Patents Examined by G. E. Schmitkons
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Patent number: 4457830Abstract: A process for catalytic hydroconversion of heavy petroleum feedstocks containing preasphaltenes to produce lower-boiling hydrocarbon liquid products. In the process, an inorganic acid is added to the reactor effluent residual fraction boiling above about 950.degree. F. to produce substantial precipitation of the preasphaltene materials. The clarified overhead fraction is recycled to the reaction zone, and the precipitated preasphaltene material is passed to further processing, such as coking to recover additional light oils. The reactor can advantageously be an upflow ebullated catalytic bed type and may use fine size catalyst for increased hydroconversion.Type: GrantFiled: December 28, 1981Date of Patent: July 3, 1984Assignee: HRI, Inc.Inventor: Paul H. Kydd
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Patent number: 4454025Abstract: A process for economically converting carbo-metallic oils to lighter products. The carbo-metallic oils contain 650.degree. F. plus material which is characterized by a carbon residue on pyrolysis of at least about 1 and a Nickel Equivalents of heavy metals content of at least about 4 parts per million. This process comprises flowing the carbo-metallic oil together with particulate cracking catalyst through a progressive flow type reactor having an elongated reaction chamber, which is at least in part vertical or inclined, for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds, at a temperature of about 900.degree. to about 1400.degree. F., and under a pressure of about 10 to about 50 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 50% to about 90% while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.Type: GrantFiled: May 13, 1981Date of Patent: June 12, 1984Assignee: Ashland Oil, Inc.Inventor: William P. Hettinger, Jr.
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Patent number: 4435278Abstract: A process for hydroprocessing a hydrocarbonaceous feedstock containing constituents boiling above 350.degree. C. comprises contacting said feedstock with hydrogen under hydroprocessing conditions with a catalyst composition comprising a rigidly interconnected pack containing inorganic matrix oxide and about 10-95% fluid catalytic cracking catalyst microspheroids, based upon the total weight of said matrix oxide and said microspheroids, said pack characterized by a pore volume of at least 0.15 cc. per cc., at least about 30% of said pore volume present as pores having diameters within the range of 50-250 Angstroms and at least about 5% of said pore volume present as pores having diameters greater than 1,000 Angstroms.Type: GrantFiled: June 9, 1980Date of Patent: March 6, 1984Assignee: Chezon Research Co.Inventor: Hong C. Chen
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Patent number: 4432864Abstract: A method is disclosed for cracking a carbo-metallic oil feed containing high amounts of coke forming carbonaceous materials as characterized by a Conradson carbon value of more than 1 and containing a level of nickel and/or vanadium of greater than 5 ppm. The method includes contacting the feed with catalyst particles and liquid water containing hydrogen sulfide. At least a portion of the water may be recycled water from prior catalytic cracking of an oil feed containing sulfur.Type: GrantFiled: December 18, 1981Date of Patent: February 21, 1984Assignee: Ashland Oil, Inc.Inventors: George D. Myers, Lloyd E. Busch
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Patent number: 4431520Abstract: The hydroconversion of a heavy hydrocarbon charge containing asphaltenes and metal, sulfur and nitrogen impurities is performed in the presence of a catalyst comprising:(a) soot particles of the cenosphere type(b) a compound of a metal selected from the groups V B, VI B, VII B and VIII of the periodic classification.Type: GrantFiled: August 11, 1982Date of Patent: February 14, 1984Assignee: Institut Francais du PetroleInventors: Pierre Giuliani, Yves Jacquin, Christian Busson, Jean-Francois Josserand
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Patent number: 4427539Abstract: The method and means for effecting selective visbreaking of residual oil feeds comprising metallo-organic compounds with a fluid solid sorbent particle material in the presence of process sour water and wet gas recycle material is described to provide a gas oil rich product more suitable for crystalline zeolite fluid catalytic cracking operations.Type: GrantFiled: September 7, 1982Date of Patent: January 24, 1984Assignee: Ashland Oil, Inc.Inventors: Lloyd E. Busch, Gerald O. Henderson
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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: 4419223Abstract: A method is disclosed for cracking a carbo-metallic oil feed containing high amounts of coke forming carbonaceous materials as characterized by a carbon residue on pyrolysis of at least about 1 and by a level of heavy metal(s) of at least about 5.5 ppm by weight of Nickel Equivalents. The method includes contacting the feed with cracking catalyst bearing an accumulation of at least about 3,000 ppm by weight of Nickel Equivalents of heavy metal(s) and with additional material including water. The resultant stream flows through a progressive flow type reactor for a vapor residence time of about 0.5 to about 6 seconds at conditions sufficient for causing a conversion per pass of about 60% to about 90%. The additional material is added in a weight ratio relative to feed of up to about 0.4 and includes water in a weight ratio relative to feed of at least about 0.04. The water may be introduced as steam and/or liquid water.Type: GrantFiled: April 30, 1982Date of Patent: December 6, 1983Assignee: Ashland Oil, Inc.Inventors: George D. Myers, Lloyd E. Busch
