With Hydrogen Patents (Class 208/89)
  • Patent number: 5770043
    Abstract: Disclosed is a catalytic cracking process which includes more than one catalytic cracking reaction step. The process integrates a hydroprocessing process step between the catalytic cracking reaction steps in order to maximize olefins production, mid-distillate quality and naphtha octane level in the cracked products. Preferably, a first cracked hydrocarbon product is obtained from a first cracking stage and separated into a mid-distillate and gas oil containing fraction having an initial boiling point of at least 300.degree. F., the distillate and gas oil containing fraction is hydroprocessed, and a naphtha fraction and a gas oil containing bottoms fraction of the hydroprocessed material are cracked in a second cracking stage.
    Type: Grant
    Filed: August 23, 1996
    Date of Patent: June 23, 1998
    Assignee: Exxon Research and Engineering Company
    Inventors: Edward S. Ellis, Ramesh Gupta, Martin G. Bienstock
  • Patent number: 5741414
    Abstract: There is provided a method of manufacturing gas oil containing low-sulfur and low-aromatic-compound content, said method including a first step of putting distilled petroleum to contact with hydrogen gas in the presence of a hydrotreating catalyst to reduce the sulfur concentration to not higher than 0.05 wt % and a second step of reducing the aromatic compound concentration in the presence of a noble metal type catalyst, with at least a pair of high temperature high pressure gas liquid separators arranged between the two steps to separate the gaseous and liquid components of distilled petroleum and hydrogen gas or hydrogen containing gas is introduced into the liquid component in each of the separators.
    Type: Grant
    Filed: September 1, 1995
    Date of Patent: April 21, 1998
    Assignee: Nippon Oil Co., Ltd.
    Inventors: Toshio Waku, Masanari Akiyama
  • Patent number: 5693191
    Abstract: A process is provided for the recovery of hydrogen chloride in anhydrous form from a dry (containing less than about 500 parts per million by weight of water) mixture of hydrogen chloride with one or more non-condensable gases and which may also contain components heavier than hydrogen chloride, which process comprises distilling the mixture to produce an overheads stream containing the non-condensable gases and about 95 percent or more by weight of the hydrogen chloride in the mixture and a bottoms stream containing about 95 percent or greater by weight of all components heavier than hydrogen chloride, and compressing and refrigerating the overheads stream whereby a selected proportion of the hydrogen chloride in the overheads stream is produced in a liquid anhydrous form containing less than about 50 parts per million by weight of water.
    Type: Grant
    Filed: November 23, 1994
    Date of Patent: December 2, 1997
    Assignee: The Dow Chemical Company
    Inventors: Katherine A. Pividal, Tom C. Tsai
  • Patent number: 5685972
    Abstract: Cracked naphtha feeds such as FCC naphtha and coker naphtha are upgraded to produce chemical grade BTX (benzene, toluene, xylene with ethylbenzene) while co-producing a low sulfur gasoline of relatively high octane number. The cracked, sulfur-containing naphtha is processed by hydrodesulfurization followed by treatment over an acidic catalyst, preferably a zeolite such as ZSM-5 or zeolite beta with a hydrogenation component, preferably 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 to permit a low sulfur gasoline of blending quality to be obtained with the BTX. The BTX can be extracted from the second stage effluent, preferably from a C.sub.6 -C.sub.8 fraction of this effluent.
    Type: Grant
    Filed: July 14, 1995
    Date of Patent: November 11, 1997
    Inventors: Hye Kyung C. Timken, Philip J. Angevine
  • Patent number: 5643441
    Abstract: Low sulfur gasoline of relatively high octane number is produced from a thermally cracked sulfur-containing naphtha such as coker naphtha, by hydrodesulfurization followed by treatment over an acidic catalyst, preferably a zeolite such as ZSM-5 or zeolite beta with a hydrogenation component, preferably molybdenum.
