Preparing By Reacting An Olefin And An Organic Hydroxy Containing Compound (h Of -oh May Be Replaced By A Group Ia Or Iia Light Metal) Patents (Class 568/697)
  • Patent number: 5105024
    Abstract: Isobutane and propane are separately charged to different catalytic dehydrogenation zones. The reaction products, including principally propylene and isobutylene, are combined, followed by separation of steam condensate, carbon dioxide and fuel gas from the mixture of effluents from the two separate dehydrogenation reaction zones. Propane and propylene are then separated from the isobutylene. The propylene product is recovered, and isobutylene is charged to an etherification reactor and there reacted with methanol to yield methyltertiarybutyl ether (MTBE). The etherification reactor effluent is fractionated to separate MTBE from n-butane and from isobutane. The latter is separated from n-butane and recycled to the isobutane dehydrogenation zone. Unreacted propane is also recovered and recycled.
    Type: Grant
    Filed: April 20, 1990
    Date of Patent: April 14, 1992
    Assignee: Phillips Petroleum Company
    Inventors: Dwight L. McKay, Michael L. Gray
  • Patent number: 5102428
    Abstract: A process is disclosed for integrating etherification to produce diisopropyl ether (DIPE) with processes to convert oxygenates and hydrocarbons to gasoline boiling range hydrocarbons in a manner which eliminates the requirement to recycle unreacted C.sub.3 hydrocarbons to the DIPE etherification zone. In the novel integrated process the unreacted C.sub.3 hydrocarbons are separated as vapor and passed to a conversion zone in contact with acidic metallosilicate catalyst. Depending on the conversion conditions the unreacted C.sub.3 hydrocarbons are converted to gasoline, distillate and/or aromatics, preferably in conjunction with additional feedstock containing lower oxygenates, olefins or paraffins. Also, isopropanol (IPA) and minor by-product dimers and trimers of propene from the DIPE reaction are separated and passed as a feedstream to the oxygenates and hydrocarbon conversion zone.
    Type: Grant
    Filed: October 20, 1989
    Date of Patent: April 7, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Hartley Owen, Mohsen N. Harandi
  • Patent number: 5100534
    Abstract: An improved process for upgrading paraffinic naphtha to high octane fuel by contacting a naphtha feedstock, such as virgin naphtha feedstock stream containing predominantly C.sub.7 -C.sub.12 alkanes and naphthenes, with solid medium pore acid zeolite cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt % selectivity C.sub.4 -C.sub.5 isoalkene. Cracking effluent is separated to obtain a light olefinic fraction rich in C.sub.4 -C.sub.5 isoalkene and a C.sub.6 + liquid fraction of enhanced octane value containing less than 50 wt % aromatic hydrocarbons. In a multistage operation enhanced octane products are obtained by etherifying the isoalkene fraction and by contacting the C.sub.6 + normally liquid fraction with reforming catalyst under moderate reforming conditions at elevated temperature to obtain a reformate product of enhanced octane value.
    Type: Grant
    Filed: November 6, 1990
    Date of Patent: March 31, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Quang N. Le, Paul H. Schipper, Hartley Owen
  • Patent number: 5100533
    Abstract: Process and apparatus for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream medium pore acid cracking catalyst comprising MCM-22 zeolite under low pressure selective cracking conditions effective to produce increased yield of total C4-C5 branched aliphatic hydrocarbhons. The preferred feedstock is straight run naptha containing C7+ alkanes, at least 15 wt % C7+ cycloaliphatic hydrocarbons and less than 20% aromatics, which can be converted with a fluidized bed catalyst in a vertical riser reactor during a short contact period.The isoalkene products of cracking are etherified to provide high octane fuel components.
    Type: Grant
    Filed: November 1, 1990
    Date of Patent: March 31, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Quang N. Le, Hartley Owen, Paul H. Schipper
  • Patent number: 5095156
    Abstract: A catalyzed, continuous vapor phase process to convert a C.sub.2 or higher alcohol and, optionally, one or more C.sub.1 or higher alcohols, for example methanol and ethanol, to a mixture containing at least one higher molecular weight alcohol, for example, isobutanol, over a catalyst which is essentially magnesium oxide. The process also may have a lower aldehyde and/or ketone in the feed.
    Type: Grant
    Filed: May 20, 1991
    Date of Patent: March 10, 1992
    Assignee: Amoco Corporation
    Inventors: Cecelia A. Radlowski, Gary P. Hagen
  • Patent number: 5091590
    Abstract: A process for upgrading olefin feedstock containing a mixture of iso-olefin and linear olefin to produce tertiary-alkyl ether and high octane gasoline components comprising dimerized iso-olefin. Product recovery is integrated between primary and secondary reaction stages.In a preferred embodiment, a two stage etherification process employs a secondary solid acid regenerable catalyst bed to dimerize unconverted iso-butene in the debutanizer overhead stream of a conventional MTBE primary reactor stage. Both stages can utilize a regenerable acid catalyst such as ZSM-5 or Zeolite Beta for etherification and to upgrade unconverted alkenes and methanol from the primary stage.
