With Solid Catalyst Or Absorbent Patents (Class 208/213)
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Patent number: 5413698Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment in a second step over a a first catalyst zone comprising a large pore size zeolite material and a second catalyst zone comprising an intermediate pore size material. Preferably, the large pore size material is zeolite beta and the intermediate pore size material is ZSM-5. The treatment in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. In favorable cases, using feeds of extended end point such as heavy naphthas with 95 percent points above about 380.degree. F. (about 193.degree. C.), improvements in both product octane and yield relative to the feed may be obtained.Type: GrantFiled: August 5, 1992Date of Patent: May 9, 1995Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Mohsen N. Harandi, Michael S. Sarli, Stuart S. Shih
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Patent number: 5411658Abstract: Low sulfur gasoline of relatively high octane number is produced from a cracked, sulfur-containing olefinic naphthas by hydrodesulfurization followed by treatment over an acidic catalyst comprising zeolite beta with a metal hydrogenation component, preferably a mild hydrogenation component such as molybdenum. The treatment over the acidic catalyst in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. In favorable cases, using feeds of extended end point such as heavy naphthas with 95 percent points above about 380.degree. F. (about 193.degree. C.), improvements in both product octane and yield relative to the feed may be obtained.Type: GrantFiled: October 8, 1993Date of Patent: May 2, 1995Assignee: Mobil Oil CorporationInventors: Birbal Chawla, Dominik N. Mazzone, Michael S. Sarli, Stuart S. Shih, Hye Kyung C. Timken
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Patent number: 5409596Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5. The treatment over the acidic catalyst in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. In favorable cases, using feeds of extended end point such as heavy naphthas with 95 percent points above about 380.degree. F. (about 193.degree. C.), improvements in both product octane and yield relative to the feed may be obtained.Type: GrantFiled: March 12, 1992Date of Patent: April 25, 1995Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
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Patent number: 5407559Abstract: A process is provided for producing low sulfur gasoline of relatively high octane number from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst comprising crystals having the structure of ZSM-12. The treatment over the acidic catalyst comprising ZSM-12 in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. In favorable cases, using feeds of extended end point such as heavy naphthas with 95 percent points above about 380.degree. F. (about 193.degree. C.), improvements in both product octane and yield relative to the feed may be obtained.Type: GrantFiled: June 1, 1992Date of Patent: April 18, 1995Assignee: Mobil Oil CorporationInventors: Thomas F. Degnan, Stuart S. Shih
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Patent number: 5401391Abstract: A process for desulfurizing a hydrocarbon stream which includes at least 100 ppmw sulfur in the form of organic sulfur compounds, and C.sub.4 -hydrocarbons. The hydrocarbon stream is contacted in the absence of added hydrogen with a fluidized bed of an acidic catalyst having a structure of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, MCM-22, MCM-36, MCM-49, zeolite Y, zeolite beta or mixtures thereof to convert the organic sulfur compounds to hydrogen sulfide. The catalyst contacts the hydrocarbon stream at a pressure of from 0.0 psig to about 400 psig, a temperature of from about 400.degree. F. to about 900.degree. F., and a weight hourly space velocity of from about 0.1 hr..sup.-1 to about 10.0 hr..sup.-1. Thereafter, the hydrogen sulfide is removed from the hydrocarbon stream.Type: GrantFiled: March 8, 1993Date of Patent: March 28, 1995Assignee: Mobil Oil CorporationInventors: Nick A. Collins, Mohsen N. Harandi, Raymond D. McGraw
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Patent number: 5399258Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst under endothermic conditions in a second reaction zone. Heat is added to the endothermic reaction zone to initiate and maintain octane restoring reactions. The preferred acidic catalyst is an intermediate pore size zeolite such as ZSM-5. The treatment over the acidic catalyst in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. The addition of heat at the second zone prolongs hydrodesulfurization catalyst life by allowing a lower hydrodesulfurization reactor temperature. The addition of heat also maximizes octane increase in the second zone.Type: GrantFiled: December 10, 1992Date of Patent: March 21, 1995Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih, Stephen J. McGovern, Douglas S. Diez, Mohsen N. Harandi, Timothy L. Hilbert
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Patent number: 5371311Abstract: Forms of zeolite Omega synthesized by hydrothermal crystallization from reaction systems containing alkali metal cations and organic templating agents, modified by calcination in air, ion-exchange, steam calcination and treatment with a low-pH aqueous ammonium ion solution, are significantly improved with respect to surface area, catalytic activity and adsorption capacities for large molecular species.The zeolite compositions of the invention may be used in a variety of hydrocarbon conversion reactions.Type: GrantFiled: July 27, 1993Date of Patent: December 6, 1994Assignee: UOPInventors: Vinayan Nair, Donald F. Best, Gregory J. Gajda