    Type: Grant
    Filed: April 24, 1995
    Date of Patent: July 1, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Hye Kyung C. Timken, Sherri L. Riedinger
  • Patent number: 5624547
    Abstract: Disclosed is a process for pretreatment of hydrocarbon feed containing sulfur and nitrogen compounds and aromatics prior to hydrocracking or fluid catalytic cracking which comprises:contacting said feedstock with a sulfided catalyst comprising a metal of non-noble Group VIII and Group VIB, and, optionally one or more elements selected from Group IIIA and Group VA of the Periodic Table on a carbon support consisting essentially of activated carbon, optionally on a carbon support treated with phosphorus, having a B.E.T. (Braunauer-Emmett Teller) surface area of at least 100 m.sup.2 /g and an average Pore Diameter greater than 12.ANG. and a Total Pore Volume greater than 0.3 cc/g.
    Type: Grant
    Filed: November 13, 1995
    Date of Patent: April 29, 1997
    Assignee: Texaco Inc.
    Inventors: Chakka Sudhakar, Paul O. Fritz, Carl J. Kjellson, Hua-Min Huang, Gerald G. Sandford
  • Patent number: 5603824
    Abstract: The instant invention discloses a process of upgrading a waxy hydrocarbon feed mixture containing sulfur compounds which boils in the distillate range, in order to reduce sulfur content and 85% point while preserving the high octane of naphtha by-products and maximizing distillate yield. The process employs a single, downflow reactor having at least two catalyst beds and an inter-bed redistributor between the beds. The top bed contains a hydrocracking catalyst, preferably zeolite beta, and the bottom bed contains a dewaxing catalyst, preferably ZSM-5. A desulfurization catalyst may be added to either bed depending on sulfur distribution in the feed. The feed is separated into a lighter, lower boiling stream and a heavier, higher boiling stream. The effluent of the top bed cascades without interbed separation to the inter-bed redistributor, where it is recombined with the lighter stream. The recombined stream then enters the bottom bed for dewaxing.
    Type: Grant
    Filed: August 3, 1994
    Date of Patent: February 18, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Chwan P. Kyan, Paul J. Oswald
  • Patent number: 5599439
    Abstract: A low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization followed by octane enhancing treatment in a fluidized bed catalytic process, in the presence of an aromatics-rich feedstream. The process converts the hydrodesulfurized intermediate and the aromatics-rich feedstream to a gasoline boiling range fraction of high octane number. The fluidized bed catalytic process is carried out over zeolite catalyst particles in a turbulent reactor bed at a temperature of about 600.degree. to 800.degree. F. (316.degree. to 427.degree. C.) and pressure of about 100 to 250 psig (790 to 825 kPa. The catalyst has an apparent particle density of about 0.9 to 1.6 g/cm.sup.3 and a size range of about 1 to 150 microns, and average catalyst particle size of about 20 to 100 microns containing about 10 to 25 weight percent of fine particles having a particle size less than 32 microns.
    Type: Grant
    Filed: October 14, 1994
    Date of Patent: February 4, 1997
    Assignee: Mobil Oil Corporation
    Inventors: Nick A. Collins, Mohsen N. Harandi, Edward F. Kondis, Hartley Owen
  • Patent number: 5582711
    Abstract: Disclosed is a catalytic cracking process which includes more than one catalytic cracking reaction step. The process integrates a hydroprocessing step between the catalytic cracking reaction steps in order to maximize olefins production, distillate quality and octane level of the overall cracked product. Preferably, the hydroprocessing step is included between the reaction stages, and a portion of the hydroprocessed products, i.e., a naphtha and mid distillate fraction, is combined with cracked product for further separation and hydroprocessing. It is also preferred that the first catalytic cracking reaction step be a short contact time reaction step.
    Type: Grant
    Filed: August 17, 1994
    Date of Patent: December 10, 1996
    Assignee: Exxon Research and Engineering Company
    Inventors: Edward S. Ellis, Ramesh Gupta, Martin G. Bienstock
  • Patent number: 5580442
    Abstract: A process is disclosed for producing feedstocks for manufacturing high quality lube base oil utilizing unconverted oil, which is produced from a fuels hydrocracker unit. The first step of the process is the distillation of an atmospheric residue under vacuum in a first vacuum distillation unit to produce a vacuum gas oil. The vacuum gas oil is then hydrotreated in a first reaction unit to remove impurities and produce a treated vacuum gas oil. The treated vacuum gas oil is then subjected to hydrocracking in a second reaction unit to yield light hydrocarbons. The light hydrocarbons are then subjected to a series of fractional distillations to separate light oil products and an unconverted oil. All or a fraction of the unconverted oil is fed to a second vacuum distillation unit to produce feedstocks of high quality lube base oil and a remaining portion. The remaining portion and, optionally, a fraction of the unconverted oil is recycled from the second vacuum distillation unit to the second reaction unit.