    Type: Grant
    Filed: August 22, 1990
    Date of Patent: February 25, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5080691
    Abstract: Light olefins are converted to gasoline with a high enough content of ethers to provide a significant octane improvement over a base (or `cracking`) gasoline (clear RON=90-92; clear MON=79-80). One portion of the olefins is hydrated to produce alcohols, and the other is used to synthesize an olefin-rich gasoline. The alcohols are used to etherify the gasoline. The combination of unit operations minimizes the energy needed to run the process for which no external solvent is needed. The process capitalizes on the higher solubility in gasoline of ethanol, propanol and butanol, compared to methanol. Besides having very low solubility in gasoline, etherification with methanol or ethanol produces an inadequately rewarding increase in octane number, compared to propanol or isopropanol. Taking advantage of the inherent chemical and physical properties of C.sub.3 -C.sub.
    Type: Grant
    Filed: April 4, 1990
    Date of Patent: January 14, 1992
    Assignee: Mobil Oil Corp.
    Inventors: Charles M. Sorensen, Sadi Mizrahi, Samuel A. Tabak
  • Patent number: 5078751
    Abstract: A process is disclosed for upgrading C.sub.5 -C.sub.8 olefin-containing gasoline to a high octane motor gasoline blending component.C.sub.3 -C.sub.4 olefins are hydrated to alcohols and then selectively removed from the aqueous hydration reactor effluent stream via liquid extraction with the gasoline feedstream. The alcohol enriched gasoline extract stream is then etherified and unreacted alcohols are extracted to yield a high octane gasoline blending component free of metal-bearing additives.
    Type: Grant
    Filed: April 4, 1990
    Date of Patent: January 7, 1992
    Assignee: Mobil Oil Corporation
    Inventors: Sadi Mizrahi, Charles M. Sorensen, Samuel A. Tabak
  • Patent number: 5047070
    Abstract: Alcohol feedstock containing water is extracted with olefinic liquid and reacted catalytically to produce tertiary ether. Unreacted alcohol and olefin vapor separated from etherification effluent is converted along with aqueous alcoholic raffinate in a zeolite catalysis step to produce gasoline and paraffinic intermediate. By dehydrogating the C.sub.3 -C.sub.5 paraffins, an olefinic liquid rich in isoalkenes is obtained for recycle to the extractor as solvent for alcohol feedstock.
    Type: Grant
    Filed: May 30, 1989
    Date of Patent: September 10, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5041690
    Abstract: Methanol or other alcohol is converted to high octane gasoline components by an integrated process wherein crude aqueous alcohol feedstock is extracted with a liquid extractant stream containing C.sub.4 +iso-olefin and reacted to form tertiary-alkyl ethers, such as MTBE. The aqueous raffinate is converted to olefinic hydrocarbons in a MTO catalytic reactor. Propene from the MTO reaction is reacted with water to produce di-isopropyl ether, which may be blended with MTBE and C.sub.6 +MTO hydrocarbons to produce high octane gasoline. Isobutylene and isoamylenes from the MTO reaction can be recovered and recycled as a liquid extractant stream.
    Type: Grant
    Filed: August 3, 1990
    Date of Patent: August 20, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5030768
    Abstract: A process for preparing an alkyl-tert-alkyl ether wherein an olefin having a double bond on a tertiary carbon atom and a primary alcohol are reacted in the presence of a catalyst under conditions sufficient to produce an azeotropic alcohol/ether/hydrocarbon mixture containing the alkyl-tert-alkyl ether. The azeotropic alcohol/ether/hydrocarbon mixture is subjected to a cyclic liquid phase adsorption process sequence to selectively remove the alcohol. The resulting non-azeotropic ether/hydrocarbon stream can then be easily separated by distillation to provide the desired alkyl-tert-alkyl ether product and a hydrocarbon product. The cyclic adsorption process employed to separate the alcohol from the ether/hydrocarbon mixture comprises introducing the alcohol/ether/hydrocarbon mixture into a plurality of adsorption colums containing an alcohol selective adsorbent, wherein each respective absorption column undergoes successive steps of adsorption and desorption.
    Type: Grant
    Filed: March 30, 1990
    Date of Patent: July 9, 1991
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Michael S. Chen, Shivaji Sircar
  • Patent number: 5026529
    Abstract: Improved operating techniques and apparatus for converting methanol or the like to intermediate olefins and etherification products, such as methyl t-butyl ether, by extracting crude methanol feedstock with an olefinic liquid hydrocarbon stream containing C.sub.4.sup.+ iso-olefins. The methanol extract phase is reacted under etherification conditions. The aqueous methanol raffinate stream is converted catalytically to olefins for recovery of C.sub.4.sup.+ olefinic liquid hydrocarbons useful as extraction solvent.
