WO1990008120A1 - Procede de conversion d'olefines en alcools et/ou en ethers - Google Patents

Procede de conversion d'olefines en alcools et/ou en ethers Download PDF

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Publication number
WO1990008120A1
WO1990008120A1 PCT/US1990/000135 US9000135W WO9008120A1 WO 1990008120 A1 WO1990008120 A1 WO 1990008120A1 US 9000135 W US9000135 W US 9000135W WO 9008120 A1 WO9008120 A1 WO 9008120A1
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Prior art keywords
zeolite
olefin
zsm
alcohol
water
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PCT/US1990/000135
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English (en)
Inventor
David Owen Marler
Charles Mitchel Sorensen, Jr.
Philip Varghese
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Mobil Oil Corporation
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Publication of WO1990008120A1 publication Critical patent/WO1990008120A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof

Definitions

  • This invention relates to a process for the catalytic conversion of olefins to provide alcohols, ethers and their mixtures useful, inter alia , as high octane blending stocks for gasoline.
  • Lower molecular weight alcohols and ethers such as isopropyl alcohol (IPA) and diisopropyl ether (DIPE) are in the gasoline boiling range and are known to have a high blending octane number.
  • IPA isopropyl alcohol
  • DIPE diisopropyl ether
  • by-product propylene from which IPA and DIPE can be made is usually available in a fuels refinery.
  • the petrochemicals industry also produces mixtures of light olefin streams in the C_ to C_ molecular weight range and the conversion of such streams or fractions thereof to alcohols and/or ethers can also provide products useful as solvents and as blending stocks for gasoline.
  • lower olefins in particular, propylene
  • a zeolite catalyst having a silica to alumina molar ratio of at least 12 and a Constraint Index of 1-12, e.g. ZSM-5, to provide the corresponding alcohol, essentially free of ether and hydrocarbon by-product.
  • an olefin is hydrated to the corresponding alcohol in the presence of hydrogen ordenite or hydrogen zeolite Y having a molar ratio of 20-500.
  • the use of such a catalyst is said to result in higher yields of alcohol than olefin hydation processes which employ conventional solid acid catalysts.
  • Use of the catalyst is also said to offer the advantage over ion-exchange type olefin hydration catalysts of nc . being restricted by the hydration temperature.
  • U.S. Patent No 4783S55 describes an olefin hydra ion process employing a medium pore zeolite as hydration catalyst. Specific cataysts mentioned are theta-1, ferrierite, ZSM-22, ZSM-23 and Nu-10
  • U.S. Patent No. 4,042,633 discloses the preparation of diisopropyl ether (DIPE) from i ⁇ opropyl alcohol (IPA) employing a montmorillonite clay catalyst, optionally in the presence of added propylene.
  • DIPE diisopropyl ether
  • a mixed C stream containing isobutylene is reacted with . aqueous ethanol to form a mixture of ethyl tertiary butyl ether (ETBE) and tertiary butyl alcohol (TBA) .
  • EBE ethyl tertiary butyl ether
  • TSA tertiary butyl alcohol
  • U.S. Patent No. 4,418,219 discloses a process for preparing methyl tertiary butyl ether (MTBE) by reacting isobutylene and methanol in the presence of boron phosphate, blue tungsten oxide or a crystalline aluminosilicate zeolite having a silica to alumina mole ratio of at least 12:1 and a Constraint Index of from 1 to 12 as catalyst.
  • MTBE methyl tertiary butyl ether
  • alkyl tert- alkyl ethers such as MTBE and tertiary a yl methyl 5 ether (TAME) are prepared by the reaction of a primary alcohol with an olefin having a double bond on a tertiary carbon atom employing as catalyst an acidic zeolite having a Constraint Index of from 1 to 12, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23 dealuminized zeolite Y and rare 10 earth-exchanged zeolite Y.
  • TAME tertiary a yl methyl 5 ether