    Type: Grant
    Filed: May 13, 1994
    Date of Patent: December 3, 1996
    Assignee: Yukong Limited
    Inventors: Sook-hyung Kwon, Wha-sik Min, Yun-kil Lee
  • Patent number: 5554275
    Abstract: A method and operating technique for treating organosulfur compound-containing aliphatic streams by introducing the light hydrocarbon stream at a top portion of a vertical stripping tower having an upper catalytic contact zone containing a bed of solid hydrodesulfurization catalyst particles and a lower contact zone, and introducing a light gas stream containing hydrogen at a lower portion of said stripping tower. Hydrodesulfurization is effected by flowing the light hydrocarbon stream and light gas stream countercurrently in contact with the solid hydrodesulfurization catalyst particles under hydrodesulfurization and stripping conditions, thereby converting the organosulfur compound in the upper contact zone.
    Type: Grant
    Filed: November 28, 1994
    Date of Patent: September 10, 1996
    Assignee: Mobil Oil Corporation
    Inventor: Mohsen N. Harandi
  • Patent number: 5552033
    Abstract: An integrated process for increasing C.sub.6 to C.sub.8 aromatics content in reformate prepared from C.sub.9.sup.+ aromatics-containing feed comprises:1) pretreating a raw naphtha feedstream containing C.sub.9.sup.+ aromatics and sulfur by contacting with a) a hydrodesulfurization catalyst under hydrodesulfurization conditions to produce a hydrodesulfurized feedstream and thereafter b) cascading said hydrodesulfurized feedstream over a noble metal- and/or Group VIA metal-containing porous crystalline inorganic oxide catalyst comprising pores having openings of 12-member rings under conditions sufficient to effect conversion of C.sub.9.sup.+ aromatics, thereby providing a pretreated effluent stream of enhanced C.sub.8.sup.- aromatics content relative to that obtained in the absence of said cascading; and2) reforming at least a portion of said pretreated effluent stream to provide a reformate stream.
    Type: Grant
    Filed: December 1, 1994
    Date of Patent: September 3, 1996
    Assignee: Mobil Oil Corporation
    Inventor: Stuart S. Shih
  • Patent number: 5525209
    Abstract: A process for the joint production of middle distillates and oil bases (viscosity index between 95 and 150) particularly from vacuum distillates and/or deasphalted oils, comprises a first step in which the feedstock is brought into contact with an amorphous catalyst containing at least one metal or metallic compound with a hydro-dehydrogenating function, such as Ni, Mo, W or Co, at a temperature of between 350.degree. C. and 430.degree. C., a pressure of between 5 and 20 MPa, a space velocity of between 0.1 and 5 h.sup.-1 in the presence of hydrogen in a ratio H.sub.2 /HC of 150 to 2,000 by volume. The product from the first step is brought into contact in a second step with a second catalyst comprising a support, a Y zeolite, at least one group VIB element and at least one group VIII metal at a temperature of between 350.degree. C. and 430.degree. C., a pressure of between 5 and 20 MPa and a space velocity of between 0.1 and 5 h.sup.-1.
    Type: Grant
    Filed: October 24, 1994
    Date of Patent: June 11, 1996
    Assignee: Institut Francais Du Petrole
    Inventors: Alain Billon, Jean-Pierre Peries, Pierre-Henri Bigeard
  • Patent number: 5512166
    Abstract: A process for the simultaneous replacement of a first catalyst by a second catalyst which first catalyst is circulating as a moving bed of solid particles in a hydrocarbon treating unit, which unit comprises at least one processing reactor. The first catalyst is withdrawn downstream of the reactor, or of each reactor, in the direction of catalyst circulation. The second catalyst is simultaneously injected upstream of the reactor or of each reactor. The bulk density of the material withdrawn downstream of the reactor, or of each reactor, is measured continuously. The withdrawal of the first catalyst and the injection of the second catalyst into the reactor concerned are interrupted when the bulk density so measured is equal to that of the second catalyst.
