Chemical Treatment (refining Or Modification Except Mere Solvent Extraction) Patents (Class 208/27)
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Patent number: 5376260Abstract: Heavy waxy oil is dewaxed by a mild cracking and isomerization process using a catalyst comprising SSZ-32 and at least one Group VIII metal. The heavy oil contains naphthenic wax, which includes only a relatively small amount of normal alkanes. Naphthenic wax containing a minor amount of oil may also be dewaxed using the process.Type: GrantFiled: April 5, 1993Date of Patent: December 27, 1994Assignee: Chevron Research and Technology CompanyInventors: Donald S. Santilli, Stacey I. Zones
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Patent number: 5370788Abstract: Charge waxy hydrocarbon is converted to lube oil base stock by hydrotreating in the presence of catalyst characterized by its ability to convert a waxy hydrocarbon distillate of high pour point to a hydrocarbon product of reduced pour point and high viscosity index, suitable for use as a lube oil base stock, which comprises a support containing about 2-50 w % silica and 50-98 w % alumina, bearing 2-10 w % of a non-noble Group VIII metal, as metal, metal oxide, or metal sulfide, about 8-20 w % of a Group VI-B metal, as metal, metal oxide, or metal sulfide, less than 0.5% halogen; and 0-2 w % of phosphorus, the atom ratio of Group VIII metal to Group VI-B metal being about 0.3-2:1, said catalyst being characterized by a micropore mode of about 60-130 .ANG. diameter, a Total Surface Area of about 150-300 m.sup.2 /g, a Total Pore Volume of about 0.45-0.9 cc/g and a Pore Volume of pores with pore diameter >500 .ANG. of about 0.02-0.25 cc/g.Type: GrantFiled: December 18, 1992Date of Patent: December 6, 1994Assignee: Texaco Inc.Inventors: Pei-Shing E. Dai, Joseph A. Durkin, Bobby R. Martin
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Patent number: 5292989Abstract: A catalyst useful for hydroisomerizing wax containing feeds comprises a Group VIII metal on an alumina or silica-alumina support having less than about 35 wt % silica and is surface treated with at least about 0.5 wt % silica or a silica precursor.Type: GrantFiled: January 8, 1993Date of Patent: March 8, 1994Assignee: Exxon Research & Engineering Co.Inventor: Stephen M. Davis
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Patent number: 5292426Abstract: Hydrocarbon lube boiling range stock of high Pour Point may be catalytically hydrotreated to yield a product of high viscosity index and reduced Pour Point which is suitable as a lube base oil.Type: GrantFiled: October 18, 1991Date of Patent: March 8, 1994Assignee: Texaco Inc.Inventors: John B. Holland, Gerald F. Prescott, Dann G. Roy, Avilino Sequeira, Jr., James R. Whiteman
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Patent number: 5290426Abstract: A novel, high porosity, high surface area catalyst is disclosed which is useful in wax isomerization processes, especially for the production of high viscosity index, low pour point lubricating oil base stocks or blending stocks. The catalyst contains a catalytically active metal component selected from the group consisting of Group VIB and Group VIII metals, and mixtures thereof, preferably Group VIII metals, and mixtures thereof, more preferably noble Group VIII metals and mixtures thereof, most preferably platinum which catalytically active metal component is present in the range of about 0.01 to 5.0 wt %, and a fluorine content in the range of about 0.01 to about 10.0. The catalyst employs a refractory metal oxide support material, one preferably predominantly (i.e., at least 50 wt %) alumina, most preferably completely alumina, e.g., gamma or eta alumina. The finished catalyst has a porosity, expressed in terms of pore volume, of at least about 0.Type: GrantFiled: August 20, 1992Date of Patent: March 1, 1994Assignee: Exxon Research and Engineering CompanyInventors: Ian A. Cody, David H. Dumfries, Arthur H. Neal, Kenneth L. Riley
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Patent number: 5288395Abstract: Petroleum wax feeds are converted to high viscosity index lubricants by a two-step hydrocracking-hydroisomerization process in which the wax feed is initially subjected to hydrocracking under mild conditions with a conversion to non-lube range products of no more than about 40 weight percent of the feed. The hydrocracking is carried out at a hydrogen pressure of at least 1,000 psig (7,000 kPa) using an amorphous or mesoporous crystalline catalyst which preferentially removes the aromatic components present in the initial feed. The hydrocracked effluent is then subjected to hydroisomerization in a second step using a low acidity hydroisomerization catalyst which effects a preferential isomerization on the paraffin components to less waxy, high VI isoparaffins. The second stage, which is carried out at relatively low temperature, typically from 600.degree. to 650.degree. F. with a 650.degree. F.Type: GrantFiled: July 24, 1991Date of Patent: February 22, 1994Assignee: Mobil Oil CorporationInventors: David O. Marler, Dominick N. Mazzone