  • U.S. Patent No. 4,714,787 discloses the preparation of ethers by the catalytic reaction of linear monoolefins with primary or secondary alcohols employing, as a catalyst, a zeolite having a pore size greater than 5 15 Angstroms, e.g., ZSM-5, zeolite Beta, zeolite X and zeolite Y.
  • a zeolite having a pore size greater than 5 15 Angstroms e.g., ZSM-5, zeolite Beta, zeolite X and zeolite Y.
  • MIPE methyl isoopropyl ether
  • an olefin is reacted with an alcohol - ⁇ to provide an ether, e.g., isobutene and methanol are reacted to provide MTBE, in the presence of an acidic zeolite such as zeolite Beta, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-48, as a catalyst.
  • an acidic zeolite such as zeolite Beta, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-48, as a catalyst.
  • zeolite catalyst 30 It is a common practice in zeolite catalyst 30 manufacture to extrude the active zeolite component with an inorganic oxide binder component such as alumina.
  • the binder serves as a matrix for the zeolite and facilitates the extrusion process resulting in a composite product possessing good mechanical strength.
  • the binder component contributes little to the observed catalytic activity and can be regarded as an inert diluent for the catalytically active zeolite component.
  • the activity and selectivity of zeolite catalysts used in olefin hydration/etherification may be significantly influenced by the nature of the binders with which the zeolites are composited.
  • the invention resides in a process for converting an olefin to an alcohol and/or an ether comprising reacting the olefin with water and/or an alcohol in the presence of a catalyst comprising a zeolire and a refractory binder comprising a metal of Group IVA and/or IVB of the Periodic Table of Elements.
  • the present invention is applicable to the conversion of individual light olefins and mixtures of olefins of various structures, preferably within the C_. range. Accordingly, the invention is applicable to the conversion of ethylene, propylene, butene ⁇ , pentenes, hexenes, heptenes, mixtures of these and other olefins such as gas plant, off-gas containing ethylene and • -. - * . propylene, naphtha cracker off-gas containing light olefins, fluidized catalytic cracked (FCC) light gasoline containing pentenes, hexenes and heptenes, and refinery- FCC propane/propylene streams.
  • a typical FCC light olefin stream possesses the following composition:
  • the process of the invention is especially applicable to the conversion of propylene and propylene-containing streams to mixtures of IPA and DIPE.
  • the reaction can be regarded as one of hydration although, of course, some product alcohol can, and does, react with the olefin feed to co-produce ether.
  • the reaction can be regarded as one of etherification.
  • the resulting conversion involves both hydration and etherification reactions.
  • other reactions such as the chemical dehydration of alcohol to ether may occur to some extent.
  • Lower alcohols which are suitable for reaction with light olefins herein, optionally together with water, include alcohols having from 1 to 6 carbon atoms, i.e., methanol, ethanol, propanol, isopropyl alcohol, n-butanol, tert-butanol, the pentanols and the hexanols.
  • the operating conditions of the improved olefin conversion process herein are not especially critical. They include a temperature ranging from ambient (20°C) to 300°C, preferably from 50 to 220°C and more preferably from 100 to 200°C, a total system pressure of at least 5 atm (500kPa) , preferably at least 20 atm (2000kPa)and more preferably at least 40 atm (4000kPa) , a total water and/or alcohol to olefin mole ratio of from 0.1 to 30, preferably from 0.2 to 15 and most preferably from 0.3 to 5.