    Type: Grant
    Filed: July 10, 1992
    Date of Patent: April 30, 1996
    Assignee: Total Raffinage Distribution, S.A.
    Inventors: Patrice Herrenschmidt, Fran.cedilla.ois-Xavier Cormerais, Thierry Patureaux
  • Patent number: 5510016
    Abstract: A process for catalytically desulfurizing cracked fractions in the gasoline boiling range to acceptable sulfur levels uses an initial hydrotreating step to desulfurize the feed with some reduction in octane number, after which the desulfurized material is treated with a self-bound or binder-free zeolite to restore lost octane. The process may be utilized to desulfurize catalytically and thermally cracked naphthas such as FCC naphtha as well as pyrolysis gasoline and coker naphthas, while maintaining octane so as to reduce the requirement for reformate and alkylate in the gasoline blend. The self-bound catalyst offers advantages in activity and permits the process to be carried out at lower temperatures.
    Type: Grant
    Filed: September 9, 1994
    Date of Patent: April 23, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Timothy T. Hilbert, Dominick N. Mazzone, Michael S. Sarli
  • Patent number: 5503734
    Abstract: 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 a catalyst comprising an intermediate pore size zeolite, such as ZSM-5, and a large pore size zeolite, including a metal hydrogenation function, such as a faujasite, preferably USY, which contains nickel and 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. Use of the intermediate pore size zeolite and the large pore size zeolite is expected to provide more boiling point conversion than either zeolite alone under the same conditions.
    Type: Grant
    Filed: December 30, 1994
    Date of Patent: April 2, 1996
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5500108
    Abstract: 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 an intermediate pore size zeolite such as zeolite ZSM-5 in combination with molybdenum. The use of the molybdenum in combination with the zeolite has been found to give improved catalytic acitivity coupled with lower coking, longer catalyst life and other advantages.
    Type: Grant
    Filed: September 9, 1994
    Date of Patent: March 19, 1996
    Assignee: Mobil Oil Corporation
    Inventors: Paul P. Durand, Hye K. C. Timken
  • Patent number: 5470454
    Abstract: A process for the preparation of a lubricating base oil, comprising treating a hydrocarbonaceous product with hydrogen, at elevated temperature and pressure and in the presence of a catalyst, which hydrocarbonaceous product has been prepared by contacting hydrocarbons and/or derivatives thereof with an active hydrogen-containing system by a process which comprises generating a hydrogen-containing plasma and allowing contact of the hydrocarbons and/or derivatives thereof in liquid form with the plasma-generated system and recovering the hydrocarbonaceous product.
    Type: Grant
    Filed: June 2, 1993
    Date of Patent: November 28, 1995
    Assignee: Shell Oil Company
    Inventors: Pierre Grandvallet, Daniel G. P. Allais, Pierre E. J. G. Dejaifve
  • Patent number: 5439583
    Abstract: A process is disclosed for removing residual sulfur from a hydrotreated naphtha feedstock. The feedstock is contacted with molecular hydrogen under reforming conditions in the presence of a less sulfur sensitive reforming catalyst to convert trace sulfur compounds to H.sub.2 S, and to form a first effluent. The first effluent is contacted with a solid sulfur sorbent to remove the H.sub.2 S and form a second effluent. The second effluent is then contacted with a highly selective reforming catalyst under severe reforming conditions. Also disclosed is a method using a potassium containing sulfur sorbent made from nitrogen-free potassium compounds.