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Patent number: 5282958Abstract: A process is disclosed for dewaxing a hydrocarbon feed to produce a dewaxed lube oil. The feed includes straight chain and slightly branched chain paraffins having 10 or more carbon atoms. In the process the feed is contacted under isomerization conditions with an intermediate pore size molecular sieve having a crystallite size of no more than about 0.5.mu. and pores with a minimum diameter of at least 4.8.ANG. and with a maximum diameter of 7.1.ANG. or less. The catalyst has sufficient acidity so that 0.5 g thereof when positioned in a tube reactor converts at least 50% of hexadecane at 370.degree. C., a pressure of 1200 psig, a hydrogen flow of 160 ml/min, and a feed rate of 1 ml/hr. It also exhibits 40 or greater isomerization selectivity when used under conditions leading to 96% conversion of hexadecane to other chemicals. The catalyst includes at least one Group VIII metal. The contacting is carried out at a pressure from about 15 psig to about 3000 psig.Type: GrantFiled: July 20, 1990Date of Patent: February 1, 1994Assignee: Chevron Research and Technology CompanyInventors: Donald S. Santilli, Mohammad M. Habib, Thomas V. Harris, Stacey I. Zones
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Patent number: 5277792Abstract: A lube hydrocracking process uses a catalyst which is based on an ultra-large pore crystalline material. The crystalline material exhibits unusually large pores of at least 13 .ANG. diameter and a high sorption capacity demonstrated by its benzene adsorption capacity of greater than about 15 grams benzene/100 grams at 50 torr and 25.degree. C. The crystalline material is characterized by an X-ray diffraction pattern with at least one d-spacing greater than about 18 .ANG. and in a particularly preferred form, a hexagonal arrangement of pores of at least 13 .ANG. diameter which can be indexed with a d.sub.100 value greater than about 18 .ANG.. The hydrocracking catalysts based on these materials are capable of producing hydrocracked lube products of good viscosity index in high yields without the use of fluorine or other promoters.Type: GrantFiled: July 24, 1991Date of Patent: January 11, 1994Assignee: Mobil Oil CorporationInventors: David O. Marler, Dominick N. Mazzone
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Patent number: 5264116Abstract: A process for producing high quality lubricants by the hydrocracking and hydroisomerization of petroleum waxes uses a catalyst which is based on an ultra-large pore crystalline material. The crystalline material exhibits unusually large pores of at least 13 .ANG. diameter and a high sorption capacity demonstrated by its benzene adsorption capacity of greater than about 15 grams benzene/100 grams at 50 torr and 25.degree. C. The crystalline material is characterized by an X-ray diffraction pattern with at least one d-spacing greater than about 18 .ANG. and in a particularly preferred form, a hexagonal arrangement of pores of at least 13 .ANG. diameter which can be indexed with a d.sub.100 value greater than about 18 .ANG.. The hydrocracking catalysts based on these materials are capable of producing lube products with a high VI of at least 120 and usually higher, values of 135 and higher e.g. 143.Type: GrantFiled: July 24, 1991Date of Patent: November 23, 1993Assignee: Mobil Oil CorporationInventors: Minas R. Apelian, Thomas F. Degnan, Jr., David O. Marler, Dominick N. Mazzone
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Patent number: 5246566Abstract: The present invention relates to a process for producing a lube oil having a low pour point and excellent viscosity and viscosity index comprising isomerizing a waxy feed over a catalyst comprising a molecular sieve having generally oval 1-D pores having a minor axis between about 4.2 .ANG. and about 4.8 .ANG. and a major axis between about 5.4 .ANG. and about 7.0 .ANG. and at least one group VIII metal. SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 and ZSM-35 are examples of useful catalysts.Type: GrantFiled: June 29, 1992Date of Patent: September 21, 1993Assignee: Chevron Research and Technology CompanyInventor: Stephen J. Miller
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Patent number: 5212128Abstract: The isomerization activity of hydroisomerization catalyst is recovered by subjecting the catalyst to a wash using light aromatic solvents at elevated temperature, e.g. toluene at 300.degree. C. This hot aromatic solvent wash may be preceded by a hot hydrogen containing gas strip. Catalyst activity can be maintained by the continuous or periodic addition of light aromatic solvent or light aromatic containing materials to the feeds sent to the isomerization catalyst.Type: GrantFiled: November 29, 1991Date of Patent: May 18, 1993Assignee: Exxon Research & Engineering CompanyInventors: James J. Schorfheide, Biddanda U. Achia