  • the olefin conversion process of this invention can be carried out under liquid phase, vapor phase or mixed vapor-liquid phase conditions in batch or in a continuous manner using a stirred tank reactor or fixed bed flow reactor, e.g. , of the trickle-bed, liquid-up-flow, liquid-down-flow, counter-current and co-current type. Reaction times of from 20 minutes to 20 hours when operating in batch and an LHSV of from 0.1 to 25 when operating continuously are generally suitable. It may, of course, be advantageous to recover any unreacted olefin and recycle it to the reactor.
  • the aqueous product effluent from the olefin hydration reactor containing alcohol and ether can be introduced into a separator, e.g., a distillation column, for recovery of ether.
  • the dilute aqueous solution of alcohol may be then introduced into a second separator, e.g., another distillation column, where a water/alcohol azeotrope is recovered.
  • a fraction of the azeotrope may be fed into a conventional dehydra t ion reactor to provide a further quantity of ether which can be combined with the ether previously recovered from the olefin hydration reactor.
  • alcohol/ether mixtures By blending various product streams, almost any ratio of alcohol/ ether can be obtained.
  • this capability for adjusting the ratios of alcohol to ether offers great flexibility in meeting the octane requirements for given gasoline compositions.
  • alcohol/ether mixtures e.g., IPA/DIPE mixtures, can cons itx ⁇ te up tc about 20 weight percent of the gasoline to which they are added.
  • a particularly advantageous procedure for producing mixtures of alcohol and ether, and in particular IPA and DIPE, from the hydration of an olefin-containing feed (a propylene-containing feed in the case of IPA/DIPE mixtures) employing a large pore zeolite such as zeolite Y or zeolite Beta is described in EP-A-323137.
  • a fresh propane/propylene-containing feed (readily available in many petroleum refineries) and fresh water are cofed, together with recycled unreacted propylene and recycled water from a decanter, into a hydration reactor.
  • the reactor effluent is passed to a separator unit with propane and unconverted propylene being recycled to the 5 reactor, part of the gaseous mixture being purged in order to avoid build-up of propane in the recycle loop.
  • the liquid products from the separator unit are introduced into a distillation unit where an azeotropic mixture of IPA, DIPE, water and propylene oligomers (mostly C___
  • the upper layer contains mostly DIPE, e.g., 90 weight percent or more, end relatively little water, e.g., 1 weight percent or so.
  • the lower layer is largely water
  • the quantity of the decanter overheads which is recycled can be regulated so as to control the water content in the final product.
  • the bottom fraction of the distillation unit, mainly IPA, is combined with DIPE in the decanter
  • the propylene component of a mixed propane/propylene feed undergoes hydration in the presence of a large pore zeolite olefin hydration catalyst, e.g., zeolite Y or zeolite Beta, in a hydration reactor with the effluent therefrom being passed to a separator operating
  • a large pore zeolite olefin hydration catalyst e.g., zeolite Y or zeolite Beta
  • the resulting phase separation provides a DIPE product containing at most negligible amounts of IPA and water, e.g., 1.0 weight percent and 0.5 weight percent of these materials, respectively.
  • the remaining aqueous phase can be recycled to the reactor.
  • the catalyst employed in the olefin conversion process of this invention can include any zeolite which is effective for the catalysis of the reaction of olefin ( ⁇ ) with water and/or alcohol(s) to produce alcohol ( ⁇ ) , ether( ⁇ ) or their mixtures.
  • zeolites which are u ⁇ eful herein are zeolite Beta, zeolite X, zeolite L, zeolite Y, ultra ⁇ table zeolite Y (USY) , dealuminized Y (Deal Y) , ordenite, ZSM-3 , ZSM-5, ZSM-12, ZSM-20, Z-5M ⁇ 23 r ZSM-35, ZSM-50, and ixture ⁇ of any of the foregoing.
  • Zeolite Beta i ⁇ described in U.S. Rei ⁇ ue Patent No. 28,341 (of original U.S. Patent No. 3,308,069) .
  • Zeolite X is described in U.S. Patent No. 2,882,244.
  • Zeolite L i ⁇ described in U.S. Patent No. 3,216,789.
