With Catalyst Rehabilitation By Reversion From Different Compound Or Hf Complex Patents (Class 585/710)
  • Patent number: 8633346
    Abstract: The present invention provides process for preparing an alkylate comprising contacting in a reaction zone a hydrocarbon mixture comprising at least an isoparaffin and an olefin with an acidic ionic liquid catalyst under alkylation conditions to obtain an alkylate-comprising effluent, in which process: —solids are formed in the reaction zone; —a solids-comprising effluent comprising hydrocarbons and acidic ionic liquid is withdrawn from the reaction zone; and—at least part of the solids-comprising effluent is treated to remove at least part of the solids to obtain a solids-depleted effluent. The invention further provides a process for treating an acidic ionic liquid comprising at least 0.1 wt % of solids based on the total weight of the acidic ionic liquid, wherein at least part of the solids are removed.
    Type: Grant
    Filed: August 5, 2010
    Date of Patent: January 21, 2014
    Assignee: Shell Oil Company
    Inventors: Zhichang Liu, Chunming Xu, Rui Zhang, Xianghai Meng, Ana Cecilia Patroni, Peter Anton August Klusener, Albertus Vincentius Petrus Van Den Bosch
  • Patent number: 8487154
    Abstract: A process comprising adjusting a level of conjunct polymers in an ionic liquid catalyst between a low level that favors production of C5+ products boiling at 137.8° C. or below and a higher level that favors production of both C5+ products boiling at 137.8° C. or below and C5+ products boiling above 137.8° C.; wherein the adjusting is done in response to market demand. A process unit, comprising a reactor that operates with an ionic liquid catalyst comprising a low level or a higher level of conjunct polymers, and the alkylation reactor is switched between operating with the low and the higher levels in response to market demand. A process unit, comprising a reactor that operates in an alkylate mode and a distillate mode, and a catalyst regenerator that operates with varying severity to adjust the level of conjunct polymers in response to demand for gasoline or distillate.
    Type: Grant
    Filed: March 17, 2010
    Date of Patent: July 16, 2013
    Assignee: Chevron U.S.A. Inc.
    Inventors: Hye-Kyung Timken, Shawn Winter, Howard S. Lacheen, Sven Ivar Hommeltoft
  • Patent number: 8455708
    Abstract: A process for producing hydrocarbon products, comprising: a) operating a process unit in an alkylate mode wherein greater than 50 wt % of a C5+ hydrocarbon stream from the process unit boils at 137.8° C. or below, b) adjusting one or more process conditions in the process unit, and c) after the adjusting step, operating the process unit in a distillate mode wherein greater than 50 wt % of the C5+ hydrocarbon stream from the process unit boils above 137.8° C. Also, a process unit, comprising: a) an alkylation reactor; and b) a control system that enables the alkylation reactor to be operated in the alkylate mode and in the distillate mode; wherein the alkylation reactor can switch back and forth from operating in the alkylate mode to the distillate mode.
    Type: Grant
    Filed: March 17, 2010
    Date of Patent: June 4, 2013
    Assignee: Chevron U.S.A. Inc.
    Inventors: Hye-Kyung Timken, Shawn Winter, Howard S. Lacheen, Sven Ivar Hommeltoft
  • Publication number: 20120165592
    Abstract: The present invention provides a method for revamping an HF or sulphuric acid alkylation unit to an ionic liquid alkylation unit, wherein the HF or sulphuric acid alkylation unit comprise at least: a reactor unit for contacting catalyst and hydrocarbon reactants; a separator unit for separating a reactor effluent into a catalyst phase and an alkylate-comprising hydrocarbon phase; a fractionator unit for fractionating the alkylate-comprising hydrocarbon phase into at least one stream comprising alkylate; and which method includes: providing a second separator unit suitable for the separation of solids from liquids downstream of the reactor unit suitable to reduce the solids content in at least part of the reactor effluent.
    Type: Application
    Filed: August 5, 2010
    Publication date: June 28, 2012
    Inventors: Zhichang Liu, Chunming Xu, Rui Zhang, Xianghai Meng, Ana Cecilia Patroni, Peter Anton August Klusener, Albertus Vincentius Petrus Van Den Bosch
  • Patent number: 8163969
    Abstract: An improved alkylation process utilizing a solid-acid catalyst comprising a rare earth containing zeolite and a hydrogenation metal is disclosed.
