WO1990012855A1 - Conversion d'alcools en essence riche en ether - Google Patents

Conversion d'alcools en essence riche en ether Download PDF

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Publication number
WO1990012855A1
WO1990012855A1 PCT/US1990/002205 US9002205W WO9012855A1 WO 1990012855 A1 WO1990012855 A1 WO 1990012855A1 US 9002205 W US9002205 W US 9002205W WO 9012855 A1 WO9012855 A1 WO 9012855A1
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WIPO (PCT)
Prior art keywords
methanol
liquid
water
feedstock
stream
Prior art date
Application number
PCT/US1990/002205
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English (en)
Inventor
Mohsen Nadimi Harandi
Hartley Owen (Nmn)
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Mobil Oil Corporation
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Publication date
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Publication of WO1990012855A1 publication Critical patent/WO1990012855A1/fr

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20—C2-C4 olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/22—Higher olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • This invention relates to techniques for converting crude methanol or other C.-C. lower aliphatic alcohols to alkyl tertiary-alkyl ethers, di-isopropyl ether (DIPE) , and gasoline range hydrocarbons.
  • this invention relates to an integrated system for converting crude methanol to valuable products by etherifying lower branched olefins, such as C . -C- normally liquid iso-olefins.
  • isobutylene and other isoalkenes produced by hydrocarbon cracking may be reacted with methanol over an acidic catalyst to provide methyl tertiary butyl ether (MTBE) and isoamylenes may be reacted with methanol over an acidic catalyst to produce tertiary-amyl methyl ether (TAME) .
  • MTBE methyl tertiary butyl ether
  • TAME tertiary-amyl methyl ether
  • Those ethers having the formula CH 3 -0-R, where R is a tertiary alkyl radical are particularly useful as octane improvers for liquid fuels, especially gasoline.
  • MTBE and TAME are known to be high octane ethers.
  • M+O 83
  • the blending value of MTBE at the 10% level is 103.
  • the blending value of 10% MTBE is 114.
  • Methanol may be readily obtained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes.
  • the methanol may be obtained from natural gas by other conventional processes, such as steam reforming or partial oxidation to make the intermediate syngas. Crude methanol from such processes usually contains a significant amount of water, usually in the range of 4 to 20 wt%; however, the present invention is useful for removing water in lesser amounts or greater.
  • the present invention provides a novel and economic technique for removing excess water from crude methanol feedstocks, including novel operating methods and equipment for treating these oxygenate feedstocks prior to etherification and disposing of raffinate containing methanol. It has been discovered that aqueous methanol streams, such as etherification feedstock extraction byproduct can be economically upgraded by catalytic conversion concurrently with hydrocarbons.
  • a continuous technique has been found for converting crude methanol to high octane gasoline and mixed ethers.
  • a process is provided for converting crude aqueous alcohol feedstock to tertiary-butyl ether and tertiary-amyl methyl product in contact with acid catalyst comprising the steps of: contacting the aqueous alcohol feedstock with liquid hydrocarbon extractant comprising C 4 ⁇ C 5 mixed olefinic hydrocarbons comprising isobutylene and isoamylenes under liquid extraction conditions; recovering an aqueous raffinate phase containing alcohol and a major amount of water introduced with the feedstock; recovering an organic extract phase comprising the hydrocarbon extractant and a portion of alcohol introduced in the feedstock sufficient to etherify a major amount of tertiary olefins in the extract phase; and catalytically converting alcohol in the raffinate phase to predominantly lower olefins rich in propene and isoalkene hydrocarbons; reacting extracted alcohol with the
  • Isoalkenes produced by catalytic conversion of alcohol can be recovered in a C.-C 8 liquid stream and employed as liquid extractant.
  • propene recovered from alcohol conversion with water to produce di-isopropyl ether, an additional octane booster ether product is obtained.
  • a significant process improvement is provided wherein byproduct isopropanol is coproduced with di-isopropyl ether by reaction of propene with water.
  • the isopropanol may be converted to hydrocarbons concurrently with raffinate alcohol, or at least a portion of the byproduct isopropanol, di-isopropyl ether and tertiary-alkyl ether may be blended with liquid C & + hydrocarbons to produce high octane gasoline produc .
  • a typical t-alkyl ether catalyst is sulfonic acid resin and the methanol is converted to olefinic hydrocarbons advantageously with a medium pore shape selective metallosilicate catalyst, such as ZSM-5 zeolite.
  • Fig. 1 of the drawing is a schematic etherification process flowsheet depicting the present invention
  • Fig. 2 is a typical fluidized bed reactor system adaptable for conversion of methanol.
  • Typical feedstock materials for etherification reactions include crude methanol commercially available from syngas processes, which may contain up to 30 wt% water, which must be removed, preferably to a methanol purity of 99.8 wt%. It has been found that more than 75% of crude feedstock methanol can be recovered by liquid extraction with light olefinic liquid extractant, such as butenes and C g + light olefinic naphtha.
  • the typical hydrocarbon feed ratio range is 2 to 8 parts per part by weight of extracted methanol.
  • Typical processing equipment operatively connected according to the present invention includes a continuous feedstock separation and etherification reactor system for converting crude methanol oxygenate feedstock and iso-olefin to methyl t-alkyl ether