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Patent number: 5362376Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst system comprising an intermediate pore size zeolite having crystallites of an effective radius of at least 0.25 micron. The treatment over the large crystal acidic catalyst in the second step restores the octane loss which takes place as a result of the hydrogenation treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha, with the large crystal size improving gasoline yield by reducing conversion of branched paraffins.Type: GrantFiled: August 13, 1992Date of Patent: November 8, 1994Assignee: Mobil Oil CorporationInventors: Stuart S. Shih, Philip J. Angevine
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Patent number: 5358634Abstract: A process for treating heavy oil by contacting the oil with hydrogen in a reactor containing an activated carbon catalyst having a specified range of Alpha value, and average pore diameter, and pore distribution, to reduce the content of nickel and vanadium in the feedstock and to achieve conversion of the carbon residue for producing a lighter oil.Type: GrantFiled: October 30, 1992Date of Patent: October 25, 1994Assignee: Mobil Oil CorporationInventor: Lillian A. Rankel
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Patent number: 5352354Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst defined by its x-ray diffraction pattern and preferably comprising the synthetic zeolite MCM-22. The treatment over the acidic catalyst in the second step restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. In favorable cases, using feeds of extended end point such as heavy naphthas with 95 percent points above about 380.degree. F. (about 193.degree. C.), improvements in both product octane and yield relative to the feed may be obtained.Type: GrantFiled: June 1, 1992Date of Patent: October 4, 1994Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Timothy L. Hilbert, Stephen J. McGovern, Michael S. Sarli, Stuart S. Shih
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Patent number: 5348641Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5. The treatment over the acidic catalyst in the second step, which is carried out in a hydrogen atmosphere which is essentially free of hydrogen sulfide and ammonia, restores the octane loss which takes place as a result of the hydrogenative treatment and results in a low sulfur gasoline product with an octane number comparable to that of the feed naphtha. The hydrogen supplied to the second step may be make-up hydrogen with recycle hydrogen routed to the hydrodesulfurization step after removal of ammonia and hydrogen sulfide in a scrubber.Type: GrantFiled: May 8, 1992Date of Patent: September 20, 1994Assignee: Mobil Oil CorporationInventor: Stuart S. Shih
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Patent number: 5346609Abstract: A process for producing a desulfurized gasoline boiling range product of relatively high octane number from a sulfur containing feed boiling in the naphtha boiling range by converting the feed in a first stage over a conventional hydrodesulfurization catalyst, and then converting at least the normally liquid portion of the product of this first stage conversion over a catalyst comprising a zeolitic behaving refractory solid having acid activity and shape selectivity to produce a product having a sulfur content within the required specifications, and an octane number which at least approaches the octane number of the feed.Type: GrantFiled: August 15, 1991Date of Patent: September 13, 1994Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
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Patent number: 5344553Abstract: There is provided a process for upgrading hydrocarbon feedstocks, such as resids or shale oil. The process uses a catalyst comprising at least one Group VIA or Group VIII metal, such as nickel and molybdenum, and an ultra-large pore oxide material. The ultra-large pore oxide material is used in decreasing pore size from top to bottom of the reactor.Type: GrantFiled: February 22, 1993Date of Patent: September 6, 1994Assignee: Mobil Oil CorporationInventor: Stuart S. Shih
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Patent number: 5292428Abstract: Liquid sulphur-containing hydrocarbon feedstock is passed through two or more hydrodesulfurization zones and connected in a series each containing a packed bed of solid sulfurized catalyst. The liquid is passed from the first zone to the next until the final zone. Make up hydrogen is supplied to a hydrodesulfurization zone (i) other than the first hydrodesulfurization zone; hydrogen-containing gas is recovered from each hydrodesulfurization zone. The first hydrodesulfurization zone is supplied with hydrogen-containing gas recovered from a subsequent hydrodesulfurization zone. Hydrogen-containing gas recovered from the first hydrodesulfurization zone is purged. Liquid material recovered from the first hydrodesulfurization zone is recycled to the inlet of the hydrosulfurization zone so as to provide diluent for admixture with liquid feedstock.Type: GrantFiled: December 11, 1991Date of Patent: March 8, 1994Assignee: Davy McKee (London) Ltd.Inventors: George E. Harrison, Donald H. McKinley, Alan J. Dennis
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Patent number: 5290427Abstract: Low sulfur gasoline is produced from a catalytically cracked, sulfur-containing naphtha by fractionating the naphtha feed into a number of fractions of differing boiling range and hydrodesulfurizing them by by feeding them into a hydrodesulfurization reactor at spaced locations along the length of the reactor in order of descending boiling range, with the highest boiling fraction first. Staged introduction of the feed into the hydrodesulfurization reactor in this way promotes desulfurization of the sulfur-rich, olefin poor back end of the feed while reducing the saturation of the high octane olefins in the olefin-rich, sulfur-poor front end, so preserving octane while achieving the desired desulfurization. The hydrodesulfurization is followed by treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5.Type: GrantFiled: August 5, 1992Date of Patent: March 1, 1994Assignee: Mobil Oil CorporationInventors: David L. Fletcher, Timothy L. Hilbert, Michael S. Sarli, Stuart S. Shih
