provide increased hydroconversion and improved yields of low boiling hydrocarbon liquids. In the process, a coal is slurried with a hydrogenated coal-derived liquid and heated to only a limited extent, as defined by a temperature-time severity unit index (STTU) less than about 0.1, so as to avoid depleting the hydrogen donor capacity of the solvent liquid, and the slurry is then fed directly into an ebullated bed catalytic reaction zone maintained at 650.degree.-900.degree. F. temperature and 1000-5000 psi hydrogen partial pressure. Supplemental heat is provided to the reaction zone as needed by heating recycled reactor liquid and recycled hydrogen streams to temperatures above the reaction zone temperature.Type: GrantFiled: January 26, 1984Date of Patent: January 22, 1985Assignee: HRI, Inc.Inventors: Alfred G. Comolli, Edwin J. Hippo
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Quenching hydrocarbon effluent from catalytic reactor to avoid precipitation of asphaltene compounds
Patent number: 4495060Abstract: A process for high hydroconversion of petroleum residua containing at least about 25 V % material boiling above 1000.degree. F. to produce lower boiling hydrocarbon liquid products and avoid undesirable precipitation of asphaltene compounds. In the process, the feedstock is at least about 50 percent catalytically hydroconverted to material boiling below 975.degree. F. and containing a mixture of gas and liquid fractions, after which the gas fraction is removed and the resulting liquid fractions is pressure-reduced and quenched to a temperature below about 775.degree. F. To avoid precipitation of asphaltene compounds which causes operational difficulties in the downstream equipment, the quench liquid used should have an API gravity not more than about 22.degree. API higher than the API gravity of the first pressure-reduced liquid fraction.Type: GrantFiled: December 27, 1982Date of Patent: January 22, 1985Assignee: HRI, Inc.Inventor: Lawrence M. Abrams -
Patent number: 4457831Abstract: A two-stage catalytic hydroconversion process for heavy hydrocarbon feedstocks usually containing fine particulate solids to produce lower boiling hydrocarbon liquid and gas products. The feedstock is fed into a first stage ebullated bed reactor containing fine sized catalyst and operated at moderate reaction conditions for hydroconversion to produce hydrocarbon gas and liquid fractions, from which a low boiling liquid fraction is separated and withdrawn as a product. The remaining gas and heavier liquid fractions are recombined and fed to a second stage ebullated bed reactor containing larger size catalyst for further hydroconversion reactions at less severe conditions to produce lower boiling hydrocarbon liquid fractions. Following product distillation steps, liquid product fractions are withdrawn and a portion of vacuum bottoms material is recycled to the second stage reactor to provide increased hydroconversion and improved yields of the light hydrocarbon liquid product.Type: GrantFiled: August 18, 1982Date of Patent: July 3, 1984Assignee: HRI, Inc.Inventor: Jeffrey L. Gendler
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Patent number: 4443330Abstract: An improved process for upgrading a coal liquid where the coal liquid is catalytically converted by hydrogenating and hydrocracking. In the process of upgrading a coal liquid where the coal liquid is fed with hydrogen into a catalytic reactor, the improvement comprises the feeding of a sulfur-containing liquid with the coal liquid. The sulfur-containing liquid ranges from about 0.2 to about 2.0 weight percent of the coal liquid feed. The sulfur-containing liquid is a high boiling hydrocarbon sulfur compound of the formula RSR.sub.1, where R is an alkyl group having 2 to 20 carbon atoms or a phenyl group and R.sub.1 is H, an alkyl group having 2 to 20 carbon atoms or a phenyl group.Type: GrantFiled: June 1, 1981Date of Patent: April 17, 1984Assignee: HRI, Inc.Inventor: Govanon Nongbri
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Patent number: 4441943Abstract: The present invention provides a method of tagging a substance to allow subsequent identification thereof comprising incorporating in the substance a polypeptide. Typically, the polypeptide is a synthetic polypeptide having a specific sequence of amino acids to constitute a particular molecular code which can be easily and readily identified.Type: GrantFiled: September 13, 1982Date of Patent: April 10, 1984Assignee: HRI Inc.Inventor: Paul H. Kydd