  • the unit operation apparatus includes: extractor means for contacting crude feedstock liquid containing a minor amount of water with a liquid hydrocarbon extraction stream under extraction conditions favorable to selective extraction of methanol, thereby providing an extract liquid stream containing sufficient methanol for etherification and an aqueous raffinate stream lean in methanol; first catalytic reactor means operatively connected for contacting the extract stream in a catalytic reaction zone with acid etherification catalyst in an etherification reaction zone under process conditions to convert a major portion of methanol to ether; second catalytic reactor means for contacting said raffinate stream with methanol conversion catalyst in the presence of hydrocarbon to produce olefinic hydrocarbons; means for charging at least a portion of said olefinic hydrocarbon rich in C.-C_ is
  • a continuous stream of crude methanol (MeOH) feedstock is introduced via conduit 10 with a stream of C 4.+ olefinic hydrocarbon liquid extractant introduced via conduit 12 to a top inlet of extraction separation unit 14, operated at about 35-40'C. These streams are contacted under liquid extraction conditions to provide an aqueous raffinate phase.
  • An aqueous stream containing a major amount of the water present in the crude feedstock is withdrawn via conduit 16.
  • the lighter organic extract phase containing hydrocarbon extraction solvent and the major amount of feedstock methanol is recovered from extraction unit 14 via conduit 18, and introduced under temperature and process conditions suitable for conversion of methanol in contact with etherification catalyst in a first reactor unit 30.
  • the effluent product stream passes to a debutanizer or fractionation tower (not shown) , where the C 5 + methyl tert-alkyl ether product is recovered as a liquid stream 32, along with unreacted C 5 + hydrocarbons in the extractant.
  • Tower overhead comprising unreacted C.+ hydrocarbons and methanol are recovered by line 34.
  • the aqueous raffinate stream 16 consists essentially of water, partitioned methanol (50-80 wt%) and a trace of hydrocarbon. This stream is reactive at elevated temperature in the presence of an acid zeolite catalyst, such as medium pore shape selective zeolite, such as, ZSM-5, etc., in a MTO conversion unit 40, typically a fluidized bed reaction zone.
  • an acid zeolite catalyst such as medium pore shape selective zeolite, such as, ZSM-5, etc.
  • the aqueous methanol raffinate stream may be coreacted with unextracted feedstream 19, which bypasses the flow control valve FCV associated with etherification reactant flow. Olefinic light gas and/or other reactive hydrocarbon feedstreams may also be converted in a MTO reaction section, as described by Owen et al in U.S. Patent 4,746,762.
  • the aqueous methanol may be introduced as a liquid directly to the reaction zone (bottom or middle section) , as herein described with regard to Fig. 2, or vaporized and mixed with diluent and/or supplemental hydrocarbon feed.
  • the propene-rich C, Stream 42 and a portion of byproduct water from the MTO unit 40 are contacted with an acid etherification catalyst in DIPE unit 50 to produce di-isopropyl ether, which may be recovered by conventional fractionation to provide product stream 54 and unreacted C3's 56.
  • Byproduct isopropanol may be recovered as product stream 52 or fed via line 53 to be converted in MTO or MTBE unit 50 to produce additional hydrocarbons or ethers.
  • the alcohol feedstock may comprise one or more C.-C. lower aliphatic alkanols
  • the preferred crude material is methanol containing 2 to 20%, preferrably 4 to 17% by weight water.
  • the extraction contact unit may be a stirred multi-stage vertical extraction column adapted for continuous operation at elevated pressure. Any suitable extraction equipment may be employed, including cocurrent, cross-current or single contactors, wherein the liquid methanol feedstock is intimately contacted with a substantially immiscible liquid hydrocarbon solvent, which may be a mixture of C.+ aliphatic components including lower alkanes, n-alkenes or relatively pure isoalkenes, such as isobutylene, etc. This unit operation is described in Kirk-Othmer Encyclopedia of Chemical Technology (Third Ed.), 1980, pp.672-721. Other equipment for extraction is disclosed in US Patents 4,349,415
  • the methanol extraction step can be performed advantageously in a countercurrent multistage design, such as a simple packed column, rotating disk column, agitated column with baffles or mesh, or a series of single stage mixers and settlers.
  • a preferred catalyst is a polysulfonic acid resin, such as "Amberlyst 15" resin.
  • Zeolite catalysis technology for upgrading lower aliphatic hydrocarbons and oxygenates to lower olefins and liquid hydrocarbon products are well known.
  • Commerial Methanol-to-Gasoline (MTG) , methanol-to olefins (MTO) and Mobil Olefin to Gasoline/Distillate (MOG/D) processes employ shape selective medium pore zeolite catalysts for these processes. It is understood that the present zeolite conversion unit operation can have the characteristics of these catalysts and processes to produce a variety of hydrocarbon products, especially C -C_ olefins, and liquid aliphatic and aromatics in the C 8 -C_ gasoline range.
  • ZSM-5 medium pore siliceous materials having similar pore geometry. Most prominent among these intermediate pore size zeolites is ZSM-5, which is usually synthesized with Bronsted acid active sites by incorporating a tetrahedrally coordinated metal, such as Al, Ga, Fe or mixtures thereof, within the zeolitic framework. These medium pore zeolites are favored for acid catalysis; however, the advantages of ZSM-5 structures may be utilized by employing highly siliceous materials or cystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity. ZSM-5 crystalline structure is readily recognized by its X-ray diffraction pattern, which is described in U.S. Patent No. 3,702,866 (Argauer, et al.).
  • Zeolite hydrocarbon upgrading catalysts preferred for use herein include the medium pore (i.e., 5-7A) shape-selective crystalline aluminosilicate zeolites having a silica-to-alumina ratio of.at least 12, a constraint index of 1 to 12 and acid cracking activity (alpha value) of 1-250, preferably 3 to 80 based on total catalyst weight.
  • the coked catalyst may have an apparent activity (alpha value) of 3 to 80 under the process conditions to achieve the required degree of reaction severity.