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Patent number: 5266188Abstract: A process, catalyst, and method of making a catalyst are provided for the selective hydrotreating of a selective hydrotreating feedstock comprising reacting the feedstock with hydrogen at hydrotreating conditions in the presence of a catalyst comprising a hydrogenation component and a support component. The hydrogenation component comprises a Group VIB metal component and a Group VIII metal component wherein the Group VIB metal component is present in an amount ranging from about 4 wt % to about 20 wt % and the Group VIII metal component is present in an amount ranging from about 0.5 wt % to about 10 wt %, both calculated as oxides and based on the total catalyst weight. The support component comprises from about 0.5 wt % to about 50 wt % of a magnesium component and from about 0.02 wt % to about 10 wt % of an alkali metal component, both calculated as oxides and based on the total catalyst weight.Type: GrantFiled: December 5, 1991Date of Patent: November 30, 1993Assignee: Amoco CorporationInventors: Simon G. Kukes, P. Donald Hopkins, Riitta L. A. Ollendorff, Pablo D. Hendler, Cynthia D. Ontiveros, Don M. Washecheck
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Patent number: 5264188Abstract: Apparatus is provided whereby the heat released from exothermic hydrodemetallization reactions is recovered in order to provide either a lower operating cost of a two-stage hydrotreating process or protection of process equipment against excessive operating temperatures.Type: GrantFiled: October 2, 1992Date of Patent: November 23, 1993Assignee: Phillips Petroleum CompanyInventor: Lawrence E. Lew
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Patent number: 5252198Abstract: A hydrodesulfurization process is provided for continuously effecting hydrodesulfurization of a liquid sulfur-containing hydrocarbon feedstock which comprises: (a) providing a hydrodesulfurization zone maintained under hydrodesulfurization conditions and comprising a column reactor having a plurality of reaction trays therein mounted one above another, each tray defining a respective reaction stage adapted to hold a predetermined liquid volume and a charge of a sulfided solid hydrodesulfurization catalyst therein, liquid downcomer means associated with each reaction tray adapted to allow liquid to pass down the column reactor from that tray but to retain solid catalyst thereon, and gas upcomer means associated with each reaction tray adapted to allow gas to enter that tray from below and to agitate the mixture of liquid and catalyst on that tray; (b) supplying liquid sulfur-containing hydrocarbon feedstock to the uppermost one of said plurality of reaction trays; (c) supplying hydrogen-containing gas below thType: GrantFiled: December 11, 1991Date of Patent: October 12, 1993Assignee: Davy McKee (London) Ltd.Inventors: George E. Harrison, Donald H. McKinley, Alan J. Dennis
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Patent number: 5248412Abstract: A process is described for producing a catalyst composition for hydrodesulfurization of hydrocarbon oil, which comprises:drying and calcining a carrier comprising alumina or an alumina-containing material impregnated with a solution mixture of(A) at least one of an alkoxide, a chelate compound, or a glycoxide of molybdenum or chromium;(B) at least one of an alkoxide, a chelate compound, or a glycoxide of cobalt or nickel; andan organic solvent capable of dissolving (A) and (B).Also described is a process for hydrodesulfurizing hydrocarbon oil using the same catalyst composition.Type: GrantFiled: February 20, 1992Date of Patent: September 28, 1993Assignees: Cosmo Research Institute, Cosmo Oil Co., Ltd.Inventors: Takashi Fujikawa, Kazushi Usui, Katsuyoshi Ohki
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Patent number: 5230790Abstract: Hydrocarbon conversion reactions are carried out over a catalyst composition containing forms of zeolite Omega synthesized by hydrothermal crystallization from reaction systems containing alkali metal cations and organic templating agents which have been modified by calcination in air, ion-exchange, steam calcination and treatment with a low-pH aqueous ammonium ion solution.Type: GrantFiled: May 18, 1992Date of Patent: July 27, 1993Assignee: UOPInventors: Vinayan Nair, Donald F. Best
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Patent number: 5230791Abstract: Spent or inactive alumina-supported catalysts removed from a catalytic hydrotreating process and having carbonaceous and metallic deposits thereon are reactivated. After a solvent wash to remove process oils, the spent catalyst is treated with an organic solvent, such as N-methyl-2-pyrrolidone, at a temperature of 200.degree. to about 500.degree. F. for a period of about 1 to about 12 hours to form the reactivated catalyst suitable for reuse in a catalytic hydrotreating process. Optionally, the solvent treated catalyst can be regenerated by contact with an oxygen-containing gas at a temperature of about 700.degree. to about 900.degree. F. to remove carbon deposits from the catalyst, or, alternatively, the solvent treated catalyst can be acid leached to remove undesired metals and then contacted with an oxygen-containing gas at an elevated temperature to remove carbon deposits.Type: GrantFiled: July 3, 1991Date of Patent: July 27, 1993Assignee: Texaco Inc.Inventor: David E. Sherwood, Jr.