    Type: Grant
    Filed: January 4, 1993
    Date of Patent: August 8, 1995
    Assignee: Chevron Research and Technology Company
    Inventors: Richard C. Robinson, Robert L. Jacobson, Harris E. Kluksdahl, William A. Blanton, Dennis L. Holtermann, Leslie A. Field
  • Patent number: 5413697
    Abstract: 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 containing, preferably an intermediate pore size zeolite such as ZSM-5 and a zeolite such as 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: Grant
    Filed: July 15, 1992
    Date of Patent: May 9, 1995
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5413696
    Abstract: 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 comprising zeolite beta. 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: Grant
    Filed: June 1, 1992
    Date of Patent: May 9, 1995
    Assignee: Mobile Oil Corporation
    Inventors: David L. Fletcher, Timothy L. Hilbert, Stephen J. McGovern, Michel S. Sarli, Stuart S. Shih
  • Patent number: 5413698
    Abstract: 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: Grant
    Filed: August 5, 1992
    Date of Patent: May 9, 1995
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Mohsen N. Harandi, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5411658
    Abstract: 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: Grant
    Filed: October 8, 1993
    Date of Patent: May 2, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Birbal Chawla, Dominik N. Mazzone, Michael S. Sarli, Stuart S. Shih, Hye Kyung C. Timken
  • Patent number: 5409596
    Abstract: 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: Grant
    Filed: March 12, 1992
    Date of Patent: April 25, 1995
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5407559
    Abstract: 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: Grant
    Filed: June 1, 1992
    Date of Patent: April 18, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Thomas F. Degnan, Stuart S. Shih
  • Patent number: 5401365
    Abstract: A process is provided for separating benzene from non-aromatics in a highly aromatic stream containing olefins in a concentration range of from about 0.05 to about 5.0, which process comprises predistilling said highly aromatic stream to produce a distilled fraction having a concentration of C.sub.8 and heavier compounds of less than about 0.1 wt percent; and extracting said distilled fraction with a solvent comprising substituted morpholines in an extractive distillation zone to produce a highly-pure benzene stream.
    Type: Grant
    Filed: October 27, 1993
    Date of Patent: March 28, 1995
    Assignee: Chevron Research & Technology
    Inventors: George T. Chen, Brenda M. Balaban, Gerd Emmrich, Bernhard Firnhaber
  • Patent number: 5401385
    Abstract: A process combination is disclosed to selectively upgrade catalytically cracked gasoline to obtain products suitable for further upgrading to reformulated fuels. A naphtha feedstock, preferably heavy naphtha, is hydrogenated to saturate aromatics, followed by selective isoparaffin synthesis to yield light and heavy synthesis naphtha and isobutane. The heavy synthesis naphtha may be processed by reforming, light naphtha may be isomerized, and isobutane may be upgraded by dehydrogenation, etherification and/or alkylation to yield gasoline components from the process combination suitable for production of reformulated gasoline.
    Type: Grant
    Filed: August 10, 1993
    Date of Patent: March 28, 1995
    Assignee: UOP
    Inventors: Robert J. Schmidt, Paula L. Bogdan, R. Joe Lawson, J. W. Adriaan Sachtler
  • Patent number: 5401389
    Abstract: Light cycle oil (LCO) is upgraded to a low sulfur gasoline by co-processing the LCO with a cracked, sulfur-containing olefinic naphthas by hydrodesulfurization followed by treatment over an acidic catalyst comprising zeolite beta with a metal 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. The zeolite beta catalyst is active for conversion of the higher boiling portions of the feed to products of low sulfur content in the gasoline boiling range.
    Type: Grant
    Filed: October 12, 1993
    Date of Patent: March 28, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Dominick N. Mazzone, Samual A. Tabak, Hye Kyung C. Timken
  • Patent number: 5399258
    Abstract: 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: Grant
    Filed: December 10, 1992
    Date of Patent: March 21, 1995
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih, Stephen J. McGovern, Douglas S. Diez, Mohsen N. Harandi, Timothy L. Hilbert
  • Patent number: 5391288
    Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha and benzene-rich fraction by hydrodesulfurization in a first reaction zone and treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5 in a second reaction zone to reduce the octane loss which takes place as a result of the hydrodesulfurization. The benzene-rich fraction can be cofed to the first reaction zone or the second reaction zone. The benzene-rich fraction is preferably a heart-cut reformate.