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Patent number: 4415438Abstract: A process for converting residual oil comprising vacuum bottoms in the presence of a cracking catalyst of high surface area and comprising an ultrastable zeolite is described. More particularly, a conversion process particularly contributing to producing cycle oil and gasoline boiling range products with reduced carbon deposition in combination with a relatively high regeneration temperature operation of at least 1350.degree. F. and above, and a short contact time riser hydrocarbon conversion operation contributing to reducing slurry oil product in favor of lower boiling products is described. A fluid cracking catalyst comprising a special ultrastable crystalline zeolite of high silica to alumina ratio provides hydrothermal stability of acceptable tolerance in the environment employed.Type: GrantFiled: November 24, 1981Date of Patent: November 15, 1983Inventors: Robert R. Dean, Warren S. Letzsch, Jean L. Mauleon
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Patent number: 4414098Abstract: A process is disclosed for upgrading a hydrocarbon oil feed having a significant content of metals, especially vanadium, to provide a higher grade of oil products by contacting the feed under sorbing conditions in an upgrading zone with a high surface area, high pore volume sorbent material containing an added alkaline metal to neutralize acidic cracking sites. Upgrading conditions are such that coke and metals are deposited on the sorbent in the upgrading zone. Coked sorbent is regenerated by contact with an oxygen containing gas under regeneration conditions to remove the coke, and regenerated sorbent is recycled to the upgrading zone for contact with fresh feed. The added alkaline metal is present on the sorbent in an amount sufficient to neutralize substantially all of the acidic cracking sites and provide a sorbent material having a MAT relative activity in the range of about 0 to about 1 percent.Type: GrantFiled: July 30, 1981Date of Patent: November 8, 1983Assignee: Ashland Oil, Inc.Inventors: Oliver J. Zandona, William P. Hettinger, Jr.
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Patent number: 4411770Abstract: This invention provides an improved process for hydroconversion of a heavy hydrocarbon oil having a CCR content of 8-30 weight percent, which process involves contacting the heavy oil in a hydrovisbreaking zone containing a low acidity zeolite catalyst and recovering and fractionating the visbroken effluent to provide distillate products and a 1000.degree. F.+ fraction which has a Kinematic Viscosity between about 30,000-60,000 centistokes at 100.degree. F.Type: GrantFiled: April 16, 1982Date of Patent: October 25, 1983Assignee: Mobil Oil CorporationInventors: Nai Y. Chen, Eric J. Scott, David S. Shihabi
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Patent number: 4409094Abstract: A process for treating liquid hydrocarbons to remove toxic, mutagenic and/or carcinogenic aromatic hydrocarbons comprises feeding the hydrocarbons into a reactor where vapors are thermally treated in contact with a catalyst consisting essentially of calcium oxide or a calcium oxide containing mineral. Thermally treating liquid hydrocarbons in contact with calcium oxide preferentially increases the cracking of aromatics thus producing a product having a reduced amount of aromatic compounds.Type: GrantFiled: August 8, 1980Date of Patent: October 11, 1983Assignee: Massachusetts Institute of TechnologyInventors: John P. Longwell, William A. Peters
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Patent number: 4409093Abstract: A method for decreasing the amount of coke produced during the cracking of hydrocarbon feedstock to lower molecular weight products in a reaction zone is disclosed, where the feedstock contains at least two metal contaminants selected from the class consisting of nickel, vanadium and iron, and where these contaminants become deposited on the catalyst. The method comprises passing catalyst from the reaction zone through a regeneration zone operated under net reducing conditions and through a reduction zone maintained at an elevated temperature for a time sufficient to at least partially passivate the catalyst.Type: GrantFiled: July 22, 1981Date of Patent: October 11, 1983Assignee: Exxon Research and Engineering Co.Inventors: Roby Bearden, Jr., Gordon Stuntz
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Patent number: 4407714Abstract: A process for economically converting carbo-metallic oils to lighter products. The carbo-metallic oils contain 650.degree. F..sup.+ material, at least a portion of said 650.degree. F..sup.+ material containing components which will not boil before about 1025.degree. F., said 650.degree. F..sup.+ material further being characterized by a carbon residue on pyrolysis of at least about 1 and a Nickel Equivalents of heavy metals content of at least about 4 parts per million. This process comprises providing a cracking catalyst having an average pore volume of at least about 0.2 cc per gram and an average particle diameter in the range of about 20 microns to about 150 microns, flowing the carbo-metallic oil together with the cranking catalyst through a progressive flow type reactor having an elongated reaction chamber, which is at least in part vertical or inclined, for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds, at a temperature of about 900.degree. to about 1400.Type: GrantFiled: May 13, 1981Date of Patent: October 4, 1983Assignee: Ashland Oil, Inc.Inventors: George D. Myers, deceased, William P. Hettinger, Jr., Stephen M. Kovach