  • Representative of the ZSM-5 type medium pore shape selective zeolites are ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, and ZSM-48.
  • Aluminosilicate ZSM-5 is disclosed in U.S. Patent No. 3,702,886 and U.S. Patent No. Re. 29,948.
  • Other suitable zeolites are disclosed in U.S. Patents 3,709,979; 3,832,449; 4,076,979; 3,832,449; 4,076,842; 4,016,245; 4,414,423; 4,417,086; 4,517,396 and 4,542,251.
  • zeolites having a coordinated metal oxide to silica molar ratio of 20:1 to 200:1 or higher
  • a standard ZSM-5 having a silica alumina molar ratio of 25:1 to 70:1, suitably modified if desired to adjust acidity.
  • Certain of the ZSM-5 type medium pore shape selective catalysts are sometimes known as pentasils.
  • the gallosilicate, and ferrosilicate materials may be employed.
  • ZSM-5 type pentasil zeolites are particularly useful in the process because of their regenerability, long life and stability under the extreme conditions of operation.
  • the zeolite crystals have a crystal size from 0.01 to 2 microns or more.
  • the zeolite catalyst crystals are bound with a suitable inorganic oxide, such as silica, alumina, etc. to provide a zeolite concentration of 5 to 95 wt. %.
  • a suitable inorganic oxide such as silica, alumina, etc.
  • 25% H-ZSM-5 catalyst calcined with 75% silica-alumina matrix binder is employed unless otherwise stated.
  • Suitable feedstreams to the methanol conversion unit comprise various alcohols, such as methanol and, optionally, isopropanol obtained from the DIPE etherification operation.
  • the reaction severity conditions can be controlled to optimize yield of the desired olefins, gasoline or C 8 -C 8 BTX hydrocarbons, according to product demand by providing either fresh or regenerated catalyst having the desired properties.
  • Reaction temperatures and contact time are also significant factors in the reaction severity, and the process parameters are followed to give a substantially steady state condition wherein the reaction severity is maintained within the limits which yield a desired weight ratio of propane to propene in the reaction effluent. -10-
  • a turbulent fluidized catalyst bed the conversion reactions are conducted in a vertical reactor column by passing hot reactant vapor upwardly through the reaction zone at a velocity greater than dense bed transition velocity and less than transport velocity for the average catalyst particle.
  • a continuous process is operated by withdrawing a portion of coked catalyst from the reaction zone, oxidatively regenerating the withdrawn catalyst and returning regenerated catalyst to the reaction zone at a rate to control catalyst activity and reaction severity to effect feedstock conversion.
  • the methanol and olefinic feedstream is converted in a catalytic reactor under moderate pressure (ie-100 to 2500 kPa) .
  • liquid methanol- containing raffinate 16 from the extractor is passed under pressure via feed conduit 116 for injection into vertical reactor vessel 110 above a feed distributor grid 112, which provides for distribution of hot vapor feed passing via conduit 114 through the small diameter holes in the grid 112.
  • Fluidization is effected in the bottom portion of the bed by upwardly flowing gas introduced via conduit 114, which may be supplemented with additional reactive gas 114A, such as ethylenic fuel gas or the like.
  • Thermodynamic conditions in the reaction vessel can be controlled by adjusting liquid injection rate, vapor feed temperature, catalyst temperature and rate, or by heat exchange means 115.
  • Regenerated catalyst is returned to the reactor fluid bed 110 through conduit means 122 provided with flow control valve means.
  • the hot regenerated catalyst is charged to the catalyst bed sufficiently below the upper interface to achieve good mixing in the fluid bed.
  • the product effluent separated from catalyst particles in the cyclone separating system then passes to effluent separation system 130.
  • the product effluent is cooled and separated to recover a propene-rich C_ stream, C.-C 5 iso-olefins, C g + liquid gasoline range hydrocarbons , fuel gas, along with byproduct water.
  • the preferred fluid bed reactor systems are described in U.S. Patents 4,547,616 (Avidan et al) ; 4,751,338 (Harandi & Owen)ed; and in U.S. Patent 4,579,999 (Tabak et al) .
  • a typical single pass reactor unit employs a temperature controlled in the usual operating range of 250"C to 650*C, preferably at average reactor temperature of 350 ⁇ C to 580*C, at moderate pressure of 100 to 3000 kPa (atmospheric to 400 psig) .
  • the weight hourly space velocity (WHSV, based on total alcohol in the feedstream) usually is 0.1-5 WHSV.
  • DIPE Reaction Olefin hydration to provide ethers and alcohols is well known.
  • Reaction of propene with water to produce DIPE and byproduct isopropyl alcohol (IPA) is an acid catalyzed process step, as described in U. S. Patents 4,214,107 and 4,499,313 and EP-A-0 323 268 to Bell et al.
  • the preferred catalytic methods for making DIPE employ solid acid catalysts, such as zeolites Y, Beta and/or ZSM-5 aluminosilicate. DIPE etherification conditions may vary widely in choice of temperature, pressure and reaction time.
  • the preferred method of Bell et al reacts propene with water in a fixed bed of zeolite Beta at 90 to 200 ⁇ C and pressure of at least 4000 kPa.
  • the unit operations described herein can be conducted with any number of specific process steps within the skill of the art.
  • the present invention is particularly advantageous in the economic dewatering of crude methanol, thus avoiding expensive and energy-intensive prefractionation by distillation.
  • By extracting methanol from the crude feedstock with olefinic hydrocarbon reactant liquid substantial utilities and equipment savings are realized.
  • Various modifications can be made to the system, especially in the choice of equipment and non-critical processing steps.
  • an integrated multi-reactor methanol conversion process according to the present invention is compared to a conventional prior art MTO single reactor process in Table 1, wherein the two continuous process flowrates are given in parts by weight, based on 100 parts methanol feedstock.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