    Type: Grant
    Filed: January 17, 1989
    Date of Patent: June 25, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5024679
    Abstract: An integrated process for the production of ether-rich liquid fuels containing MTBE and TAME by etherifying a hydrocarbon feedstock containing C.sub.4 + isoalkenes in the presence of a high stoichiometric excess of lower alkyl alcohol. Unreacted alcohol and olefins are passed to a zeolite catalyzed conversion reactor under olefinic and oxygenates conversion condition whereby gasoline and light hydrocarbons are produced. The light hydrocarbon fraction comprising C.sub.4 -C.sub.5 paraffins is dehydrogenated and C.sub.4 -C.sub.5 olefins are recycled to the etherification reactor.
    Type: Grant
    Filed: February 15, 1990
    Date of Patent: June 18, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5015782
    Abstract: A process for preparing lower molecular weight unsymmetrical ethers such as methyl t-butyl (MTBE) and t-amyl methyl ether (TAME) from an iso-olefin and methanol, the process comprising a preliminary step of contacting the iso-olefin and methanol with a medium-pore zeolite conversion catalyst in at least one reaction zone under conditions sufficient to convert the iso-olefin and methanol to an unsymmetrical ether and then feeding effluent from the preliminary step to an etherification reaction zone containing a macroreticular polystyrenesulfonic acid resin catalyst.
    Type: Grant
    Filed: March 19, 1990
    Date of Patent: May 14, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5015783
    Abstract: Processes for the production of ethers from alcohols and isoolefins are disclosed. Isoolefins having four to five carbon atoms per molecule are combined with a monohydroxy alcohol having from one to five carbon atoms per molecule and with a recycle stream comprising alcohol and water to form an etherification zone feed stream which is passed through an etherification zone to produce the desired ether. The effluent from the etherification zone is separated into an ether product and an aqueous product containing unreacted alcohol which is recycled to provide a portion of the etherification zone feed stream. Distillation can be employed to separate the effluent from the etherification zone into a bottoms product stream, comprising the ether, a distillate product comprising other hydrocarbons and the above-mentioned recycle stream. When producing ethyl-tertiary-butyl ether (ETBE), azeotropic grade ethanol, i.e., about 5 vol. % water, is preferably utilized.
    Type: Grant
    Filed: December 4, 1989
    Date of Patent: May 14, 1991
    Assignee: UOP
    Inventors: Bipin V. Vora, Peter R. Pujado, Charles P. Luebke
  • Patent number: 5013329
    Abstract: A process is disclosed for converting a light hydrocarbon feedstock that contains a mixture of linear and branched olefins to ether-rich high octane gasoline streams that include tertiary alkyl and isoalkyl ethers such as MTBE, TAME, methyl isopropyl ether (MIPE), and methyl sec-butylether (MSBE). The conversion is achieved by utilizing the differing reactivity of tertiary olefins under selected conditions compared to linear olefins in the catalyzed etherification processes. The discovery has been made that unreacted olefins from the etherification reactions can be converted to gasoline boiling range hydrocarbons by contacting them with zeolite catalyst at elevated temperature. Further, it has been discovered that unreacted paraffins in the integrated process can be dehydrogenated to produce C.sub.3 -C.sub.4 olefins which can be recycled to the etherification process.
    Type: Grant
    Filed: March 31, 1989
    Date of Patent: May 7, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Weldon K. Bell, Werner O. Haag, Mohsen N. Harandi, Hartley Owen
  • Patent number: 5011506
    Abstract: A method is disclosed combining the process for the hydration or etherification of light linear olefins, such as the production of diisopropyl ether (DIPE), with the process for the etherification of C.sub.4 + or C.sub.4 hydrocarbons containing isobutylene to produce alkyl tertiary butyl ether or ether-rich gasoline in a manner which effectively dewaters alkanol using the iso-olefin hydrocarbon feedstream as extractant. The combined process leads to the production of isopropyl tert-alkyl ethers. In the integrated process the high octane ethers produced may include methyl tert-butyl ether, methyl tert-amyl ether, isopropyl tert-butyl ether and diisopropyl ether. The process also results in the production of a gasoline stream rich in high octane ethers.
    Type: Grant
    Filed: September 29, 1989
    Date of Patent: April 30, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 5008468
    Abstract: This invention provides an improved process for the conversion of reactant into a reaction product, in the presence of a solid acid catalyst comprising sulfonic acid groups covalently bonded to a polymeric chain, wherein the improvement comprises increasing the rate of conversion, on an equivalent sulfonic acid basis, by providing, as said polymeric chain a compound represented by the general formula:M(O.sub.3 ZO.sub.x R).sub.nwherein M is a tetravalent metal ion; Z is a pentavalent atom, selected from the group consisting of elements of Group V of the Periodic Table of the Elements having an atomic weight greater than 30; x varies from 0 to 1; R is select d from the group consisting or organo radicals and mixtures of hydrogen radicals and organo radicals; and n varies from 1 to 2; provided that n is 1 when R is terminated with a tri- or tetraoxy pentavalent atom.
    Type: Grant
    Filed: August 21, 1989
    Date of Patent: April 16, 1991
    Assignee: Catalytica, Inc.