    Type: Grant
    Filed: January 28, 2008
    Date of Patent: April 24, 2012
    Assignee: Albemarle Netherlands B.V.
    Inventors: Emanuel Hermanus Van Broekhoven, Mark Hendrikus Harte, Gijsbertus Klaver, Jan Nieman
  • Patent number: 7947232
    Abstract: An improved reactor for an HF alkylation unit of the shell-and-tube heat exchanger type has an axial tube bundle to provide cooling for the reactor and a centrally-located axial sparger system for injecting and dispersing the hydrocarbon reactants into the flow path in the reactor. The sparger comprises an axially-extensive tube with outlet nozzles for the hydrocarbon reactants arranged around the tube, preferably with differing radial angles, at different locations along the length of the sparger.
    Type: Grant
    Filed: November 30, 2007
    Date of Patent: May 24, 2011
    Assignee: ExxonMobil Research & Engineering Company
    Inventors: Ramon A. Strauss, Ramesh R. Hemrajani
  • Publication number: 20090221863
    Abstract: An HF alkylation process for producing gasoline boiling range alkylate product by the alkylation of a light olefin with an isoparaffin in the presence of hydrogen fluoride as an alkylation catalyst, in which the content of organic fluorides in the alkylation product stream is reduced by recontact with additional HF alkylation acid after which the hydrocarbon phase and the denser acid-containing phase are separated in a hydrocyclone. The use of the hydrocyclone enables the acid inventory of the unit to be significantly reduced which still achieving satisfactory removal of the unwanted fluoride by-products.
    Type: Application
    Filed: January 26, 2009
    Publication date: September 3, 2009
    Applicant: ExxonMobil Research and Engineering Comapny
    Inventors: Ramon A. Strauss, Brian A. Cunningham, Jeffrey M. Fitt, Ramesh R. Hemrajani
  • Patent number: 6844479
    Abstract: A process for the alkylation of paraffins with olefins includes contacting the paraffin with the olefin under alkylation conditions with a zeolite having an AAI number of at least about 1.0. In a preferred process isobutane is alkylated with cis-2-butene to produce a high octane (RON) gasoline product containing trimethylpentane isomers.
    Type: Grant
    Filed: April 24, 2003
    Date of Patent: January 18, 2005
    Assignee: ABB Lummus Global Inc.
    Inventors: Chuen Y. Yeh, Xingtao Gao, Philip J. Angevine
  • Patent number: 6492571
    Abstract: This invention relates to a process for alkylation of an isoparaffin with an olefin over a solid-acid catalyst, wherein at least two parallel reactors are used at the same time. When the solid acid catalyst in one or more reactors need to be regenerated, the catalyst is contacted in-situ in the reactor with a solvent to wash out the macromolecular hydrocarbons deposited on the surface of the catalyst in order to resume the high selectivity of catalyst in alkylation.
    Type: Grant
    Filed: July 20, 2000
    Date of Patent: December 10, 2002
    Assignees: China Petroleum Corporation, Research Institute of Petroleum Processing, Sinopec
    Inventors: Yigong He, Yufeng He, Wenhua Xie, Qiang Fu
  • Publication number: 20020173684
    Abstract: A method of alkylating aliphatic or aromatic hydrocarbons with olefins using solid hydrogen fluoride-equivalent catalysts is described. Preferred catalysts comprise solid polymeric onium polyhydrogen fluoride complexes.
    Type: Application
    Filed: May 17, 2001
    Publication date: November 21, 2002
    Inventor: George A. Olah
  • Patent number: 6187986
    Abstract: A slipstream of high pressure, cooled isobutane recycle from within an alkylation process unit is used to withdraw hydrofluoric acid from a storage vessel by means of an eductor and discharges the same into a reactor section of the unit. The eductor is preferably constructed of HASTELLOY “C” which provides both corrosion resistance to HF acid and has excellent surface hardness to withstand the highly erosive eductor application. This eductor eliminates potential release of HF acid due to failure of conventional rotating equipment seals or sealing systems, is low cost, has no moving parts, and is fireproof (will not lose containment during a fire).