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Patent number: 5211837Abstract: A hydrocarbon feedstock is catalytically reformed to effect dehydrocyclization of paraffins in a process combination comprising a first reforming zone and a sulfur-removal zone utilizing a manganese component to preclude sulfur from the feed to a second reforming zone. The process combination shows substantial benefits over prior art processes in the stability of the extremely sulfur-sensitive catalyst utilized in the second reforming zone.Type: GrantFiled: February 27, 1992Date of Patent: May 18, 1993Assignee: UOPInventors: Michael B. Russ, Roger L. Peer, Joseph Zmich, Chi-Chu D. Low
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Patent number: 5207892Abstract: Novel catalyst compositions comprising a metal hydrogenation component and a modified form of zeolite Y are found to be highly effective in the hydrocarbon conversion processes carried out in the presence of added hydrogen and involving hydrogenation as an essential reaction mechanism. The modified form of zeolite Y is prepared from a starting zeolite Y which has been ammonium cation exchanged to lower the alkali metal content to less than 3.0 weight percent. The starting composition is then steamed at temperatures above about 550.degree. C. to reduce the unit cell dimension and then contacted with an aqueous ammonium ion solution having a pH below about 4 to increase the bulk Si/Al.sub.2 ratio to the range of about 6.5 to 20.Type: GrantFiled: December 24, 1990Date of Patent: May 4, 1993Assignee: UOPInventors: James G. Vassilakis, Donald F. Best
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Patent number: 5198099Abstract: A process for producing ultra clean distillate and naphtha products wherein a distillate boiling range stream which contains heteroatoms and aromatics to subjected to three stage processing. The first stage is conventional hydrotreating, wherein the resulting effluent is further hydrotreated, but with a noble metal zeolite catalyst which is typically used for hydrocracking. The effluent from this second stage, which is now substantially free of heteroatoms, is passed to a third stage. This third stage is a hydrocracking stage, the severity of which will determine if the ultimate product will be a distillate or a naphtha.Type: GrantFiled: August 12, 1991Date of Patent: March 30, 1993Assignee: Exxon Research and Engineering CompanyInventors: Kenneth L. Trachte, Willian Lasko, Edward Effron, Gordon F. Stuntz, Karl D. Chomyn
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Patent number: 5186818Abstract: The hydrotreating of petroleum feedstock is improved by using a layered transition metal catalyst, a mixture of such catalysts or a stocked bed of transition metal catalysts that has a selected ratio of edge to rim sites sufficient to provide a product having a predetermined sulfur and nitrogen content.Type: GrantFiled: August 12, 1991Date of Patent: February 16, 1993Assignee: Exxon Research and Engineering CompanyInventors: Michel Daage, Russell R. Chianelli
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Patent number: 5176820Abstract: Method and apparatus are provided whereby the heat released from exothermic hydrodemetallization reactions is recovered in order to provide either a lower operating cost of a two-stage hydrotreating process or protection of process equipment against excessive operating temperatures.Type: GrantFiled: January 22, 1991Date of Patent: January 5, 1993Assignee: Phillips Petroleum CompanyInventor: Lawrence E. Lew
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Patent number: 5176817Abstract: This invention relates to molecular sieve compositions and processes for using the molecular sieves. The molecular sieves have a three-dimensional microporous crystalline framework structure of tetrahedral oxide units of AlO.sub.2, SiO.sub.2, TiO.sub.2 and/or FeO.sub.2. These molecular sieves can be prepared by contacting a starting zeolite with a solution or slurry of a fluoro salt of titanium and/or iron under effective process conditions to extract aluminum from the zeolite framework and substitute titanium and/or iron. The molecular sieves can be used as catalysts in hydrocarbon conversion processes and other processes.Type: GrantFiled: December 16, 1991Date of Patent: January 5, 1993Assignee: UOPInventors: Gary W. Skeels, Richard Ramos