    Inventors: David L. King, Michael D. Cooper, Michael A. Faber
  • Patent number: 5008467
    Abstract: An integrated process of producing MTBE by the dehydrogenation of isobutane and the etherification of the resulting isobutene with methanol is simplified by directly charging the effluent of a dehydrogenation zone without prior separation to an etherification zone arranged to provide countercurrent contact of isobutene and the methanol reactants such that an MTBE product is recovered as a bottoms stream and a relatively isobutene-free overhead stream is recycled to the dehydrogenation zone. Overall separation facilities are simplified by only separating C.sub.3 hydrocarbons from the etherification zone product stream. This arrangement eliminates C.sub.3 separation facilities ahead of the etherification zone and reduces the quantity of C.sub.4 hydrocarbons that are received by the separation zone. The reaction zone may contain a series of beds arranged to further eliminate the carry over of isobutene to the separation facilities. This arrangement also allows a recovery of unreactive or unreacted C.sub.
    Type: Grant
    Filed: December 4, 1989
    Date of Patent: April 16, 1991
    Assignee: UOP
    Inventors: Bipin V. Vora, Norman H. Scott
  • Patent number: 5008465
    Abstract: The invention relates to the use of hydrogen ion-exchanged layered clays in organic reactions which are catalyzed by protons. Such organic reactions include the production of ethers by the reaction of an alcohol with an olefin or an olefin oxide, the production of an ether by the reaction of a primary or secondary aliphatic alcohol or an olefin oxide, the production of an alkyl aromatic compound by the reaction of an aromatic hydrocarbon with an olefin or a C.sub.2 or higher alcohol and the production of an alcohol by the hydration of an olefin.
    Type: Grant
    Filed: May 17, 1990
    Date of Patent: April 16, 1991
    Assignee: The British Petroleum Company p.l.c.
    Inventors: James A. Ballantine, Reginald Gregory, John H. Purnell, John M. Thomas, David J. Westlake
  • Patent number: 5008466
    Abstract: Alkenes having a terminal double bond can be isomerized to give alkenes having an internal double bond if alkenes having a terminal double bond or hydrocarbon feedstock having a content of alkenes of this type having a terminal double bond are subjected to treatment, in the presence of hydrogen, over a macroporous or gel-like cation exchanger in the H.sup.+ form which contains 0.001 to 10 g of one or more metals of the VIth and/or VIIth and/or VIIIth sub-group of the periodic system of the elements in elementary form per liter of dry cation exchanger and which has a degree of crosslinking of 2 to 65% and a specific surface area of 5 to 750 m.sup.2 /g of dry exchange resin. The treatment is carried out in the liquid phase at a temperature from 0.degree. to 120.degree. C.
    Type: Grant
    Filed: April 12, 1989
    Date of Patent: April 16, 1991
    Assignee: EC Erdolchemie GmbH
    Inventors: Bernhard Schleppinghoff, Hans-Dieter Kohler, Christian Gabel, Hans-Volker Scheef
  • Patent number: 5003112
    Abstract: A method is disclosed for the preparation of tertiary amyl methyl ether by reaction of methanol and a C-5 olefin over a catalyst comprising an acidic smectite clay, particularly a palladium-modified acidic montmorillonite silica-alumina clay. The method allows for high conversions with yields of up to 93-99 mole %. Further the method is capable of operating efficiently at high LHSVs.
    Type: Grant
    Filed: January 2, 1990
    Date of Patent: March 26, 1991
    Assignee: Texaco Chemical Company
    Inventor: John F. Knifton
  • Patent number: 5001292
    Abstract: An integrated process is disclosed that substantially reduces the cost of producing MTBE and other alkyl tert-alkyl ethers by eliminating a major portion of the equipment and operating costs associated with the downstream processing of the etherification reactor effluent. The integrated process combines the process for the etherification of isoolefins and methanol, or other alkanols, to produce methyl tertiary alkyl ethers such as MTBE and/or TAME with the catalytic process for converting feedstock such as oxygenates, light olefins and paraffins to higher molecular weight hydrocarbons. Unconverted reactants from the etherification reaction, which may comprise unreacted alkanol and unreacted hydrocarbons or just unreacted hydrocarbons, are separated from the product ethers and passed to the catalytic conversion process reactor for conversion to gasoline boiling range hydrocarbons.
    Type: Grant
    Filed: October 16, 1989
    Date of Patent: March 19, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4990712
    Abstract: Gasoline octane number and yield are improved while excess fuel gas production is decreased in a catalytic cracking process by integrating etherification and oxygenate/aliphatic upgrading processes into the catalytic cracking unit product fractionation section.
    Type: Grant
    Filed: May 18, 1990
    Date of Patent: February 5, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4988366
    Abstract: Isopentene, or isoamylene, conversion to methyl tert-amyl ether can be substantially improved while high conversion of isobutylene to methyl tert-butyl ether can be maintained by carrying out the overall etherification process with alkanol in a staged manner, wherein the first stage is methanol etherification of a C.sub.5 +, or C.sub.5, hydrocarbon feedstream rich in isoamylene and the second stage is etherification to produce MTBE and additional TAME from a C.sub.4 +, or C.sub.4, feedstream. Unreacted methanol and hydrocarbons from the first etherification are uniquely separated by fractionation from the TAME product by using the second stage C.sub.4 + feedstream as a reflux stream to the fractionator and passed to the second etherification zone. Products from the second etherification zone are separated by distillation to produce MTBE, TAME and C.sub.5 +, or C.sub.5, hydrocarbons as a bottom stream.