    Type: Grant
    Filed: October 4, 1999
    Date of Patent: February 13, 2001
    Assignee: Marathon Ashland Petroleum, LLC
    Inventor: Dan R. Schlaeppi
  • Patent number: 5672798
    Abstract: Hydrocarbons are alkylated in a fluidized riser-reactor using a solid catalyst which is regenerated within the process by contact with hydrogen. The alkylation and regeneration steps are separated to prevent the admixture of hydrogen and any olefins present in the process. Two separate modes of regeneration are performed simultaneously: a mild liquid-phase washing and a vapor-phase hot hydrogen stripping operation.
    Type: Grant
    Filed: February 5, 1996
    Date of Patent: September 30, 1997
    Assignee: UOP
    Inventors: Scott Yu-Feng Zhang, Christopher David Gosling, Paul Alvin Sechrist, Gregory A. Funk
  • Patent number: 5489727
    Abstract: The disproportionation of isopentane(s) in the presence of hydrogen fluoride as the catalyst is improved by adding at least one C.sub.6 -C.sub.18 (preferably C.sub.6 -C.sub.8) isoalkane to the isopentane feed.
    Type: Grant
    Filed: May 25, 1995
    Date of Patent: February 6, 1996
    Assignee: Phillips Petroleum Company
    Inventors: Bruce B. Randolph, Marvin M. Johnson
  • Patent number: 5354938
    Abstract: The surface properties of hydrofluoric acid are modified by the addition of a perfluoro compound in order to reduce the tendency of the HF to form an aerosol upon any release of HF alkylation acid from an HF alkylation unit. The perfluoro compounds which are used are the perfluorosulfonic acid fluorides and perfluorocarboxylic acid fluorides.
    Type: Grant
    Filed: June 21, 1991
    Date of Patent: October 11, 1994
    Assignee: Mobil Oil Corporation
    Inventors: Costandi A. Audeh, Saverio G. Greco
  • Patent number: 5336832
    Abstract: Refining processes for recovering HF from acid soluble oils (ASO) generated by the HF recovery unit of an HF alkylation unit are provided. ASO containing HF is removed from the HF recovery unit and contacted with water to form a system having two phases, an aqueous HF containing phase and an organic phase. After phase separation, the aqueous HF containing phase passes through a bed of fluidized NaF crystals, where the NaF reacts with the HF to form salts having the general formula NaF.nHF. Flow of the aqueous HF containing phase to the bed continues until exhaustion of the bed, as determined by the detection of HF in the effluent. After exhaustion of the bed, the process provides for the regeneration of the bed and release of anhydrous HF which is then returned to the HF alkylation unit.
    Type: Grant
    Filed: November 6, 1992
    Date of Patent: August 9, 1994
    Assignee: Conoco Inc.
    Inventor: Alfred E. Keller
  • Patent number: 5258568
    Abstract: A single path process for alkylating a hydrocarbon feedstock containing an olefin and an isoparaffin is disclosed. The process includes dispersing an acid-based liquid alkylation catalyst into a reaction zone for contact with a continuous hydrocarbon phase. The process further includes separating the hydrocarbon phase from the acid catalyst upon completion of the alkylation reaction and providing a continuous on-line regeneration of the entire volume of catalyst once it has been separated from the hydrocarbon phase.
    Type: Grant
    Filed: October 23, 1992
    Date of Patent: November 2, 1993
    Assignee: Mobil Oil Corp.
    Inventors: Jonathan E. Child, Tomas R. Melli, Sergei Yurchak
  • Patent number: 5157195
    Abstract: A process and apparatus for recovering propane product from HF alkylation process that is substantially free of HF acid. The invention allows for the improvement in the operation of an HF alkylation propane stripper by utilizing a bottoms recycle stream.
    Type: Grant
    Filed: March 27, 1991
    Date of Patent: October 20, 1992
    Assignee: Phillips Petroleum Company
    Inventors: Keith W. Hovis, Henry K. Hachmuth, Michael L. Gray
  • Patent number: 4777323
    Abstract: A continuous process for alkylating an alkylatable hydrocarbon in the presence of a acid-type catalyst. The reaction product is separated in a first separation zone into an alkylate product phase, located in the upper portion and a catalyst phase located in the lower portion. The catalyst phase is separated into a first portion and second portion, the first portion is cooled and recycled for use in the alkylation reaction zone, and the second portion is passed into a second separation zone, wherein the second portion catalyst phase is further separated into a hot rerun catalyst stream and an acid soluble oil stream. The rerun catalyst stream is passed into the alkylate product phase of the first separation zone. In order to prevent excessive pressure in the first separation zone as a result of the hot rerun catalyst stream, two liquid hydrocarbon drawoffs from the first separation zone are employed.