  • Zeolite Y is described in U.S. Patent No. 3,130,007.
  • Low sodium ultrastable zeolite Y (USY) is described in U.S. Patent No ⁇ . 3,293,192, 3,354,077, 3,375,065, 3,402,996, 3,449,070 and 3,595,611.
  • Dealuminized zeolite Y can be prepared by the method disclosed in U.S. Patent No. 3,442,795.
  • Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983.
  • Zeolite ZSM-23 is described in U.S. Patent No. 4,076,842.
  • Zeolite ZSM-35 is described in U.S. Patent No. 4,016,245.
  • Zeolite ZSM-50 is described in U.S. Patent No. 4,640,829.
  • the zeolite olefin hydration/etherification catalyst ⁇ ⁇ elected for use herein will generally possess an alpha value of at least about 1.
  • "Alpha value”, or "alpha number”, i ⁇ a measure of zeolite acidic functionality and is more fully described together with details of its measurement in J. Catalysis, 61, pp. 390-396 (1980) .
  • Zeolites of relatively low acidity e.g.
  • zeolites pos ⁇ e ⁇ ing alpha value ⁇ of less than about 200 can be prepared by a variety of techniques including (a) synthe ⁇ izing a zeolite with a high silica/alumina ratio, (b) steaming, (c) steaming followed by dealuminization and (d) substituting framework aluminum with other trivalent metal species.
  • the zeolite can be expo ⁇ ed to steam at elevated temperatures ranging from 2-60 -.to_65Q ⁇ .
  • the as-synthesized zeolite crystals ⁇ hould Prior to their use as olefin hydration/etherification catalysts, the as-synthesized zeolite crystals ⁇ hould be subjected to thermal treatment to remove part or all of any organic constituent present therein.
  • the zeolites ⁇ hould be at least partially dried prior to u ⁇ e.
  • Thi ⁇ can be done by heating the crystals to a temperature in the range of from 200 to 595°C in an inert atmosphere, such as air or nitrogen and atmospheric, subat ospheric or superatmo ⁇ pheric pressures for between 30 minute ⁇ to 48 hour ⁇ .
  • Dehydration can also be performed at room temperature merely by placing the cry ⁇ talline material in a vacuum, but a longer time is required to obtain a ⁇ ufficient amount of dehydration.
  • the original cations as ⁇ ociated with the zeolites utilized herein can be replaced by a wide variety of other cations according to techniques well known in the art, e.g., by ion-exchange. Typical replacing cations include hydrogen, ammonium, alkyl ammonium and metal cation ⁇ , and their mixture ⁇ . Metal cations can also be introduced into the zeolite.
  • metals of Groups IB to VIII of the Periodic Table including, by way .of example, iron, nickel, cobalt, copper, zinc, platinum, palladium, calcium, chromium, tungsten, molybdenum, rare earth metals, etc. These metals can also be present in the form of their oxides.
  • a typical ion-exchange technique involves contacting a particular zeolite with a salt of the desired replacing cation.
  • a salt of the desired replacing cation Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfate ⁇ .
  • Repre ⁇ entative ion-exchange techniques are di ⁇ clo ⁇ ed in a number of patent ⁇ including U.S. Patent No ⁇ . 3,140,249; 3,140,251 and 3,140,253.
  • the zeolite is then preferably wa ⁇ hed with water and dried at a temperature ranging from 65 to 315°C (150 to 600°F) and thereafter calcined in air or other inert gas at temperatures ranging from 260 to 820*C (500 to 1500°F) for periods of time ranging from 1 to 48 hours or more.
  • the catalyst employed in the proces ⁇ of the invention also include ⁇ a binder material in the form of at lea ⁇ t one e ⁇ entially non-acidic refractory oxide of a metal of Group ⁇ IVA or IVB of the Periodic Table of the Elements. Particularly useful are the oxide ⁇ of silicon, germanium, titanium and zirconium.
  • Combinations of such oxides with other oxides are also useful provided that at least 40 weight percent, and preferably at least 50 weight percent, of the total oxide i ⁇ one or a combination of the afore ⁇ aid Group IVA and/or Group IVB metal oxide ⁇ .