    Type: Grant
    Filed: June 10, 1993
    Date of Patent: February 21, 1995
    Assignee: Mobil Oil Corporation
    Inventors: Nick A. Collins, Paul P. Durand, David L. Fletcher, Mohsen N. Harandi, Edward F. Kondis, Hartley Owen, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5382349
    Abstract: A method of hydrotreatment of heavy hydrocarbon oil in the presence of catalysts which comprises hydrodemetallizing and hydrocracking the heavy hydrocarbon oil successively and thereafter hydrodesulfurizing and hydrodenitrogenating the treated heavy hydrocarbon oil. The hydrocracking is carried out in the presence of a catalyst comprising at least one metal or metal compound of the group VIA or the group VIII of the Periodic Table supported on a carrier comprising 10 to 90 weight % of an iron-containing aluminosilicate and 90 to 10 weight % of an inorganic oxide. Other methods of treatment of heavy hydrocarbon oil comprise the hydrotreatment in conjunction with fluid catalytic cracking and/or thermal hydrocracking. The methods provide a naphtha fraction, a kerosene fraction and a gas oil fraction which can be obtained from the heavy hydrocarbon oil efficiently with high yield.
    Type: Grant
    Filed: September 14, 1992
    Date of Patent: January 17, 1995
    Assignee: Idemitsu Kosan Co., Ltd.
    Inventors: Mitsuru Yoshita, Kenichi Ii, Kazuhiro Kashima, Eiichiro Kanda, Takanori Ohno, Naotake Takeuchi
  • Patent number: 5371308
    Abstract: A process for preparing lower olefins from a hydrocarbon feed having at least a fraction boiling above the boiling point range of the lower olefins, which process includes thermal cracking of the hydrocarbon feed, wherein at least part of the hydrocarbon feed is a hydroprocessed synthetic oil fraction. The hydroprocessed synthetic oil fraction may be prepared by hydrogenation and/or hydroconversion and/or hydrocracking of a synthetic oil fraction.
    Type: Grant
    Filed: August 25, 1993
    Date of Patent: December 6, 1994
    Assignee: Shell Oil Company
    Inventors: John W. Gosselink, Jacobus Eilers
  • Patent number: 5362376
    Abstract: 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: Grant
    Filed: August 13, 1992
    Date of Patent: November 8, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Stuart S. Shih, Philip J. Angevine
  • Patent number: 5362382
    Abstract: Heavy oils are advantageously preconditioned by heat soaking prior to hydrotreating with a dispersed metal catalyst to reduce coking in a two stage hydrotreating process. The effluent of a hydrotreating process is filtered to recover catalytically active coke which is recovered by backflushing and recycled to the feed stream. A mild solvent deasphalting step isolates metals in a reduced volume asphaltene fraction.
    Type: Grant
    Filed: June 24, 1991
    Date of Patent: November 8, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Roland H. Heck, Frank T. DiGuiseppi
  • Patent number: 5360532
    Abstract: Low sulfur gasoline is produced from a catalytically cracked, sulfur-containing naphtha by fractionating the naphtha feed into a low boiling fraction in which the majority of the sulfur is present in the form of mercaptans and a high-boiling fraction in which the sulfur is predominantly in non-mercaptan form such as thiophenes. The low boiling fraction is desulfurized by a non-hydrogenative mercaptan extraction process which retains the olefins which are present in this fraction. The second fraction is desulfurized by hydrodesulfurization, which results in some saturation of olefins and loss of octane. The octane loss is restored by treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5, to form a low sulfur gasoline product with an octane number comparable to that of the feed naphtha but which contains some recombined sulfur in the form or mercaptans which are removed in the non-hydrogenative mercaptan extraction step.