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Patent number: 5205923Abstract: A hydrogenation process for the hydrogenation of macro- and microcrystalline feeds in a mixed bed is disclosed, the first bed containing a catalyst of the demetallization kind, while the second bed contains a hydrotreatment catalyst. During the operation with microcrystalline feed, after the decrease in Saybolt color index, macrocrystalline feed is substituted for microcrystalline feed, whereby is restored the bed catalytic activity which in turn allows the return to the microcrystalline feed, and successively, so that operation is continuous with high Saybolt color index levels maintained for extended periods.Type: GrantFiled: April 4, 1991Date of Patent: April 27, 1993Assignee: Petroleo Brasileiro S.A. PetrobrasInventors: Guilherme Lues M. De Souza, Antonio Adolfo F. Valle, Rosa Maria P. Wodtke
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Patent number: 5149421Abstract: The present invention relates to a process for catalytically dewaxing a hydrocarbon oil feedstock by contacting the feedstock with a combination of a catalyst comprising an intermediate pore size silicoaluminophosphate molecular sieve and a hydrogenation component and an intermediate pore size aluminosilicate zeolite catalyst.Type: GrantFiled: August 31, 1989Date of Patent: September 22, 1992Assignee: Chevron Research CompanyInventor: Stephen J. Miller
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Patent number: 5135638Abstract: The present invention relates to a process for producing a lube oil having a low pour point and excellent viscosity and viscosity index comprising isomerizing a waxy feed over a catalyst comprising a molecular sieve having generally oval 1-D pores having a minor axis between about 4.2 .ANG. and about 4.8 .ANG. and a major axis between about 5.4 .ANG. and about 7.0 .ANG. and at least one group VIII metal. SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 and ZSM-35 are examples of useful catalysts.Type: GrantFiled: July 20, 1990Date of Patent: August 4, 1992Assignee: Chevron Research and Technology CompanyInventor: Stephen J. Miller
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Patent number: 5098551Abstract: Lubricating base oils having a high viscosity index, preferably at least 135, are manufactured by catalytic hydroisomerization of a hydrocarbonaceous feedstock, derived from a waxy crude oil, which feedstock has not been treated to remove a lubricating base oil fraction and which feedstock contains at least 30% by weight wax and has at least 80% by weight boiling above 300.degree. C. and at most 30% by weight boiling above 540.degree. C.Type: GrantFiled: May 16, 1990Date of Patent: March 24, 1992Inventors: Jean-Marie A. Bertaux, Jean-Claude M. Holley, Martinus M. P. Janssen
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Patent number: 5084159Abstract: The pour point and/or cloud point of the lube fractions comprising a waxy hydrocarbon feedstock containing straight and branched chain paraffins is reduced by contacting the feedstock in a dewaxing zone, preferably in the presence of added hydrogen, with a dewaxing catalyst comprising (1) an intermediate pore crystalline molecular sieve having a pore size between about 5.0 Angstroms and about 7.0 Angstroms and (2) a large pore crystalline molecular sieve having a pore size above about 7.0 Angstroms and typically selected from the group consisting of silicoaluminophosphates, ferrosilicates, aluminophosphates and Y zeolites. A hydrocarbon fraction of reduced paraffin content is recovered from the effluent of the dewaxing zone. Preferred intermediate pore crystalline molecular sieves are silicalite and a ZSM-5 type zeolite. Preferred large pore crystalline molecular sieves are silicoaluminophosphates such as SAPO-5 and ammonium exchanged and steamed Y zeolites.Type: GrantFiled: June 26, 1989Date of Patent: January 28, 1992Assignee: Union Oil Company of CaliforniaInventors: Suheil Abdo, Eric L. Moorehead, John W. Ward
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Patent number: 5059299Abstract: Slack waxes and synthetic wax are isomerized and processed into high viscosity index and very low pour point lube base stock oils and blending stocks by the process comprising the steps of hydrotreating the wax, if necessary, to remove heteroatom and polynuclear aromatic compounds and/or deoiling the wax, if necessary, to an oil content between about 5-20% oil, isomerizing the wax over a Group VI-Group VIII on halogenated refractory metal oxide support catalyst, said isomerization being conducted to a level of conversion such that .about.40% and less unconverted wax remains in the 330.degree. C..sup.+, preferably the 370.degree. C..sup.+ fraction sent to the dewaxer. The total isomerate from the isomerization unit is fractionated into a lube oil fraction boiling at 330.degree. C..sup.+, preferably 370.degree.p9 C..sup.+. This oil fraction is solvent dewaxed preferably using MEK/MIBK at 20/80 ratio and unconverted wax is recycled to the isomerization unit.Type: GrantFiled: May 11, 1990Date of Patent: October 22, 1991Assignee: Exxon Research and Engineering CompanyInventors: Ian A. Cody, James D. Bell, Theodore H. West, William A. Wachter, Biddanda U. Achia
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Patent number: 5047141Abstract: Organic compound conversion over catalyst comprising the product of a method for controlling the catalytic activity of a large pore molecular sieve which contains framework boron is provided. Control is effected by treatment with a solution of a metal salt under conditions such that metal is incorporated into the molecular sieve framework.Type: GrantFiled: January 16, 1990Date of Patent: September 10, 1991Assignee: Mobil Oil CorporationInventor: Pochen Chu