On convertit du méthanol ou un autre alcool en des constituants de l'essence à indice d'octane élevé grâce à un procédé intégré. Ce procédé consiste à extraire un substrat d'alcool brut aqueux à l'aide d'un courant de liquide d'extraction contenant une iso-oléfine C4+ et à le faire réagir pour obtenir des éthers d'alcoyle tertiaire, par exemple du MTBE (éther de butyle tertiaire de méthyle). Le produit raffiné aqueux est ensuite converti en des hydrocarbures oléfiniques dans un réacteur catalytique MTO (méthanol-essence). On fait réagir le propène provenant de la réaction MTO avec de l'eau pour produire du di-isopropyl-éther, qui peut être mélangé à du MTBE et à des hydrocarbures MTO C6+ pour produire de l'essence à indice d'octane élevé. On peut récupérer de l'isobutylène et des isoamylènes provenant de la réaction MTO et les recycler pour en faire un courant liquide d'extraction.
PCT/US1990/002205 1989-04-24 1990-04-23 Conversion d'alcools en essence riche en ether WO1990012855A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US34213389A 1989-04-24 1989-04-24
US342,133 1989-04-24
US34458589A 1989-04-28 1989-04-28
US344,585 1989-04-28

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WO1990012855A1 true WO1990012855A1 (fr) 1990-11-01