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Patent number: 5173173Abstract: A hydrocarbon feedstock is simultaneously distilled into two or more fractions while trace concentrations of contaminants in the feedstock are absorbed onto a sorbent packing material during distillation operation. The sorbent packings contain active metal components supported on porous refractory oxides. Such sorbent packings provide surfaces for mass transfer in the distillation process and concurrently absorb contaminants. Product boiling fractions from the absorption-distillation process are further processed over contaminant-sensitive catalysts such as reforming or isomerization catalyst.Type: GrantFiled: September 28, 1990Date of Patent: December 22, 1992Assignee: Union Oil Company of CaliforniaInventor: Dennis A. Vauk
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Patent number: 5171425Abstract: Process for upgrading a sulfur-containing feedstock comprising a hydrocarbon mixture substantially boiling in the gasoline range which process comprises the following steps:1) contacting the feedstock of a temparature of about 300.degree. C. to about 600.degree. C., a pressure of about 1 bar to about 40 bar and a space velocity of about 0.5 to about 10 g/g/h, with a catalyst which comprises a crystalline (metallo)silicate having an X-ray diffraction pattern containing the four strongest lines at interplanar spacings (d) expressed in .ANG., of 11.1.+-.0.2, 10.0.+-.0.2, 3.84.+-.0.07 and 3.72.+-.0.06, and2) contacting at least a fraction of the product obtained in step 1) at a temperature of about 200.degree. C. to about 600.degree. C., a pressure of about 20 bar to about 100 bar and a space velocity of about 0.Type: GrantFiled: May 24, 1991Date of Patent: December 15, 1992Assignee: Shell Oil CompanyInventor: Frederik Muller
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Patent number: 5164078Abstract: We disclose a process for removing calcium from a hydrocarbon feed having at least 1 ppm oil-soluble calcium. It comprises employing a catalyst layer characterized as a fixed bed of catalyst particles, a high volume percent of their pore volume in the form of macropores above 1000 Angstrom in diameter, or an average mesopore diameter of 100-800 .ANG., low surface area, and low hydrogenation activity, and the inclusion of Group I metals, in particular potassium, on the catalyst base.Type: GrantFiled: February 18, 1992Date of Patent: November 17, 1992Assignee: Chevron Research and Technology CompanyInventors: Chi W. Hung, Bruce E. Reynolds
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Patent number: 5164076Abstract: Processes are disclosed for the separation of hydrogen sulfide from feedstreams containing hydrogen sulfide and hydrocarbons by adsorption using a clinoptilolite adsorbent containing cations having ionic radii of from about 1.10 to 1.40 Angstroms. The processes can provide substantially enhanced adsorption capacities as compared with other adsorbents such as Zeolite 4A. As a result, a throughput of existing sulfur adsorption plants can be increased, e.g., by about 100%. The processes can be operated at elevated adsorption temperatures, e.g., greater than about 200.degree. F., and thus are particularly suitable when integrated with other processing steps such as hydrocarbon conversion reactions that utilize catalysts which are sulfur-sensitive. In addition, the clinoptilolite adsorbents of the present invention have a high tolerance to environments that comprise halides, e.g., HCl.Type: GrantFiled: January 22, 1991Date of Patent: November 17, 1992Assignee: UOPInventors: Andrew S. Zarchy, Richard Correia, Chien C. Chao
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Patent number: 5154817Abstract: Gum and sediment formation in liquid hydrocarbon mediums are inhibited by adding to the medium a branched or straight chain C.sub.1 -C.sub.8 aminoalcohol. The invention is particularly well-suited for use in hydrodesulfurizer processes wherein the hydrocarbon medium is typically a naphtha, diesel, kerosene, light gas and or residual fuel charge and the charge or medium is subjected to high temperature and pressure treatment in the presence of a catalyst. The invention also shows particular advantage in distillate fuels, such as in blended diesel fuels, both before and during heat treatment processing thereof.Type: GrantFiled: May 24, 1990Date of Patent: October 13, 1992Assignee: Betz Laboratories, Inc.Inventor: Dwight K. Reid
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Patent number: 5137705Abstract: This invention relates to a new form of crystalline material identified as zeolite ZSM-12, to a new and useful improvement in synthesizing said crystalline material and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g. hydrocarbon compound, conversion.Type: GrantFiled: April 8, 1991Date of Patent: August 11, 1992Assignee: Mobil Oil Corp.Inventor: Ernest W. Valyocsik