    Type: Grant
    Filed: October 24, 1989
    Date of Patent: January 29, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4981491
    Abstract: Methanol or other alcohol is converted to high octane gasoline components by an integrated process wherein crude aqueous alcohol feedstock is extracted with a liquid extractant stream containing C.sub.4.sup.+ iso-olefin and reacted to form tertiary-alkyl ethers, such as MTBE. The aqueous raffinate is converted to predominantly gasoline range liquid hydrocarbons in a MTG catalytic reactor, with byproduct alkanes rich in propane and isobutane. Dehydrogenation of C.sub.3 -C.sub.5 alkanes from the MTG unit provides propene and isobutene reactants for subsequent etherification steps. Propene from the MTG dehydrogenation step is reacted with water to produce di-isopropyl ether, which may be blended with MTBE and C.sub.6.sup.+ MTG hydrocarbons to produce high octane gasoline. Isobutylene and isoamylenes from the MTG dehydrogenation step can be removed and recycled as a liquid extractant stream.
    Type: Grant
    Filed: July 28, 1989
    Date of Patent: January 1, 1991
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4978807
    Abstract: A method and apparatus for conducting a catalytic distillation process is provided which allows for maintaining a liquid level in selected portions of the catalyst bed. Three particular processes disclosed are the production of methyl tertiary butyl ether, tertiary butyl alcohol and cumene. A method for the production of methyl tertiary butyl ether by reaction of isobutene with methanol in a distillation reaction column is disclosed wherein a liquid level maintained in the distillation reaction zone.
    Type: Grant
    Filed: June 29, 1989
    Date of Patent: December 18, 1990
    Assignee: Chemical Research & Licensing Company
    Inventor: Lawrence A. Smith, Jr.
  • Patent number: 4975097
    Abstract: A technique for converting olefinic light hydrocarbons to ether-rich liquid fuels and olefinic gasoline including etherification, olefin upgrading and transhydrogenation operations. The preferred process includes: reacting a fresh hydrocarbon stream containing C.sub.4 + iso-alkene with lower aliphatic alcohol in an etherification zone in contact with an acidic etherification catalyst under etherification conditions whereby an effluent stream containing C5+ tertiary-alkyl ether is produced; separating the etherification effluent stream to provide a first liquid stream comprising C5+ ether and a second stream comprising unreacted alcohol and C4+ hydrocarbons; contacting the second stream with acidic metallosilicate catalyst for conversion of oxygenates and olefins under olefin oligomerization and isomerization conditions at elevated temperature; separating oligomerization effluent to recover an intermediate hydrocarbon stream rich in C.sub.
    Type: Grant
    Filed: December 21, 1989
    Date of Patent: December 4, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4969987
    Abstract: Process and apparatus for upgrading paraffinic naphtha to high octane fuel by contacting a fresh virgin naphtha feedstock stream medium pore acid cracking catalyst under low pressure selective cracking conditions effective to produce at least 10 wt % C4-C5 isoalkene to obtain a light olefinic fraction rich in C4-C5 isoalkene and a C6+ liquid fraction of enhanced octane value. The preferred feedstock is straight run naphtha containing C7+ alkanes, at least 15 wt % C7+ cycloaliphatic hydrocarbons and less than 20% aromatics, which can be converted with a fluidized bed catalyst in a vertical riser reactor during a short contact period.The isoalkene products of cracking are etherified to provide high octane fuel components.
    Type: Grant
    Filed: November 29, 1989
    Date of Patent: November 13, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Q. N. Le, H. Owen, P. H. Schipper
  • Patent number: 4962239
    Abstract: Olefin is etherified with alcohol to provide an ether or mixture of ethers employing catalyst comprising zeolite characterized by an X-ray diffraction pattern including interplanar d-spacings at 12.36+0.4, 11.03+0.2, 8.83.+-.0.14, 6.18.+-.0.12, 6.00.+-.0.10, 4.06.+-.0.07, 3.91.+-.0.07 and 3.42.+-.0.06 Angstroms.
    Type: Grant
    Filed: December 26, 1989
    Date of Patent: October 9, 1990
    Assignee: Mobil Oil Corp.
    Inventors: Weldon K. Bell, Werner O. Haag, David O. Marler
  • Patent number: 4954660
    Abstract: Linear olefins are converted into the corresponding secondary alcohols by treatment with methyl alcohol and a tertiary alcohol, in the presence of an acidic catalyst, at a temperature ranging from 120.degree. to 200.degree. C. The product mixture substantially consists of the desired secondary alcohol and of the methyl ether of the charged tertiary alcohol.The reaction products can be easily isolated by fractionation, or, in some instances, the liquid product mixture can be used as such.Of particular interest is the direct hydration of n-butenes using tert-butyl alcohol as the tertiary alcohol. The obtained product mixture can be used as such, as an additive to methanol-containing gasolines for internal combustion engines.