    Type: Grant
    Filed: July 19, 1985
    Date of Patent: October 11, 1988
    Assignee: Phillips Petroleum Company
    Inventors: Paul D. Hann, Joe Van Pool
  • Patent number: 4677244
    Abstract: An apparatus and method for manipulating the temperature and pressure of the hydrocarbon phase in an acid settler vessel associated with a catalytic alkylation process and apparatus, wherein the hydrocarbon phase in the acid settler vessel is regulated by controlling the amount of rerun catalyst stream entering the hydrocarbon phase of the acid settler vessel. In response to a detected temperature or pressure of the hydrocarbon phase above a set point, the flow of rerun catalyst stream to the hydrocarbon phase of the acid settler vessel is decreased. This decrease in flow to the hydrocarbon phase may be accompanied by an increase in flow of rerun catalyst vapor to the catalyst phase of the acid settler vessel.
    Type: Grant
    Filed: November 29, 1985
    Date of Patent: June 30, 1987
    Assignee: Phillips Petroleum Company
    Inventors: Henry K. Hachmuth, Keith W. Hovis
  • Patent number: 4663026
    Abstract: A process for recovering HF catalyst and acid soluble oil from an HF alkylation unit acid stream containing HF and acid soluble oils. The acid stream is charged to a distillation column, wherein free HF acid, and stripping fluid added to the column, are removed as an overhead fraction. A bottoms fraction is removed from this column containing acid soluble oil and some HF. This bottoms fraction is cooled and mixed with a light hydrocarbon, and the mixture is allowed to settle. The mixture separates into an HF-lean acid soluble oil, plus solvent upper phase and an HF-rich acid soluble oil lower phase. The HF-lean phase may be withdrawn from the process as a product or upgraded to improve its quality, permitting recycle of the HF-rich phase with reduced acid soluble oil content, to the alkylation unit.
    Type: Grant
    Filed: September 4, 1985
    Date of Patent: May 5, 1987
    Assignee: Mobil Oil Corporation
    Inventors: Yuk-Mui Louie, Fred S. Zrinscak
  • Patent number: 4593135
    Abstract: A method for promoting the activity and/or extending the life of a cation-exchangeable layered clay catalyst in reactions susceptible to catalysis by protons which method comprises the addition to the catalyst of water as the sole additive. The quantity of water employed is suitably up to 40%, preferably up to 10% based on weight of reactants. The layered clay catalyst can be for example montmorillonite, bentonite or vermiculite. Suitable proton catalyzed reactions include formation of esters, (e.g. by reaction of olefin and carboxylic acid), ethers, aldehydes, thioethers and alkylation and cracking reactions.
    Type: Grant
    Filed: February 6, 1984
    Date of Patent: June 3, 1986
    Assignee: The British Petroleum Company P.L.C.
    Inventor: Reginald Gregory
  • Patent number: 4404418
    Abstract: A process for maintaining HF acid soluble oils (ASO) in an HF alkylation reaction zone in an amount sufficient to ensure formation of an alkylate containing a high octane number is provided by returning to the reaction zone a portion of acid soluble oil recovered from an HF catalyst rerun system.
    Type: Grant
    Filed: June 4, 1982
    Date of Patent: September 13, 1983
    Assignee: Phillips Petroleum Company
    Inventors: Thomas Hutson, Jr., Paul D. Hann
  • Patent number: 4239931
    Abstract: A process for the hydrofluoric acid-catalyzed alkylation of an isoparaffin with an olefin in a gravity-flow hydrofluoric acid alkylation reaction system. The process is effected without benefit of an acid regenerator. Regeneration is effected an isostripper column, and catalyst-contaminating polymeric products of the alkylation are recovered in the normally liquid alkylate product substantially free of hydrofluoric acid.
    Type: Grant
    Filed: November 5, 1979
    Date of Patent: December 16, 1980
    Assignee: UOP Inc.
    Inventor: Michael Z. Mikulicz