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Patent number: 5124136Abstract: Crystalline metalloaluminophosphate compositions having pore windows formed by 18 tetrahedral members are prepared from a forming mixture containing sources of aluminum, phosphorus and a non-aluminum, non-phosphorus element, e.g. boron or boron and silicon. The forming mixture further contains a directing agent comprising a mixture of quaternary nitrogen compound and amine in a molar ratio of 0.01 to 0.025.Type: GrantFiled: June 26, 1990Date of Patent: June 23, 1992Assignee: Mobil Oil CorporationInventor: Mark E. Davis
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Patent number: 5110444Abstract: Middle distillate petroleum streams are hydrotreated to produce a low sulfur and low aromatic product in a process employing three reaction zones in series. Hydrogen flows between the reaction zones countercurrent to the hydrocarbons. Hydrogen sulfide is removed from effluent of the first two reaction zones by hydrogen stripping. The second and third reaction zones employ a sulfur-sensitive noble metal hydrogenation catalyst. Operating pressure increases and temperature decreases from the first to third reaction zones.Type: GrantFiled: August 3, 1990Date of Patent: May 5, 1992
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Patent number: 5091073Abstract: This invention relates to a novel synthetic crystalline molecular sieve composition, MCM-37, which may contain framework +3 valence element, e.g. aluminum, and +5 valence element, e.g. phosphorus or with an addition +4 valence element, e.g. silicon, and to use thereof as a support and in catalytic conversion of organic compounds. The crystalline composition of this invention can easily be converted to catalytically active material.Type: GrantFiled: July 13, 1990Date of Patent: February 25, 1992Assignee: Mobil Oil Corp.Inventors: Clarence D. Chang, Cynthia T. W. Chu, Ralph M. Dessau, John B. Higgins, John D. Lutner, John D. Schlenker
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Patent number: 5087348Abstract: A novel treated charge zeolite is prepared by treating charge zeolite (which is essentially free of Secondary Pores) with steam for 5-60 hours at 1000.degree. F.-1500.degree. F. Product is particularly characterized by increased Secondary Pore Volume (pores of diameter of 100A-600A) in amount of as high as 0.20 cc/g.Type: GrantFiled: June 19, 1991Date of Patent: February 11, 1992Assignee: Texaco Inc.Inventors: Pei-Shing E. Dai, David E. Sherwood, Jr., Bobby R. Martin
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Patent number: 5068096Abstract: This invention relates to a new form of crystalline material identified as zeolite MCM-47, to a new and useful improvement in synthesizing said crystalline material and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g. hydrocarbon compound, conversion.Type: GrantFiled: April 8, 1991Date of Patent: November 26, 1991Assignee: Mobil Oil CorporationInventor: Ernest W. Valyocsik
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Patent number: 5045175Abstract: A hydrotreating process uses a separation section that reduces the loss of C.sub.4 and higher hydrocarbons through the use of a low hydrogen to hydrocarbon ratio in the reactor and the adsorptive removal of a majority of hydrogen sulfide from a liquid phase hydrotreater effluent. Sulfurous hydrocarbon feed is admixed with hydrogen to maintain a hydrogen to hydrocarbon ratio of less than 50 SCFB. The hydrogen and hydrocarbons are passed through a hydrotreater reactor to convert sulfur compounds to H.sub.2 S. The hydrotreater effluent is cooled and after flashing of any excess hydrogen or light ends the cooled effluent is contacted with an adsorbent material for the removal of H.sub.2 S. A hydrotreated hydrocarbon product is withdrawn from the adsorption section. The low hydrogen to hydrocarbon ratio permits the process to be used without the recycle of hydrogen thereby eliminating the need for separators and compressors that were formly used to recycle hydrogen to the hydrotreater.Type: GrantFiled: October 22, 1990Date of Patent: September 3, 1991Assignee: UOPInventors: Robert S. Haizmann, Andrew S. Zarchy, Martin F. Symoniak
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Patent number: 5011593Abstract: A hydrodesulfurization process for catalytically hydrosulfurizing highly aromatic feeds, especially catalytically cracked feeds such as light cycle oils from catalytic cracking processes and aromatic extracts, employs a hydrodesulfurization catalyst containing zeolite beta. The zeolite beta based catalyst is more effective for effecting desulfurization than comparable amorphous catalysts or catalysts based on other large pore size zeolite and is capable of achieving a high degree of desulfurization at relatively low levels of conversion. The hydrodesulfurization catalyst comprises a transition metal hydrogenation component, preferably Co/Mo, on zeolite beta together with an inert matrix. The zeolite beta based catalyst may be mixed with amorphous catalyst such as Co/Mo/alumina. The low sulfur products are useful as blending components for road diesel fuels and other distillate fuels.Type: GrantFiled: November 20, 1989Date of Patent: April 30, 1991Assignee: Mobil Oil CorporationInventors: Robert A. Ware, Stephen S. Wong