    Type: Grant
    Filed: October 28, 1988
    Date of Patent: September 4, 1990
    Assignee: Enichem Anic S.p.A.
    Inventors: Giuseppe Messina, Carmelo Nurra, Oscar Cappellazzo, Angelo Virdis, Loreno Lorenzoni
  • Patent number: 4950803
    Abstract: A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.
    Type: Grant
    Filed: June 1, 1987
    Date of Patent: August 21, 1990
    Assignee: Chemical Research & Licensing Company
    Inventors: Lawrence A. Smith, Jr., Dennis Hearn, Edward M. Jones, Jr.
  • Patent number: 4935552
    Abstract: Light olefins are catalytically converted to ethers, e.g., propylene is converted to diisopropyl ether, in a dual stage process in which product ether is recycled to a first stage reaction zone to significantly reduce the operating temperature of the olefin hydration/etherification reactions taking place in that zone. Alcohol produced in the first stage reaction zone undergoes conversion in the second stage reaction zone, e.g., by etherification with light olefin or by catalytic distillation, to provide additional product ether. The process contemplates the use of zeolites as olefin hydration/etherification catalysts.
    Type: Grant
    Filed: January 12, 1989
    Date of Patent: June 19, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Jonathan E. Child, Byung C. Choi, Francis P. Ragonese
  • Patent number: 4927977
    Abstract: A process and apparatus are provided for the substantially uniform distribution of a two-phase feed in a chemical reaction zone. As applied, for example, to the hydration/etherification of light olefin to alcohol(s) and/or ether(s), the invention results in greater process control and in particular cases, to improved reaction product selectivities.
    Type: Grant
    Filed: January 12, 1989
    Date of Patent: May 22, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Jonathan E. Child, Byung C. Choi, Francis P. Ragonese
  • Patent number: 4925455
    Abstract: A process is disclosed for converting a light hydrocarbon feedstock that contains a mixture of linear and branched olefins to ether-rich high octane gasoline streams that include tertiary alkyl and isoalkyl ethers such as MTBE, TAME, methyl isopropyl ether (MIPE), and methyl sec-butylether (MSBE). Further, it has been discovered that, following etherification unreacted paraffins in the process can be dehydrogenated to produce C.sub.3 -C.sub.4 olefins which can be recycled to the etherification process. The conversion is achieved by utilizing the differing reactivity of tertiary olefins under selected conditions compared to linear olefins in the catalyzed etherification processes. The process integrates a first stage tertiary olefin etherification, separation of ether-rich gasoline and a second stage linear olefin etherification to produce a second ether rich gasoline stream.
    Type: Grant
    Filed: March 17, 1989
    Date of Patent: May 15, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4925989
    Abstract: A process for preparing methyl tertiary-butyl ether wherein tertiary-butyl alcohol, isobutylene and methanol are continuously fed into a combination reactor distillation tower having a packed sulfonic acid resin catalyst beds where a substantially pure product of MTBE methyl tertiary-butyl ether is produced.
    Type: Grant
    Filed: June 1, 1987
    Date of Patent: May 15, 1990
    Assignee: Texaco Inc.
    Inventors: John J. Hagan, Sheldon Herbstman
  • Patent number: 4918243
    Abstract: A portion of the best of vaporization, required to separate and recover methanol from wash water used to remove methanol from a C.sub.4 raffinate resulting from the reaction of isobutene containing C.sub.4 hydrocarbons and methanol to produce MTBE is recovered by conducting the distillation of the methanol/water mixture at a pressure of 40 to 60 psig, thereby increasing the temerature of the methanol overhead to 104.degree. to 114.degree. C. and using the reaction effluent from the MTBE reactor to cool and condense the methanol overhead, said reactor effluent being correspondingly heated prior to entry into a debutanizer tower where unreacted C.sub.4 's and methanol are removed as a raffinate and MTBE product recovered. It is this raffinate that is washed with water to recover the unreacted methanol, with the methanol/water mixture being distilled as set forth above.
    Type: Grant
    Filed: October 28, 1988
    Date of Patent: April 17, 1990
    Assignee: Chemical Research & Licensing Company
    Inventors: Lawrence A. Smith, Jr., Edward M. Jones, Jr., Dennis Hearn
  • Patent number: 4906787
    Abstract: Olefins undergo conversion in the presence of water and recycled alcohol to a mixture of alcohol and ether which is then subjected to various downstream operations including distillation and extraction or decantation to provide an ether-rich product containing little if any alcohol or water. The foregoing process is especially suitable to the conversion of propylene and propylene-containing streams to diisopropyl ether which is useful, inter alia, as an octane improver for gasoline.