    Type: Grant
    Filed: April 2, 1993
    Date of Patent: November 1, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Stephen J. McGovern, John E. Sauer
  • Patent number: 5352354
    Abstract: 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: Grant
    Filed: June 1, 1992
    Date of Patent: October 4, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Timothy L. Hilbert, Stephen J. McGovern, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5348641
    Abstract: 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: Grant
    Filed: May 8, 1992
    Date of Patent: September 20, 1994
    Assignee: Mobil Oil Corporation
    Inventor: Stuart S. Shih
  • Patent number: 5346609
    Abstract: 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: Grant
    Filed: August 15, 1991
    Date of Patent: September 13, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5326463
    Abstract: Low sulfur gasoline of relatively high octane number is produced from a catalytically cracked, sulfur-containing naphtha by hydrodesulfurization and treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5 in an octane restoration step, followed by separation of a C.sub.9 -containing fraction, and recycling the C.sub.9 -containing fraction to the octane restoration step. A hydrocarbon fraction comprising C.sub.1 to C.sub.3 hydrocarbons may also be separated from the octane restored product and recycled for purposes of alkylating aromatic hydrocarbons and for this purpose, it may be advantageous to introduce a benzene-rich feed, such as a reformate, to the process. The treatment over the acidic catalyst in the octane restoration 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.
    Type: Grant
    Filed: October 28, 1992
    Date of Patent: July 5, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Timothy L. Hilbert, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5326462
    Abstract: 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 a zeolite having the topology of ZSM-5 and a zeolite sorbing 10 to 40 mg 3-methylpentane at 90.degree. C., 90 torr, per gram dry zeolite in the hydrogen form, e.g., ZSM-22, ZSM-23, or ZSM-35. The treatment over the acidic catalyst system 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.
    Type: Grant
    Filed: August 13, 1992
    Date of Patent: July 5, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Stuart S-S. Shih, Kathleen M. Keville, Daria N. Lissy
  • Patent number: 5322619
    Abstract: A fluid catalytic cracking process for producing relatively low emissions fuels. The feedstock is relatively low in nitrogen and aromatics and high in hydrogen content and the catalyst is a rare-earth promoted amorphous silica-alumina catalyst. The feedstock can be characterized as having less than about 50 wppm nitrogen; greater than about 13 wt. % hydrogen; less than about 7.5 wt. % 2+ ring aromatic cores; and not more than about 15 wt. % aromatic cores overall.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: June 21, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Stephen M. Davis, William E. Winter, Daniel F. Ryan
  • Patent number: 5320745
    Abstract: A fluid catalytic cracking process for producing relatively low emissions fuels, The feedstock is relatively low in nitrogen and aromatics and high in hydrogen content and the catalyst is an amorphous acidic catalytic material which is promoted with up to about 5000 wppm chromium. The feedstock can be characterized as having less than about 50 wppm nitrogen; greater than about 13 wt. % hydrogen; less than about 7.5 wt. % 2+ ring aromatic cores; and not more than about 15 wt. % aromatic cores overall.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: June 14, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Bruce R. Cook, William E. Winter, Daniel F. Ryan
  • Patent number: 5320742
    Abstract: A sulfur-containing catalytically cracked naphtha is upgraded to form a low-sulfur gasoline product by a process which retains the octane contribution from the olefinic front end of the naphtha. Initially, the mercaptan sulfur in the front end of the cracked naphtha is converted to higher boiling disulfides by oxidation. The front end, which is then essentially an olefinic, high octane sulfur-free material, may be blended directly into the gasoline pool. The back end, which now contains the original higher boiling sulfur components such as thiophenes, together with the sulfur transferred from the front end as disulfides, is hydrotreated to produce a desulfurized product. This desulfurized product, which has undergone a loss in octane by saturation of olefins, is then treated in a second stage, by contact with a catalyst of acidic functionality, preferably a zeolite such as ZSM-5, under conditions which produce a product in the gasoline boiling range of higher octane value.