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Patent number: 4433184Abstract: Monosaccharides, such as glucose-water solution, are catalytically hydrogenated by being passed through multiple reaction zones connected in series and each containing a high-activity supported nickel catalyst to produce 99.8 W % overall conversion to an alditol solution such as sorbitol. The pH of liquid in each reaction zone is controlled to between 4.5 and 7 by adding an alkali solution such as sodium hydroxide to the feed to prevent acid leaching of catalyst metal and to help maintain catalyst activity therein. Reaction zone conditions used are 130.degree.-180.degree. C. temperature, 500-2000 psig hydrogen partial pressure, and a ratio of hydrogen gas/feed liquid within the range of about 500-5000. Feedstream liquid space velocity is maintained within range of 0.5-16 V.sub.f /Hr/V.sub.c, with higher space velocities being used for achieving lower incremental conversion desired in the subsequent reaction zones to help maintain pH of the effluent liquid within the desired range.Type: GrantFiled: April 27, 1981Date of Patent: February 21, 1984Assignee: HRI, Inc.Inventors: Derk T. A. Huibers, James C. Chao, Rajni C. Shah
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Patent number: 4427535Abstract: A process for the catalytic hydroconversion of special petroleum feedstocks, containing 10-28 W % asphaltenes, and having Ramsbottom carbon residue of 12-35 W %, such as Cold Lake and Lloydminster crude and residua materials. In the process, high percentage conversion (65-80 V %) to lower boiling hydrocarbon products can be achieved by maintaining a narrow range of reaction conditions, preferably in an ebullated bed catalytic reactor. Reaction temperature is 780.degree.-835.degree. F., hydrogen partial pressure is 2000-3000 psig, and space velocity is 0.25-5.0 V.sub.f /hr/V.sub.r. Higher conversion of about 80 to 95 volume percent can be obtained with recycle of 975.degree. F..sup.+ vacuum bottoms fraction to the reactor. Useful catalysts have total pore volume of about 0.5-0.9 cc/gm and include cobalt-molybdenum and nickel-molybdenum on alumina support.Type: GrantFiled: November 2, 1981Date of Patent: January 24, 1984Assignee: Hydrocarbon Research, Inc.Inventors: Govanon Nongbri, Susan M. Brandt, Michael C. Chervenak
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Patent number: 4424109Abstract: An improved catalyst for a coal liquefaction process; e.g., the H-Coal Process, for converting coal into liquid fuels, and where the conversion is carried out in an ebullated-catalyst-bed reactor wherein the coal contacts catalyst particles and is converted, in addition to liquid fuels, to gas and residual oil which includes preasphaltenes and asphaltenes. The improvement comprises a catalyst selected from the group consisting of the oxides of nickel molybdenum, cobalt molybdenum, cobalt tungsten, and nickel tungsten on a carrier of alumina, silica, or a combination of alumina and silica. The catalyst has a total pore volume of about 0.500 to about 0.900 cc/g and the pore volume comprises micropores, intermediate pores and macropores, the surface of the intermediate pores being sufficiently large to convert the preasphaltenes to asphaltenes and lighter molecules. The conversion of the asphaltenes takes place on the surface of micropores.Type: GrantFiled: April 7, 1981Date of Patent: January 3, 1984Assignee: Hydrocarbon Research, Inc.Inventors: Derk T. A. Huibers, Chia-Chen C. Kang
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Patent number: 4420644Abstract: A lignin-containing feed material in particulate form is mixed with a process-derived slurrying oil and fed into an ebullated catalyst bed hydrocracking reactor. Reaction conditions are maintained at 650.degree.-850.degree. F. temperature, 500-2500 psig hydrogen partial pressure and space velocity of 1.0-10 wt. lignin/hr./wt. catalyst. The reaction products are phase separated to recover hydrogen and slurrying oil, and the resulting liquid stream is passed to a thermal hydrodealkylation step. The reacted stream is fractionated to produce phenol and benzene products, along with a heavy alkylated material which is recycled to the hydrodealkylation step to increase the yield of phenol and benzene.Type: GrantFiled: August 24, 1981Date of Patent: December 13, 1983Assignee: Hydrocarbon Research, Inc.Inventors: Derk T. A. Huibers, Hugh J. Parkhurst, Jr.