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Patent number: 5009770Abstract: A process of concurrently dedusting and upgrading particulate laden raw, whole retort oil is provided which comprises the steps of: retorting solid hydrocarbon-containing material such as oil shale to liberate an effluent stream of dust laden hydrocarbons; injecting the dust-laden retort effluent product stream into a catalytic hydrotreater; agitating the product stream in the hydrotreater to constantly maintain the particulates in suspension within the oil; catalytically hydrotreating the agitated product stream in the presence of a hydroprocessing gas at a pressure of from 500 to 3000 psi, a temperature of from 650.degree. to 850.degree. F. and a space velocity of from 0.1 to 6.0 hr.sup.-1, whereby the suspended particulates are agglomerated to facilitate solid-liquid separation and substantial amounts of sulfur and nitrogen contaminants are simultaneously removed from the resulting ungraded oil; and mechanically separating the agglomerated particulates from the upgraded whole oil.Type: GrantFiled: August 31, 1988Date of Patent: April 23, 1991Assignee: Amoco CorporationInventors: Jeffrey T. Miller, Albert L. Hensley, Jr.
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Patent number: 5009771Abstract: Disclosed is an improved process for the hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, and hydroconversion of a hydrocarbon feedstock containing asphaltenes, metals and Shell hot filtration solids precursors. The process utilizes a catalyst mixture wherein one component of the mixture is a relatively small pore catalyst and another component is a catalyst that possesses a relatively large amount of macropore volume.Type: GrantFiled: March 30, 1990Date of Patent: April 23, 1991Assignee: Amoco CorporationInventors: Frederick T. Clark, Albert L. Hensley, Jr., David Lyzinski, Lawrence B. Peck
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Patent number: 4990242Abstract: An enhanced process to reduce the sulfur content in petroleum distillate products through fractionation of a feedstock followed by segregated hydrotreating. Improved performance and more controlled desulfurization is achieved.Type: GrantFiled: June 14, 1989Date of Patent: February 5, 1991Assignee: Exxon Research and Engineering CompanyInventors: Stephen Louie, Gerald E. Markley
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Patent number: 4980046Abstract: A hydrotreating process uses a separation section that reduces the loss of C.sub.5 and higher hydrocarbons through the use of a low hydrogen to hydrocarbon ratio in the reactor and the adsorptive removal of a majority of hydrogen sulfide from a liquid phase hydrotreater effluent. Sulfurous hydrocarbon feed is admixed with hydrogen to maintain a hydrogen to hydrocarbon ratio of less than 50 SCFB. The hydrogen and hydrocarbons are passed through a hydrotreater reactor to convert sulfur compounds to H.sub.2 S. The hydrotreater effluent is cooled and after flashing of any excess hydrogen or light ends the cooled effluent is contacted with an adsorbent material for the removal of H.sub.2 S. A hydrotreated hydrocarbon product is withdrawn from the adsorption section. The low hydrogen to hydrocarbon ratio permits the process to be used without the recycle of hydrogen thereby eliminating the need for separators and compressors that were formerly used to recycle hydrogen to the hydrotreater.Type: GrantFiled: December 28, 1989Date of Patent: December 25, 1990Assignee: UOPInventors: Andrew S. Zarchy, Martin F. Symoniak, Robert S. Haizmann
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Patent number: 4969990Abstract: A catalyst useful for hydroprocessing a hydrocarbon-containing oil contains at least one hydrogenation component on an amorphous, porous refractory oxide. The catalyst is prepared by impregnating support particles having a narrow pore size distribution and a mode pore diameter from abpit 70 to 80 angstroms with a solution containing a precursor of the hydrogenation components, followed by drying and calcining. The catalyst is useful for promoting a number of hydrocarbon hydroprocessing reactions, particularly hydrogenative desulfurization, dedemetallization and denitrogenation, and most particularly, hydrodesulfurization of residuum-containing oils.Type: GrantFiled: August 31, 1989Date of Patent: November 13, 1990Assignee: Union Oil Company of CaliforniaInventor: Howard D. Simpson