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Patent number: 5037528Abstract: High viscosity index, low pour point lubricants are produced by the oligomerization of a wax-derived lubricant fraction. The fraction may be produced from slack wax or de-oiled wax by hydroisomerization over zeolite beta or hydrocracking/isomerization over an amorphous catalyst followed by selective dewaxing, preferably by catalytic dewaxing over a highly shape selective zeolite such as ZSM-23. The preferred peroxides are ditertiary alkyl peroxides such as ditertiary butyl peroxide (DTBP) and are typically used at temperatures of 100.degree.-300.degree. C.Type: GrantFiled: April 30, 1990Date of Patent: August 6, 1991Assignee: Mobil Oil CorporationInventors: William E. Garwood, Quang N. Le, Stephen S. Wong
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Patent number: 5015359Abstract: Hydrocarbon feeds are dewaxed and hydrotreated in a two-stage dewaxing-hydrotreating reactor system with interstage separation of olefinic and naphtha and light olefins. Separation of the naphtha and olefins is carried out by stripping the effluent from the dewaxing reactor with a stripping medium such as make-up hydrogen or vapor from the hydrotreater effluent. Hydrogen recycle for the dewaxer and the hydrotreater is taken from the stripper/separator after removal of the olefinic naphtha and removal of contaminants. Separation of the lighter olefins from the olefinic naphtha may be improved by the use of an oil solvent such as naphtha introduced into the top of the interstage stripper/separator so that the recycle gas from the stripper/separator is essentially free of wet gas and heavier fractions.Type: GrantFiled: January 25, 1989Date of Patent: May 14, 1991Assignee: Mobil Oil CorporationInventors: Mohsen N. Harandi, Hartley Owen
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Patent number: 5013422Abstract: A hydrocracking process is provided comprising contacting a hydrocarbon stream under hydrocracking conditions and in the presence of hydrogen with a catalyst composition which comprises a synthetic porous crystalline zeolite having a particular X-ray diffraction pattern. An embodiment of the invention provides a process for reducing the pour point of a waxy component-containing hydrocarbon oil by hydrocracking and dewaxing. Another embodiment of the invention provides a dual-stage hydrocracking process to produce premium gasoline and distillate boiling range products.Type: GrantFiled: February 14, 1990Date of Patent: May 7, 1991Assignee: Mobil Oil Corp.Inventors: Robert P. L. Absil, Thomas F. Degnan, Scott Han, David O. Marler, Richard F. Socha, Michael R. Stapleton
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Patent number: 4992159Abstract: Waxy distillates, or raffinates containing from as little as 10% wax but more typically about 30% wax or more are upgraded by a process comprising the steps of hydrotreating the waxy oil under conditions which convert less than 20% of the feed into products boiling lower than the feed to reduce the sulfur and nitrogen content of the oil followed by hydroisomerizing the hydrotreated waxy oil to reduce the wax content and increase the viscosity index. This oil having a waxy content of less than 30%, preferably less than 25%, can now be more easily dewaxed using conventional solvent dewaxing procedures. The advantage of the present process resides in the increased yield and/or stability of oil as compared to other upgrading, dewaxing processes which convert wax to light products. The isomerization catalyst is preferably a low fluorine content catalyst, more preferably a noble metal on 0.1 to less than 2 wt % fluorine on alumina catalyst, most preferably a noble Group VIII metal (e.g.Type: GrantFiled: December 16, 1988Date of Patent: February 12, 1991Assignee: Exxon Research and Engineering CompanyInventors: Ian A. Cody, David L. Brown
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Patent number: 4986894Abstract: A process for dewaxing waxy hydrocarbon feedstocks to produce distillate fuels or lubricant stocks having improved pour point properties. The process comprises catalytic hydroisomerization of the feedstock over catalyst comprising a synthetic porous crystalline material characterized in its calcined form by an X-ray diffraction pattern including interplanar d-spacings at 12.36.+-.0.4, 11.03.+-.0.2, 8.83.+-.0.14, 6.18.+-.0.12, 6.00.+-.0.10, 4.06.+-.0.07, 3.91.+-.0.07 and 3.42.+-.0.06 Angstroms, and an Alpha Value of 10 or less.Type: GrantFiled: March 19, 1990Date of Patent: January 22, 1991Assignee: Mobil Oil Corp.Inventors: Kathleen M. Keville, Quang N. Le, Wang-Tsee T. Mo, Mae K. Rubin
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Patent number: 4983274Abstract: The catalytic properties of a metal-containing shape selective crystalline silicate zeolite are significantly improved by converting said metal to an intermetallic compound. Thus, for example, zeolite beta containing the intermetallic component platinum zeolite demonstrates improved catalytic properties for dewaxing a hydrocarbon feedstock compared to zeolite beta containing platinum metal alone.Type: GrantFiled: October 6, 1988Date of Patent: January 8, 1991Assignee: Mobil Oil Corp.Inventors: Nai Y. Chen, Thomas F. Degnan, Paul B. Weisz