    Type: Grant
    Filed: December 30, 1987
    Date of Patent: March 6, 1990
    Assignee: Mobil Oil Corporation
    Inventors: Tracy J. Huang, Charles M. Sorensen, Philip Varghese
  • Patent number: 4906788
    Abstract: A combined process for the dehydrogenation of C.sub.4 -C.sub.5 paraffins in a first zone and the etherification of olefins in a second zone improves efficiency by directly charging all but the lightest components of the dehydrogenation zone effluent to the etherification zone. This process is particularly suited for the production of gasoline boiling range ethers where an isoparaffin is dehydrogenated in a first zone to produce isoolefins. After separation of hydrogen and methane, the dehydrogenation zone effluent is charged along with methanol to an etherification zone for the production of MTBE. The etherification zone effluent is separated into at least three component streams comprising light ends, isoparaffins, and the ether product. Isoparaffins, separated from the etherification zone effluent, are recycled and combined with the feed to dehydrogenation zone.
    Type: Grant
    Filed: October 26, 1988
    Date of Patent: March 6, 1990
    Assignee: UOP
    Inventors: Norman H. Scott, Bipin V. Vora
  • Patent number: 4886918
    Abstract: Light olefin is introduced at multiple points of entry into a conversion unit subdivided into first and second reaction zones. Reaction of olefin with water takes place in the first reaction zone under conditions intended to promote the production of alcohol therein and in the second reaction zone, alcohol produced in the first reaction zone is both dehydrated and reacted with olefin under conditions intended to promote the production of ether therein. The same or different shape selective acidic zeolites are employed as catalysts in both reaction zones.
    Type: Grant
    Filed: May 3, 1989
    Date of Patent: December 12, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Charles M. Sorensen, Philip Varghese
  • Patent number: 4886925
    Abstract: An integrated process is disclosed for the conversion of C.sub.2 + normal olefins into methyl tertiaryalkyl ethers and high octane gasoline. The process combines olefins interconversion with etherification and conversion of unreacted methanol and olefins in contact with acidic, shape selective metallosilicate zeolite catalyst.
    Type: Grant
    Filed: May 2, 1988
    Date of Patent: December 12, 1989
    Inventor: Mohsen N. Harandi
  • Patent number: 4876394
    Abstract: In the production of methyl tert.-alkyl ethers by the reaction of methanol with isoalkylenes, the formation of dimethyl ether as an undesirable reaction by-product is reduced by recycling dimethyl ether to the reactor, advantageously in amounts sufficient to establish an equilibrium between the amount of dimethyl ether imparted to the reactor by way of recycle and the amount of dimethyl ether leaving the reactor as a portion of the reaction product whereby the formation of dimethyl ether in the reactor is essentially nil. In the present invention the essential recycle of dimethyl ether is accomplished by providing an adsorption capacity for dimethyl ether in the adsorption unit for recovering unreacted methanol and recycling dimethyl ether in combination with recycled methanol to the reactor as an effluent from the methanol adsorption unit during regeneration with isobutylene-containing C.sub.4 hydrocarbon feedstock.
    Type: Grant
    Filed: June 29, 1988
    Date of Patent: October 24, 1989
    Assignee: UOP
    Inventors: Moez M. Nagji, Robert E. Trubac
  • Patent number: 4868343
    Abstract: This invention provides an improved process for the conversion of reactant into a reaction product, in the presence of a solid acid catalyst comprising sulfonic acid groups covalently bonded to a polymeric chain, wherein the improvement comprises increasing the rate of conversion, on an equivalent sulfonic acid basis, by providing, as said polymeric chain a compound represented by the general formula:M(O.sub.3 ZO.sub.x R).sub.nwherein M is a tetravalent metal ion; Z is a pentavalent atom, selected from the group consisting of elements of Group V of the Periodic Table of the Elements having an atomic weight greater than 30; x varies from 0 to 1; R is selected from the group consisting of organo radicals and mixtures of hydrogen radicals and organo radicals; and n varies from 1 to 2; provided that n is 1 when R is terminated with a tri-or tetraoxy pentavalent atom.
    Type: Grant
    Filed: April 16, 1986
    Date of Patent: September 19, 1989
    Assignee: Catalytica Inc.
    Inventors: David L. King, Michael D. Cooper, Michael A. Faber
  • Patent number: 4868342
    Abstract: A process for the production of propylene and high octane blending components from C.sub.3 and C.sub.4 hydrocarbons that provides the dual benefit of flexibility between alkylate and propylene products while allowing the processing of large amounts of normal butane. The process includes the steps of passing a combined feed of C.sub.3 and C.sub.4 hydrocarbons to a dehydrogenation zone, contacting the feed stream with a dehydrogenation catalyst, and recovering an effluent containing C.sub.3 and C.sub.4 olefins and admixing the effluent with another feed comprising paraffins and olefins having from 3-4 carbon atoms and recovering an intermediate stream. The intermediate stream enters a separation zone, which removes C.sub.2 hydrocarbons and lower boiling materials from the process, recovers a first propylene product stream, produces an alkylation zone feed stream containing C.sub.3 and C.sub.4 hydrocarbons, and produces a recycle stream.