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Patent number: 4941964Abstract: A process for the hydrotreatment of a sulfur and metal-containing hydrocarbon feed comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 3.0-5.0 wt. % of an oxide of a Group VIII metal, 14.5-24.0 wt. % of an oxide of a Group VIB metal and 0-2.0 wt. % of an oxide of phosphorus supported on a porous alumina support, and said catalyst is further characterized by having a total surface area of 150-210 m.sup.2 /g and a total pore volume of 0.50-0.75 cc/g with a pore diameter distribution such that micropores having diameters of 100-160A constitute 70-85% of the total pore volume of said catalyst and macropores having diameters of greater than 250A constitute 5.5-22.0% of the total pore volume of said catalyst.Type: GrantFiled: March 14, 1988Date of Patent: July 17, 1990Assignee: Texaco Inc.Inventors: Pei-Shing E. Dai, David E. Sherwood, Jr., Burton H. Bartley, Randall H. Petty
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Patent number: 4941968Abstract: Gum and sediment formation in liquid hydrocarbon mediums are inhibited by adding to the medium an alkyl 1,2-dihydroquinoline compound, dimer, trimer or polymer thereof. The invention is particularly well-suited for use in hydrodesulfurizer processes wherein the hydrocarbon medium is typically a naphtha, diesel, kerosene, light gas and or residual fuel charge and the charge or medium is subjected to high temperature and pressure treatment in the presence of a catalyst.Type: GrantFiled: July 28, 1989Date of Patent: July 17, 1990Assignee: Betz Laboratories, Inc.Inventor: Dwight K. Reid
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Patent number: 4898660Abstract: A novel family of crystalline, microporus aluminophosphate compositions is synthesized by hydrothermal crystallization at elevated temperatures of aluminophosphate gels containing a molecular structure forming template. The family comprises a number of distinct species, each with a unique crystal structure. Calcination removes volatile extraneous matter from the intracrystalline void space and yields microporus crystalline adsorbents with uniform pores, the dimensions of which vary, among the individual species, from about 3A to 10A diameter. The composition exhibit properties somewhat analogous to zeolitic molecular sieves which render them useful as catalysts or catalyst bases in chemical reactions such as hydrocarbon conversions.Type: GrantFiled: October 20, 1983Date of Patent: February 6, 1990Assignee: Union Carbide CorporationInventors: Stephen T. Wilson, Brent M. Lok, Edith M. Flanigen
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Patent number: 4894210Abstract: Desulphurization of saturated or near saturated gaseous hydrocarbon stream is effected using a bed of a particulate adsorbent comprising zinc oxide. Condensation of the higher boiling components is avoided by heating the raw gas to a temperature at least 10.degree. C. above its dew point. This heating is effected by heat exchange with the heated desulphurized gas and by heat exchange with the combustion products of a minor part stream taken from the raw gas and/or from the desulphurized product gas stream. The absorbent particles preferably have a high BET surface area and pore volume.Type: GrantFiled: June 20, 1986Date of Patent: January 16, 1990Assignee: Imperial Chemical Industries plcInventors: Patrick J. Denny, Alan E. Thomas, Peter J. Carnell
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Patent number: 4886935Abstract: A hydrocarbon-containing feedstock is desulfurized so as to contain less than 5, and preferably less than 2 ppmw of sulfur, in the first stage of a two-stage process. In the second stage, the feedstock is contacted with an isomerization catalyst useful for promoting n-paraffin isomerization reactions. A dual-function catalyst containing both Group VIII and Group IB metals and effective for simultaneously absorbing sulfur and isomerizing a hydrocarbon feedstock may be employed in the first stage. Alternatively, the dual-function catalyst may be employed in both the first and second stages. Alternatively still, the dual-function catalyst may be used to treat a feedstock containing n-paraffins in a single stage isomerization process.Type: GrantFiled: August 31, 1988Date of Patent: December 12, 1989Assignee: Union Oil Company of CaliforniaInventors: Peter Kokayeff, Suheil F. Abdo