  • mixtures of oxide ⁇ which can be used to provide the binder material herein include titania-alumina, titania-magne ⁇ ia, titania-zirconia, t . ita.p,ia-thcria, titania-beryllia, silica-alumina-magnesia- and ' • silica-titania-zirconia, zirconia-alumina and silica-zirconia.
  • colloidal metal oxide binder In preparing the refractory oxide-bound zeolite catalyst, it is generally advantageous to provide at lea ⁇ t a part of the binder in colloidal form a ⁇ this has been found to facilitate the extrusion of the bound zeolite which can otherwise be accomplished in accordance with known and conventional techniques.
  • a colloidal metal oxide binder When a colloidal metal oxide binder is employed, it can represent anywhere from 1 to 100 weight percent of the total binder present. For example, in the case of silica, amounts of colloidal silica ranging from 2 to 60 weight percent of the total binder generally provide good result ⁇ .
  • the relative proportion ⁇ of zeolite and refractory oxide binder on an anhydrou ⁇ basis can vary widely with the zeolite content 5 ranging from between 1 to 99 weight percent, and more usually in the range of from 20 to 80 weight percent, of the dry compo ⁇ ite.
  • Example ⁇ 1 and 2 are illu ⁇ trative of the 0 preparation of zeolite catalysts which are useful as catalysts herein and Example ⁇ 3 to 5 are illustrative cf the olefin conversion proces ⁇ of this invention.
  • Beta olefin hydration/etherification catalyst compo ⁇ ition ⁇ Beta olefin hydration/etherification catalyst compo ⁇ ition ⁇ .
  • zeolite Beta crystals were separately combined with titania and zirconia to form mixtures, each containing of 65 parts zeolite and 35 part ⁇ metal oxide binder. Enough water was added to the mixture so that the resulting catalyst could be formed into an extrudate.
  • the catalyst was activated by calcining first in nitrogen at 540 ° C (1000°F) followed by aqueous exchanges .with 1.0 N ammonium nitrate solution and calcining in air at 540°C (1000'F) .
  • Portion ⁇ of the ZSM-35 cry ⁇ tal ⁇ were ⁇ eparately combined with titania and zirconia to form mixture ⁇ , each containing 65 part ⁇ zeolite and 35 part ⁇ metal oxide 0 binder. Enough water wa ⁇ added to the mixture ⁇ o that the resulting ⁇ 'ca ⁇ yst .qc i . be formed into an extrudate.
  • the cataly ⁇ t was activated by calcining first in nitrogen at 540°C (1000°F) , followed by aqueous exchange ⁇ with -1.0 N ammonium nitrate solution and calcining in air at 540'C 5 (100Q-F).
  • EXAMPLE 3 This example illustrate ⁇ the improved results obtained when conducting olefin hydration/etherification with non-acidic metal oxide-bound zeolite Beta olefin 0 hydration catalysts, i.e., the titania- and zirconia-bound zeolite Beta catalyst compositions of Example l r compared with an acidic metal oxide-bound zeolite Beta, e.g., zeolite bound with 35 parts of alumina.
  • non-acidic metal oxide-bound zeolite Beta olefin 0 hydration catalysts i.e., the titania- and zirconia-bound zeolite Beta catalyst compositions of Example l r compared with an acidic metal oxide-bound zeolite Beta, e.g., zeolite bound with 35 parts of alumina.
  • the hydration conditions included the use of e ⁇ entially pure propylene a ⁇ the feed, a total system pre ⁇ ure of 7000kPa (1000 p ⁇ ig) , a temperature of 166°C (330°F) , a weight hourly space velocity (WHSV) based on propylene of 0.62 and a mole ratio of water to propylene of 0.5.
  • EXAMPLE 4 The propylene hydration/etherification operations of Example 3 were sub ⁇ tantially repeated except that the catalysts were 35 weight percent alumina-bound ZSM-35 and 35 weight percent titania-bound ZSM-35 and the mole ratio of water to propylene wa ⁇ 2.
  • the re ⁇ ults of the hydration reactions are set forth in Table II as follows: TABLE II
  • titania-bound zeolite catalyst provided much higher propylene conversion compared to the alumina-bound zeolite.
  • EXAMPLE 5 A zeolite Beta catalyst composition wa ⁇ prepared much a ⁇ de ⁇ cribed in Example 1, ⁇ upr , except that the binder wa ⁇ 17 weight part ⁇ of silica.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