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Patent number: 4975177Abstract: Lubricant basestocks of high viscosity index, typically with V.I. of at least 130 or higher, and low pour point, typically below 5.degree. F., are produced by hydroisomerizing petroleum waxes such as slack wax or de-oiled wax, over zeolite beta and then dewaxing to target pour point. A preferred process employs a solvent dewaxing after the hydroisomerization step to effect a partial dewaxing with the separated waxes being recycled to the hydroisomerization step; dewaxing is then completed catalytically, typically over ZSM-5 or ZSM-23.Type: GrantFiled: July 17, 1989Date of Patent: December 4, 1990Assignee: Mobil Oil CorporationInventors: William E. Garwood, Quang N. Le, Stephen S. Wong
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Patent number: 4952303Abstract: A process for obtaining a very high quality lube base stock is disclosed which comprises:(a) introducing an aromatic and nitrogen-and sulfur-containing feedstock selected from the group consisting of a dewaxed oil obtained from refining distillate fraction and having a 60-700 SUS at 100.degree. F. and a dewaxed oil obtained from refining vacuum resid and having a 2300-2700 SUS at 100.degree. F., and hydrogen, into a single stage hydrotreating reactor; and,(b) subjecting the feedstock to hydrotreating in said reactor in the presence of a sulfided cobalt/molybdenum hydrotreating catalyst at an average reactor temperature of from about 550.degree. to about 700.degree. F. at a hydrogen partial pressure of from about 1500 to about 3000 psia at the reactor outlet, an LHSV of from about 0.1 to about 1.Type: GrantFiled: December 22, 1988Date of Patent: August 28, 1990Assignee: Mobil Oil Corp.Inventors: Robert W. Bortz, Kenneth R. Graziani
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Patent number: 4943672Abstract: Fischer-Tropsch wax is converted to a lubricating oil having a high viscosity index and a low pour point by first hydrotreating the wax under relatively severe conditions and thereafter hydroisomerizing the hydrotreated wax in the presence of hydrogen on a particular fluorided Group VIII metal-on-alumina catalyst. The hydroisomerate is then dewaxed to produce a premium lubricating oil base stock.Type: GrantFiled: December 13, 1988Date of Patent: July 24, 1990Assignee: Exxon Research and Engineering CompanyInventors: Glen P. Hamner, deceased, Heather A. Boucher, William A. Wachter
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Patent number: 4923588Abstract: Waxes, for example waxes obtained from dewaxing hydrocarbon oils, called slack waxes, and synthetic waxes such as those obtained by Fischer-Tropsch processes, are isomerized into oils boiling in the lube oil boiling range, e.g., 370.degree. C.+, by contacting the wax under isomerization conditions and in the presence of hydrogen with an isomerization catalyst comprising a noble Group VIII metal on a small particle size refractory metal oxide support having a low total fluoride content catalyst wherein the total fluoride content is in the range of 0.1 to up to but less than 2 wt % fluoride and the support has a particle diameter of less than 1/16 inch. The small particle size refractory metal oxide support is preferably alumina or material containing alumina, preferably predominantly (i.e., >50%) alumina, more preferably an alumina such as gamma or eta. The most preferred alumina is 1/20 inch alumina trilobes. Noble metal content ranges from 0.1 to 2.0 wt %.Type: GrantFiled: December 16, 1988Date of Patent: May 8, 1990Assignee: Exxon Research and Engineering CompanyInventors: Ian A. Cody, David L. Brown
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Patent number: 4919786Abstract: A process for selectively producing middle distillate fuel products from paraffin waxes such as slack wax and Fischer-Tropsch wax by hydroisomerizing the wax to convert 60-95 weight percent per pass of the 700.degree. F..sup.+ fraction contained in said wax. The catalyst employed is a fluorided Group VIII metal-on-alumina catalyst where the fluoride within the catalyst is present predominately as aluminum fluoride hydroxide hydrate. The preferred Group VIII metal is platinum.Type: GrantFiled: December 13, 1988Date of Patent: April 24, 1990Assignee: Exxon Research and Engineering CompanyInventors: Glen P. Hamner, deceased, Willard H. Sawyer, Heather A. Boucher
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Patent number: 4911821Abstract: Lubricants of improved characteristics are produced by carrying out a solvent extraction to remove aromatic components after solvent or catalytic dewaxing. Aromatic extraction solvents such as phenol, furfural or N-methyl pyrrolidone may be used. The process is particularly useful with wax-derived lubricants produced by the hydroisomerization of a petroleum wax which has then been dewaxed.Type: GrantFiled: February 8, 1989Date of Patent: March 27, 1990Assignee: Mobil Oil CorporationInventors: James R. Katzer, Quang N. Le, Stephen S. Wong