    Type: Grant
    Filed: October 19, 1992
    Date of Patent: June 14, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Timothy L. Hilbert, David A. Pappal, David W. Rumsey, Gerald J. Teitman
  • Patent number: 5318692
    Abstract: A fluid catalytic cracking process for producing relatively low emissions fuels. The feedstock is relatively low in nitrogen and aromatics and high in hydrogen content and the catalyst is a mixture of zeolite-Y and ZSM-5, or an amorphous acid catalytic material with ZSM-5, or a combination of all three. The feedstock can be characterized as having less than about 50 wppm nitrogen; greater than about 13 wt. % hydrogen; less than about 7.5 wt. % 2+ ring aromatic cores; and not more than about 15 wt. % aromatic cores overall.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: June 7, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Paul E. Eberly, Jr., William E. Winter
  • Patent number: 5318690
    Abstract: Low sulfur gasoline is produced from a catalytically cracked, sulfur-containing naphtha by fractionating the naphtha feed into a low boiling fraction in which the majority of the sulfur is present in the form of mercaptans and a high-boiling fraction in which the sulfur is predominantly in non-mercaptan form such as thiophenes. The low boiling fraction is desulfurized by a non-hydrogenatile mercaptan extraction process which retains the olefins present in this fraction. The second fraction is desulfurized by hydrodesulfurization, which results in some saturation of olefins and loss of octane. The octane loss is restored by treatment over an acidic catalyst, preferably an intermediate pore size zeolite such as ZSM-5, to form a low sulfur gasoline product with an octane number comparable to that of the feed naphtha but which contains some recombined sulfur in the form or mercaptans which are removed in a final hydrotreatment.
    Type: Grant
    Filed: January 7, 1993
    Date of Patent: June 7, 1994
    Assignee: Mobil Oil Corporation
    Inventors: David L. Fletcher, Timothy L. Hilbert, Stephen J. McGovern, John E. Sauer
  • Patent number: 5318693
    Abstract: A fluid catalytic cracking process for producing relatively low emissions fuels. The feedstock is relatively low in nitrogen and aromatics and high in hydrogen content and the catalyst is an amorphous silica-alumina containing a separate surface silica phase. The feedstock can be characterized as having less than about 50 wppm nitrogen; greater than about 13 wt. % hydrogen; less than about 7.5 wt. % 2+ ring aromatic cores; and not more than about 15 wt. % aromatic cores overall.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: June 7, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Stephen M. Davis, William E. Winter
  • Patent number: 5318694
    Abstract: A fluid catalytic cracking process for producing relatively low emissions fuels. The feedstock is exceptionally low in nitrogen and aromatics and relatively high in hydrogen and a 345.degree. C.+ products fraction is recycled to the cracking zone. The catalyst is an amorphous silica-alumina or a zeolitic material which is iso-structural to faujasite. The feedstock can be characterized as having less than about 50 wppm nitrogen; greater than about 13 wt. % hydrogen; less than about 7.5 wt. % 2+ ring aromatic cores; and not more than about 15 wt. % aromatic cores overall.
    Type: Grant
    Filed: November 30, 1992
    Date of Patent: June 7, 1994
    Assignee: Exxon Research and Engineering Company
    Inventors: Patrick J. Maher, William L. Schuette, William E. Winter
  • Patent number: 5312543
    Abstract: A resid hydrotreating process hydrotreats a resid bottoms fraction from the reduction of crude oil. The hydrotreated bottoms fraction is then subjected to deep vacuum reduction and in some cases deasphalted by solvent extraction to produce an oil suitable for use as a catalytic cracking feedstock and a resins fraction suitable for solvating resid in a hydrotreating process.
    Type: Grant
    Filed: June 22, 1992
    Date of Patent: May 17, 1994
    Assignee: Amoco Corporation
    Inventors: James L. Taylor, William I. Beaton, Bernard Y. C. So, Jeffrey J. Kolstad
  • Patent number: 5308471
    Abstract: 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, modified to reduce surface acidity, and 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: Grant
    Filed: July 20, 1992
    Date of Patent: May 3, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Minas R. Apelian, David L. Fletcher, Michael S. Sarli, Stuart S. Shih
  • Patent number: 5302279
    Abstract: Hydrocarbon lubricants having a high viscosity index (V.I.) and low pour point are produced by hydroisomerizing, over zeolite beta, a waxy lube feed such as a waxy vacuum gas oil whose aromatic components are removed by extraction, e.g. with furfural. The zeolite beta catalyst comprises noble metal, e.g., Pt, and a low acidity zeolite beta, e.g., framework boron-containing zeolite beta.
    Type: Grant
    Filed: December 23, 1992
    Date of Patent: April 12, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Thomas F. Degnan, Quang N. Le