On effectue la conversion d'oléfines en alcools et/ou en éthers en utilisant, comme catalyseur, une zéolite acide qui a été liée à un oxyde réfractaire essentiellement non acide d'au moins un métal du groupe IVA et/ou IVB du tableau périodique de classification des éléments chimiques, tel que de la silice, de l'oxyde de titane, de la zircone et/ou de l'oxyde de germanium.
PCT/US1990/000135 1989-01-12 1990-01-10 Procede de conversion d'olefines en alcools et/ou en ethers WO1990008120A1 (fr)

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US296,110 1989-01-12

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AU (1) AU4840290A (fr)
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5532392A (en) * 1994-01-13 1996-07-02 Gheorghiu; Mihail Process for the preparation of methyl fatty acid esters starting from natural oil or fat, methyl esters obtained in this way and use thereof
CN1060686C (zh) * 1998-01-12 2001-01-17 南开大学 复合活性碳纤维固体催化剂
RU2507190C1 (ru) * 2012-11-09 2014-02-20 Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" (ООО "НПО ЕВРОХИМ") Способ получения третичного бутанола
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
CN112867700A (zh) * 2018-10-17 2021-05-28 埃克森美孚化学专利公司 烯烃的低聚
CN112867701A (zh) * 2018-10-17 2021-05-28 埃克森美孚化学专利公司 烯烃的低聚
US20220281792A1 (en) * 2019-09-30 2022-09-08 Dow Global Technologies Llc Methods of etherification

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TW321634B (fr) 1994-07-05 1997-12-01 Mitsui Toatsu Chemicals

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EP0162475A2 (fr) * 1984-05-25 1985-11-27 Asahi Kasei Kogyo Kabushiki Kaisha Procédé de production d'un alcool cyclique
EP0213884A2 (fr) * 1985-09-03 1987-03-11 Mobil Oil Corporation Fabrication d'éthers à partir d'oléfines linéaires
WO1988008329A1 (fr) * 1987-05-01 1988-11-03 Mobil Oil Corporation Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite
EP0323270A1 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation catalytique d'oléfines
EP0323269A1 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation d'oléfines
EP0323268A2 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation catalytique d'oléfines

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Publication number Priority date Publication date Assignee Title
EP0162475A2 (fr) * 1984-05-25 1985-11-27 Asahi Kasei Kogyo Kabushiki Kaisha Procédé de production d'un alcool cyclique
EP0213884A2 (fr) * 1985-09-03 1987-03-11 Mobil Oil Corporation Fabrication d'éthers à partir d'oléfines linéaires
WO1988008329A1 (fr) * 1987-05-01 1988-11-03 Mobil Oil Corporation Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite
EP0323270A1 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation catalytique d'oléfines
EP0323269A1 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation d'oléfines
EP0323268A2 (fr) * 1987-12-30 1989-07-05 Mobil Oil Corporation Procédé d'hydratation catalytique d'oléfines

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5532392A (en) * 1994-01-13 1996-07-02 Gheorghiu; Mihail Process for the preparation of methyl fatty acid esters starting from natural oil or fat, methyl esters obtained in this way and use thereof
CN1060686C (zh) * 1998-01-12 2001-01-17 南开大学 复合活性碳纤维固体催化剂
US9206093B2 (en) 2004-04-16 2015-12-08 Gtc Technology Us, Llc Process for converting gaseous alkanes to liquid hydrocarbons
US8921625B2 (en) 2007-02-05 2014-12-30 Reaction35, LLC Continuous process for converting natural gas to liquid hydrocarbons
US9133078B2 (en) 2010-03-02 2015-09-15 Gtc Technology Us, Llc Processes and systems for the staged synthesis of alkyl bromides
US9193641B2 (en) 2011-12-16 2015-11-24 Gtc Technology Us, Llc Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems
RU2507190C1 (ru) * 2012-11-09 2014-02-20 Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" (ООО "НПО ЕВРОХИМ") Способ получения третичного бутанола
CN112867700A (zh) * 2018-10-17 2021-05-28 埃克森美孚化学专利公司 烯烃的低聚
CN112867701A (zh) * 2018-10-17 2021-05-28 埃克森美孚化学专利公司 烯烃的低聚
US20220281792A1 (en) * 2019-09-30 2022-09-08 Dow Global Technologies Llc Methods of etherification

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Publication number Publication date
EP0403639A1 (fr) 1990-12-27
AU4840290A (en) 1990-08-13
CA2025016A1 (fr) 1990-07-13
JPH03503175A (ja) 1991-07-18

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