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Patent number: 4410420Abstract: A multi-zone fluidized bed hydrocarbon conversion process and apparatus for producing gas and distillable liquid products from heavy hydrocarbon feedstocks. The feedstock is introduced into an upper fluidized bed primary cracking zone maintained at temperature of 850.degree.-1400.degree. F. for cracking reactions therein, and resulting tars and coke are deposited on and within a particulate carrier material contained therein. The carrier material containing said tars and coke descends successively through a stripping zone to remove tars and an interim controlled temperature zone for secondary cracking against an upflowing hot reducing gas, then descends into a lower fluidized bed gasification zone. The gasification zone is maintained at temperature of 1600.degree.-1900.degree. F. by oxygen-containing gas and steam introduced therein to gasify the coke deposits and produce the reducing gas.Type: GrantFiled: January 15, 1982Date of Patent: October 18, 1983Assignee: HRI, Inc.Inventors: Barry Liss, Michael Calderon, Marvin S. Rakow
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Patent number: 4407367Abstract: The recovery of heavy crude oils and tars from subterranean oil bearing formations is enhanced by the injection of pressurized and heated hydrocarbon vapor into a single well drilled into the formation. Condensation of the hydrocarbon vapor heats the heavy oil and tars entrapped in the formation and dilutes the oil so as to decrease its viscosity and enhance its flow into a lower portion of the well. The oil and solvent collected are removed to the surface by pumping. The preferred hydrocarbon vapor is a low boiling fraction derived by distillation of the oil recovered from the formation, however, some stable externally-produced aromatic hydrocarbon vapors of high solvent power such as benzene or toluene or mixtures thereof may also be used and reclaimed from the oil by distillation.Type: GrantFiled: October 14, 1980Date of Patent: October 4, 1983Assignee: HRI, Inc.Inventor: Paul H. Kydd
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Patent number: 4404084Abstract: An improved process for hydrogenation of coal containing ash with agglomeration and removal of ash from an ebullated bed catalytic reactor to produce deashed hydrocarbon liquid and gas products. In the process, a flowable coal-oil slurry is reacted with hydrogen in an ebullated catalyst bed reaction zone at elevated temperature and pressure conditions. The upward velocity and viscosity of the reactor liquid are controlled so that a substantial portion of the ash released from the coal is agglomerated to form larger particles in the upper portion of the reactor above the catalyst bed, from which the agglomerated ash is separately withdrawn along with adhering reaction zone liquid. The resulting hydrogenated hydrocarbon effluent material product is phase separated to remove vapor fractions, after which any ash remaining in the liquid fraction can be removed to produce substantially ash-free coal-derived liquid products.Type: GrantFiled: March 11, 1982Date of Patent: September 13, 1983Assignee: Hri, Inc.Inventors: Derk T. A. Huibers, Edwin S. Johanson
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Patent number: 4400263Abstract: A process for converting coal and other hydrocarbonaceous materials into useful and more valuable liquid products.Type: GrantFiled: February 9, 1981Date of Patent: August 23, 1983Assignee: HRI, Inc.Inventors: Paul H. Kydd, Michael C. Chervenak, George R. DeVaux
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Patent number: 4400181Abstract: Carbonaceous solid material such as coal is gasified in a fast fluidized bed gasification system utilizing dual fluidized beds of hot char. The coal in particulate form is introduced along with oxygen-containing gas and steam into the fast fluidized bed gasification zone of a gasifier assembly wherein the upward superficial gas velocity exceeds about 5.0 ft/sec and temperature is 1500.degree.-1850.degree. F. The resulting effluent gas and substantial char are passed through a primary cyclone separator, from which char solids are returned to the fluidized bed. Gas from the primary cyclone separator is passed to a secondary cyclone separator, from which remaining fine char solids are returned through an injection nozzle together with additional steam and oxygen-containing gas to an oxidation zone located at the bottom of the gasifier, wherein the upward gas velocity ranges from about 3-15 ft/sec and is maintained at 1600.degree.-200.degree. F. temperature.Type: GrantFiled: January 28, 1982Date of Patent: August 23, 1983Assignee: Hydrocarbon Research, Inc.Inventors: George J. Snell, Paul H. Kydd