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Patent number: 4908120Abstract: A lubricant dewaxing process which is useful with difficult feeds, especially highly waxy feeds having paraffin contents in excess of 25 weight percent or feeds with high nitrogen levels, employs two-step dewaxing in which the first stage is carried out under relatively mild conditions using a binder-free zeolite dewaxing catalyst to obtain extended catalyst cycle life between successive reactivations with a constant temperature for the duration of each dewaxing cycle. The second stage dewaxing is also carried out with a binder-free catalyst under conditions which maintain the target pour point for the product with a progressively increasing temperature during each dewaxing cycle. More than one preliminary dewaxing stage may be provided in order to reduce severity in each stage with mild conditions and constant temperature being maintained in the preliminary steps. Using this process, extended catalyst cycle lives may be obtained with difficult feeds.Type: GrantFiled: August 20, 1987Date of Patent: March 13, 1990Assignee: Mobil Oil CorporationInventors: Emmerson Bowes, Fritz A. Smith
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Patent number: 4867861Abstract: The pour point and/or cloud point of the lube fractions comprising a waxy hydrocarbon feedstock containing straight and branched chain paraffins is reduced by contacting the feedstock in a dewaxing zone, preferably in the presence of added hydrogen, with a dewaxing catalyst comprising (1) an intermediate pore crystalline molecular sieve having a pore size between about 5.0 Angstroms and about 7.0 Angstroms and (2) a large pore crystalline molecular sieve having a pore size above about 7.0 Angstroms and typically selected from the group consisting of silicoaluminophosphates, ferrosilicates, aluminophosphates and Y zeolites. A hydrocarbon fraction of reduced paraffin content is recovered from the effluent of the dewaxing zone. Preferred intermediate pore crystalline molecular sieves are silicalite and a ZSM-5 type zeolite. Preferred large power crystalline molecular sieves are silicoaluminophosphates such as SAPO-5 and ammonium exchanged and steamed Y zeolites.Type: GrantFiled: July 21, 1988Date of Patent: September 19, 1989Assignee: Union Oil Company of CaliforniaInventors: Suheil F. Abdo, Eric L. Moorhead, John W. Ward
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Patent number: 4867862Abstract: I disclose a single stage, multilayered catalyst system capable of hydrodehazing and hydrofinishing a solvent dewaxed lube oil base stock. In the first layer, I catalytically dewax the solvent dewaxed stock. In the second layer, I hydrofinish the catalytically dewaxed stock. My invention also relates to a process for hydrodewaxing and hydrofinishing a solvent dewaxed lube oil base stock.Type: GrantFiled: April 20, 1987Date of Patent: September 19, 1989Assignee: Chevron Research CompanyInventor: James N. Ziemer
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Patent number: 4832819Abstract: A process for producing a pumpable syncrude from a Fischer-Tropsch wax by fractionating the wax into relatively low boiling fraction containing oxygenate compounds and a relatively high boiling fraction which is substantially free of oxygenate compounds and thereafter isomerizing/hydrocracking the low boiling fraction in the presence of hydrogen and a fluorided Group VIII metal-on-alumina catalyst. The preferred Group VIII metal is platinum.The pumpable syncrude is thereafter fractionated to produce a low boiling fraction which is thereafter isomerized/hydrocracked in the presence of hydrogen and a fluorided Group VIII metal-on-alumina catalyst to produce upgraded middle distillate fuel products. The preferred catalyst for middle distillate production is a fluorided platinum-on-alumina catalyst where a major portion of the fluoride within the catalyst is present as aluminum fluoride hydroxide hydrate.Type: GrantFiled: December 18, 1987Date of Patent: May 23, 1989Assignee: Exxon Research and Engineering CompanyInventor: Glen P. Hamner
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Patent number: 4830729Abstract: Catalytic dewaxing of wax containing hydrocarbon feedstocks is undertaken in the presence of a catalyst composition comprising a dehydrogenation metal in combination with a non-acidic microporous crystalline material to maximize liquid yield.Type: GrantFiled: December 28, 1987Date of Patent: May 16, 1989Assignee: Mobil Oil CorporationInventors: Ralph M. Dessau, Ernest W. Valyocsik, Chaya Venkat
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Patent number: 4788378Abstract: A process is provided for dewaxing hydrocarbon feedstock by isomerizing the waxy components of the feedstock over catalyst comprising a siliceous zeolite having been prepared by the method comprising providing a boron-containing zeolite Beta, treating the zeolite with silicon tetrachloride at a temperature and for a time sufficient to replace boron with silicon, and recovering the siliceous zeolite having reduced boron content but substantially preserved initial aluminum content.Type: GrantFiled: August 6, 1987Date of Patent: November 29, 1988Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, David S. Shihabi, Paul B. Weisz