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EP (1) EP0423288A1 (fr)
JP (1) JPH03505588A (fr)
AU (1) AU633080B2 (fr)
CA (1) CA2031184A1 (fr)
WO (1) WO1990012855A1 (fr)

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US8987162B2 (en) 2010-08-13 2015-03-24 Ut-Battelle, Llc Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
US8987161B2 (en) 2010-08-13 2015-03-24 Ut-Battelle, Llc Zeolite-based SCR catalysts and their use in diesel engine emission treatment
US9181493B2 (en) 2013-07-02 2015-11-10 Ut-Battelle, Llc Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock
CN105198687A (zh) * 2014-06-24 2015-12-30 环球油品公司 减少mto下游回收中的积垢的选择
US9278892B2 (en) 2013-03-06 2016-03-08 Ut-Battelle, Llc Catalytic conversion of alcohols to hydrocarbons with low benzene content
WO2016109371A1 (fr) * 2014-12-30 2016-07-07 Shell Oil Company Procédé de conversion de composés oxygénés
US9533921B2 (en) 2011-06-15 2017-01-03 Ut-Battelle, Llc. Zeolitic catalytic conversion of alochols to hydrocarbons
US10696606B2 (en) 2016-06-09 2020-06-30 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbon fractions with reduced gaseous hydrocarbon content

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JP4553231B2 (ja) * 2002-11-13 2010-09-29 日揮株式会社 ジメチルエーテルの製造方法
CN110036094B (zh) * 2016-12-07 2022-06-24 埃克森美孚科技工程公司 综合氧合物转化和烯烃低聚
CN110072973A (zh) * 2016-12-14 2019-07-30 埃克森美孚研究工程公司 在流化催化裂化器中转化含氧化合物的方法

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US8987162B2 (en) 2010-08-13 2015-03-24 Ut-Battelle, Llc Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
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US9938467B2 (en) 2011-06-15 2018-04-10 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbons
US9533921B2 (en) 2011-06-15 2017-01-03 Ut-Battelle, Llc. Zeolitic catalytic conversion of alochols to hydrocarbons
US9475039B2 (en) 2012-02-24 2016-10-25 Ut-Battelle, Llc Hydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
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US9181493B2 (en) 2013-07-02 2015-11-10 Ut-Battelle, Llc Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock
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Also Published As

Publication number Publication date
JPH03505588A (ja) 1991-12-05
EP0423288A1 (fr) 1991-04-24
AU633080B2 (en) 1993-01-21
AU5442690A (en) 1990-11-16
CA2031184A1 (fr) 1990-10-25
EP0423288A4 (fr) 1994-01-26

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