    Type: Grant
    Filed: March 4, 1988
    Date of Patent: September 19, 1989
    Assignee: UOP
    Inventor: Ronald L. Verson
  • Patent number: 4866211
    Abstract: Steam active reforming catalyst is described which in addition to converting isoparaffins to isoolefins also isomerizes 1-olefins at least in part to internal olefins. In a combined steam active reforming and ether forming operation a 1-olefin containing stream can be recycled to the steam active reforming zone whereby this 1-olefin is converted to materials which in a separation step downstream from the ether forming reaction can be readily separated from the isoparaffin, the isolefin and the 1-olefin which are recycled to the steam active reforming zone. The steam active reforming catalyst thus has both the function of a reforming (dehydrogenation) catalyst and that of an isomerization catalyst for disposing of the 1-olefin byproduct and preventing its buildup in the operation.
    Type: Grant
    Filed: February 10, 1987
    Date of Patent: September 12, 1989
    Assignee: Phillips Petroleum Company
    Inventors: Francis M. Brinkmeyer, Donald F. Rohr, Jr.
  • Patent number: 4857664
    Abstract: Olefin undergoes conversion in the presence of water to a mixture of alcohol and ether which is then subjected to various downstream operations including distillation and decantation to provide an ether-rich product containing little if any water. If desired the ether can be combined in any predetermined ratio with co-produced alcohol to provide alcohol/ether mixtures of desired composition. The foregoing process is especially suitable to the conversion of propylene and propylene-containing streams to diisopropyl ether and mixtures of isopropyl alcohol and diisopropyl ether which are useful, inter alia, as octane improves for gasoline.
    Type: Grant
    Filed: October 27, 1988
    Date of Patent: August 15, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Tracy J. Huang, Rene B. LaPierre, Samuel A. Tabak
  • Patent number: 4847430
    Abstract: The invention concerns a process for manufacturing methyl tert-butyl ether (MTBE) by reacting methanol with an isobutene-containing hydrocarbon mixture.This process is characterized by the steps of:introducing the reactants into a reaction-distillation zone containing at least two superposed and non-contiguous fixed beds (2a, 2b) of catalyst of the sulfonated resin type, wherein passage-ways are provided for a vapor phase, at least one distillation tray (4a), at least one liquid redistribution tray (5),maintaining distillation conditions in said zone so as to have a descending liquid phase and an ascending vapor phase,maintaining a continuous liquid phase in the lower part of said beds,discharging a vapor phase containing a high proportion of unconverted hydrocarbons from the top (8) of said zone, andwithdrawing a liquid phase of high MTBE content from the bottom (10) of said zone.
    Type: Grant
    Filed: March 21, 1988
    Date of Patent: July 11, 1989
    Assignees: Institut Francais Du Petrole, Elf France
    Inventors: Dang Vu Quang, Pierre Amigues, Jean-Ferdinand Gaillard, Jacques Leonard, Jean-Luc Nocca
  • Patent number: 4835329
    Abstract: An integrated process for the production of alkylate and etherate rich high octane gasoline streams comprising the etherification to produce MTBE and TAME in the presence of a high stoichiometric excess of methanol followed by the conversion of unreacted methanol in contact with zeolite-type catalyst in the presence of aromatics to produce alkylated aromatics in gasoline. The light paraffinic effluent from the methanol conversion zone is reacted in contact with zeolite catalyst under aromatization conditions to produce an aromatics feedstream for the methanol conversion reaction. A supplemental olefinic feedstream is provided to the methanol conversion zone after optionally serving as stripping medium for the separation of methanol and etherate-rich C.sub.5 + gasoline from the etherification reaction.
    Type: Grant
    Filed: December 8, 1987
    Date of Patent: May 30, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4830635
    Abstract: An etherification process for reacting a hydrocarbon mixture containing C.sub.4 -C.sub.7 iso-olefins with excess methanol to produce tertiary alkyl methyl ethers. The improved technique comprises operations for separating etherification reaction effluent to recover a liquid fraction rich in gasoline range unreacted hydrocarbons in mixture with liquid ether product, recovering from the reaction effluent a vapor fraction rich in unreacted light olefin including C.sub.4 -C.sub.5 olefins and unreacted methanol, and converting or interconverting a major portion of the light olefin to C.sub.4 + olefins and/or oligomerization products while substantially completely converting the unreacted methanol to an acid zeolite catalysis conversion product comprising olefins and normally liquid hydrocarbon product. A portion of the conversion product is recycled to the etherification process.
    Type: Grant
    Filed: December 8, 1987
    Date of Patent: May 16, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen
  • Patent number: 4831195
    Abstract: Processes and apparatus for converting methanol or the like to intermediate olefins and etherification products, such as methyl t-butyl ether by extracting crude methanol feedstock with an olefinic liquid hydrocarbon stream containing C.sub.4 + iso-olefins. The extract phase is reacted under etherification conditions. The aqueous methanol raffinate stream is converted catalytically to olefins for recovery of C.sub.4 + olefinic liquid hydrocarbons useful as extraction solvent.
    Type: Grant
    Filed: November 24, 1987
    Date of Patent: May 16, 1989
    Assignee: Mobil Oil Corporation
    Inventors: Mohsen N. Harandi, Hartley Owen