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Patent number: 4784749Abstract: A process is provided for converting feedstock comprising hydrocarbon compounds to product comprising hydrocarbon compounds of lower molecular weight than feedstock hydrocarbon compounds over a catalyst comprising a siliceous zeolite prepared by the method comprising providing zeolite Beta containing boron and aluminum, treating the zeolite with silicon tetrachloride at a temperature and for a time sufficient to replace boron with silicon, and recovering the siliceous zeolite having reduced boron content but substantially preserved initial aluminum content. In particular embodiments, the conversion is selective cracking for waxes and the process is useful for reducing the pour point of fuel oils and lubricants.Type: GrantFiled: August 6, 1987Date of Patent: November 15, 1988Assignee: Mobil Oil CorporationInventors: Clarence D. Chang, David S. Shihabi, Paul B. Weisz
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Patent number: 4781818Abstract: Improved noncatalytic nonreactive alumina-silica solid for removing carbonaceous and metallic contaminants including nickel and vanadium from hydrocarbon feedstock by short term, high temperature contact comprises mullite and crystalline silica. In the decarbonizing and demetallizing process, impurities are deposited on the particles of the solid and the major portion of the feedstock is vaporized. After burning carbonaceous deposit from the particles, the hot particles containing nickel and vanadium are recycled into contact with incoming charges of contaminated feedstock. Periodically metals are removed from coke-depleted particles by extraction with a mineral acid at elevated temperature without dissolving or otherwise destroying the alumina-silica particles. The particles are then reintroduced into the system.Type: GrantFiled: January 21, 1988Date of Patent: November 1, 1988Assignee: Engelhard CorporationInventors: William J. Reagan, David W. White, William R. Schultz, L. Alan Jarnagin
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Patent number: 4776946Abstract: A novel siliceous crystalline composition of matter further comprising one or more metals is prepared by admixing a basic silica salt and a dissolved metal salt in the presence of a quarternary ammonium ion and subsequently heating under pressurized conditions. This novel composition of matter is useful as a catalyst for oxidation, alkylation, disproportionation, synthesis gas conversion, hydrocracking, and hydrodewaxing.Type: GrantFiled: May 1, 1987Date of Patent: October 11, 1988Assignee: Union Oil Company of CaliforniaInventor: Eric L. Moorehead
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Patent number: 4750984Abstract: A method of producing high quality, homogenous asphalt comprising the steps of mixing and heating a hydrocarbon feedstock not normally suited for asphalt production with elemental sulfur and agitating the resulting mixture. A halide catalyst may be added to the mixture to promote the reaction of the hydrocarbon feedstock with the sulfur. If desired, the agitated mixture may be air blown in any conventional manner to increase its hardness.Type: GrantFiled: November 18, 1985Date of Patent: June 14, 1988Inventor: Clifford J. Ott
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Patent number: 4695365Abstract: A spindle oil is hydrotreated and then hydrodewaxed in the presence of a catalyst containing at least 70 percent by weight of an intermediate pore molecular sieve in the support so as to produce a selected fraction having a low pour point and viscosity comparable to the original spindle oil, said fraction being then suitable as a "cutter stock" for lowering the pour point of fuel oils.Type: GrantFiled: July 31, 1986Date of Patent: September 22, 1987Assignee: Union Oil Company of CaliforniaInventors: Donald B. Ackelson, Eric L. Moorehead, John W. Ward, Jon D. Probst
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Patent number: 4686029Abstract: Dewaxing processes for hydrocarbon feedstocks are disclosed using novel catalysts comprising titanoaluminosilicates. The products of the instant dewaxing processes are characterized by lower pour points than the hydrocarbon feedstock.Type: GrantFiled: December 6, 1985Date of Patent: August 11, 1987Assignee: Union Carbide CorporationInventors: Regis J. Pellet, Frank P. Gortsema, Gary N. Long, Jule A. Rabo
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Patent number: 4622130Abstract: This invention discloses an economic series flow dewaxing scheme having a first solvent dewaxing step followed by a catalytic dewaxing step. The use of methylisopropyl ketone as a key component in the solvent dewaxing step produces a solvent dewaxed effluent with an intermediate pour point which may be readily catalytically dewaxed to a pour point suitable for lubricant applications. The catalytic dewaxing unit can also be used to recover lost oil yield from the soft wax product of the solvent dewaxing zone (sometimes referred to as footsoil) and thereby sustain, if not increase, overall lubricating oil yield.Type: GrantFiled: December 9, 1985Date of Patent: November 11, 1986Assignee: Shell Oil CompanyInventor: Stephen C. Stem