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Patent number: 4406773Abstract: A process for economically converting carbo-metallic oils to lighter products. The carbo-metallic oils contain 650.degree. F. plus material which is characterized by a carbon residue on pyrolysis of at least about 1 and a Nickel Equivalent of heavy metals content of at least about 4 parts per million. This process comprises flowing the carbo-metallic oil together with particulate cracking catalyst through a progressive flow-type reactor having an elongated reaction chamber, which is at least in part vertical or inclined, for a predetermined vapor riser residence time in the range of about 0.5 to about 10 seconds, at a temperature of about 900.degree. to about 1400.degree. F., and under a pressure of about 10 to about 50 pounds per square inch absolute sufficient for causing a conversion per pass in the range of about 50% to about 90% while producing coke in amounts in the range of about 6 to about 14% by weight based on fresh feed, and laying down coke on the catalyst in amounts in the range of about 0.Type: GrantFiled: May 13, 1981Date of Patent: September 27, 1983Assignee: Ashland Oil, Inc.Inventors: William P. Hettinger, Jr., Roger M. Benslay
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Patent number: 4405441Abstract: Distillates are prepared from asphaltenes-rich feeds by a process comprising subjecting the feed to catalytic hydroconversion, and subjecting the distillation residue of the hydroconverted product to a combination of solvent deasphalting and thermal cracking.Type: GrantFiled: September 30, 1982Date of Patent: September 20, 1983Assignee: Shell Oil CompanyInventors: Robert H. Van Dongen, John R. Newsome
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Patent number: 4405445Abstract: An improved process for economically converting carbo-metallic oils to lighter products. Enhanced catalyst activity is enjoyed through use of a select process to vaporize and atomize the high boiling portion of a carbo-metallic oil feed. The carbo-metallic oil feed is dispersed into droplets having a diameter of at least smaller than 350 microns and preferably 100 microns or less. These small droplets ensure more even coverage of the catalyst surface and decrease diffusion problems. The water utilized for dispersion of the carbo-metallic oil feed is present as a homogenized mixture in fine oil droplets with an average diameter below 1,000 microns. The water is dispersed in the carbo-metallic oil feed through use of a select mixing apparatus and can be dispersed as finer droplet sizes through use of an emulsifying or dispersing agent. The ratio of water to carbo-metallic oil feed ranges from about 0.04 to 0.25 by weight and the concentration of emulsifying agent ranges from 0.01 to 10 wt.Type: GrantFiled: August 21, 1981Date of Patent: September 20, 1983Assignee: Ashland Oil, Inc.Inventors: Stephen M. Kovach, Edward B. Cornelius
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Patent number: 4404087Abstract: The formation of carbon on metals exposed to hydrocarbons in a thermal cracking process is reduced by contacting such metals with an antifoulant selected from the group consisting of tin, a combination of tin and antimony, a combination of germanium and antimony, a combination of tin and germanium and a combination of tin, antimony and germanium.Type: GrantFiled: September 30, 1982Date of Patent: September 13, 1983Assignee: Phillips Petroleum CompanyInventors: Larry E. Reed, Randall A. Porter, Floyd E. Farha, Jr., Jack P. Guillory
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Patent number: 4404088Abstract: A hydrocracking process of improved flexibility comprises three hydroprocessing stages and a fractionating zone such that the effluent from the first hydroprocessing stage is fractionated into a first fraction consisting of gasoline and lower boiling components, a second fraction, the residuum, having a normal boiling point greater than about 700.degree. F. (370.degree. C.), and a third fraction, the middle and heavy distillate, consisting of the remainder of the effluent of the first hydroprocessing stage. The second fraction undergoes hydrocracking in a second hydroprocessing stage with recycle of the effluent from said second hydroprocessing stage to the fractionation zone, and the third fraction undergoes hydrocracking in a third hydrocracking stage.Type: GrantFiled: October 2, 1981Date of Patent: September 13, 1983Assignee: Chevron Research CompanyInventors: Robert W. Bachtel, Dennis R. Cash
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Patent number: 4404090Abstract: A contaminating metal on a cracking catalyst used for the cracking of hydrocarbons is passivated by contacting the catalyst with a hydrocarbon gas or mixture of gases comprising molecules of three carbon atoms or less at passivation reaction conditions prior to the cycling of the catalyst to the cracking zone, which gas or mixture of gases is first saturated with water at specific conditions.Type: GrantFiled: July 16, 1982Date of Patent: September 13, 1983Assignee: UOP Inc.Inventors: Carmen Castillo, John C. Hayes