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Patent number: 4400468Abstract: A process is provided for producing adipic acid from a renewable resource, i.e., biomass. The process comprises: hydrolyzing the renewable resource to provide 5-hydroxymethylfurfural, hydrogenating the 5-hydroxymethylfurfural in the presence of a catalyst to provide 2, 5-tetrahydrofurandiomethanol, treating the 2, 5-tetrahydrofurandiomethanol with hydrogen in the presence of a catalyst to provide 1, 6 hexanediol, and oxidizing the 1, 6 hexanediol in the presence of a microorganism to provide adipic acid. The formation of the adipic acid is provided with the microorganism of Gluconobacter oxydans subsp. oxydans. The renewable resources are wastes selected from the group consisting of paper, wood, corn stalks, and logging residues.Type: GrantFiled: October 5, 1981Date of Patent: August 23, 1983Assignee: Hydrocarbon Research Inc.Inventor: Marcel Faber
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Patent number: 4398852Abstract: A method for adding and removing fine particles from a pressurized reactor is provided, which comprises connecting the reactor to a container, sealing the container from the reactor, filling the container with particles and a liquid material compatible with the reactants, pressurizing the container to substantially the reactor pressure, removing the seal between the reactor and the container, permitting particles to fall into or out of the reactor, and resealing the container from the reactor. An apparatus for adding and removing particles is also disclosed.Type: GrantFiled: February 17, 1981Date of Patent: August 16, 1983Assignee: HRI, Inc.Inventor: John D. Milligan
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Patent number: 4381986Abstract: A process and apparatus for cooling and solidifying a stream of heavy hydrocarbon material normally boiling above about 850.degree. F., such as vacuum bottoms material from a coal liquefaction process. The hydrocarbon stream is dropped into a liquid bath, preferably water, which contains a screw conveyor device and the stream is rapidly cooled, solidified and broken therein to form discrete elongated particles. The solid extrudates or prills are then dried separately to remove substantially all surface moisture, and passed to further usage.Type: GrantFiled: July 27, 1981Date of Patent: May 3, 1983Assignee: Hydrocarbon Research, Inc.Inventors: Salvatore J. Antieri, Alfred G. Comolli
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Patent number: 4380678Abstract: Aldoses such as glucose solution are catalytically hydrogenated in a multiple-stage fixed-bed reaction process to produce glycerol and other polyol products. The feedstream pH to each reactor is controlled to between about 7 and 14 by adding an alkaline promotor material such as calcium hydroxide. First-stage reaction zone conditions are 130.degree.-180.degree. C. temperature, 500-2000 psig hydrogen partial pressure, and feedstream liquid space velocity is within range of 0.5-3.5 V.sub.f /Hr/V.sub.c. The first reactor uses a high activity nickel catalyst to produce at least about 98 W % conversion to alditol such as sorbitol solution.The resulting alditols such as 15-40 W % sorbitol solution in water is catalytically hydrocracked in a second-stage fixed-bed reaction zone preferably using a high-activity nickel catalyst to produce at least about 30 W % conversion to glycerol and glycols products. Second-stage reaction zone conditions are 420.degree.-520.degree. F.Type: GrantFiled: March 20, 1981Date of Patent: April 19, 1983Assignee: Hydrocarbon Research, Inc.Inventor: Amalesh K. Sirkar