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Patent number: 4608151Abstract: A process for producing high quality, high molecular weight microcrystalline wax from a hydrocracked, undewaxed bright stock, comprising hydrodenitrification, mild hydrofinishing, and solvent dewaxing.Type: GrantFiled: December 6, 1985Date of Patent: August 26, 1986Assignee: Chevron Research CompanyInventor: Stephen J. Miller
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Patent number: 4604261Abstract: A hydroprocessing trickle reactor construction which will facilitate the catalytic dewaxing of liquid petroleum or lube feedstocks in a highly efficient and economical manner, particularly through the use of reactors employing stationary bed of a defined, shape-selective crystalline aluminosilicate zeolite catalyst, preferably ZSM-5. Pursuant to one embodiment of the hydroprocessing reactor, the latter is essentially constituted of a trickle bed reactor wherein a plurality of vertically tiered and staggered trays support the beds of catalyst material, such as the crystalline zeolite, and through which the liquid petroleum feedstock trickles downwardly from the upper end of the reactor, while hydrogen is concurrently injected into the catalyst on each of the trays. This causes the hydrogen to percolate through the catalyst bed and to contact and efficiently strip the downwardly trickling stream of liquid petroleum feedstock of low boiling conversion products or waxy components, such as naphtha.Type: GrantFiled: June 29, 1984Date of Patent: August 5, 1986Assignee: Mobil Oil CorporationInventors: Nai Y. Chen, Thomas F. Degnan
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Patent number: 4550090Abstract: A novel method is provided for regenerating deactivated crystalline zeolite catalysts at low temperature. The organic residue is contacted with a source of alkali or alkaline earth metal cations, or a source of ammonia, and the organic residue, including nitrogenous compounds, is extracted with an organic solvent. The method is particularly useful with deactivated ZSM-5 type dewaxing catalyst.Type: GrantFiled: October 10, 1984Date of Patent: October 29, 1985Assignee: Mobil Oil CorporationInventors: Thomas F. Degnan, Malvina Farcasiu
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Patent number: 4186078Abstract: A catalyst and process are described for hydrofining petroleum wax comprising contacting the wax with hydrogen in the presence of a catalyst comprising at least one metal hydrogenating component on a porous alumina/silica carrier containing from about 0.2 to 5 wt.% of an alkali metal component, the catalyst having a specific surface area of about 200 to 300 m.sup.2 /g and being further characterized in that (a) the volume of pores having a diameter in the range of 60 to 150 A is greater than 80% of the volume of pores having a diameter in the range of 0 to 150 A and (b) the volume of pores having a diameter in the range of 0 to 600 A is in the range of about 0.45 to 0.60 ml/g.Type: GrantFiled: April 20, 1978Date of Patent: January 29, 1980Assignee: Toa Nenryo Kogyo Kabushiki KaishaInventors: Takuji Itoh, Satoshi Sakurada, Shohei Okano, Takashi Obayashi, Takeo Toyoizumi, Osami Iwata
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Patent number: 4180408Abstract: This invention relates to polyvalent metal salts of oxidized and amidified non-benzenoid hydrocarbon waxes, and to uses thereof, particularly in carbon paper inks.Type: GrantFiled: February 6, 1978Date of Patent: December 25, 1979Assignee: Petrolite CorporationInventors: Joseph O. Bienvenu, Ashvinkumar N. Jagtap
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Patent number: 4148711Abstract: High melting, deoiled and mildly deasphalted tank bottoms wax is catalytically refined in two stages using a catalyst comprising nickel molybdate on alumina. The first stage is maintained at a temperature at least about 50.degree. F. higher than the second stage and the temperature in the second stage is allowed to go no higher than about 575.degree. F. Hydrofined wax product from the second stage is recycled back into same and the temperature in the first stage is periodically increased in order to counteract deactivation of the catalyst. By using a judicious combination of process conditions, unrefined high melting tank bottoms microwax stocks can be made into high quality, high melting point microwax having excellent color and meeting FDA purity requirements.Type: GrantFiled: July 5, 1977Date of Patent: April 10, 1979Assignee: Exxon Research & Engineering Co.Inventor: Clinton H. Holder
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Patent number: 4140619Abstract: The molecular weight of a solid paraffin wax having an oil content of no more than about 2% by weight is increased by contacting the wax at elevated temperature with at least about 5% by weight of an organic peroxide.Type: GrantFiled: September 26, 1977Date of Patent: February 20, 1979Assignee: Shell Oil CompanyInventors: Anton VAN DER Wiel, Bernardus C. Ernsting