WO1990012778A1 - Integrated process for production of gasoline and ether from alcohol with feedstock extraction - Google Patents
Integrated process for production of gasoline and ether from alcohol with feedstock extraction Download PDFInfo
- Publication number
- WO1990012778A1 WO1990012778A1 PCT/US1990/002203 US9002203W WO9012778A1 WO 1990012778 A1 WO1990012778 A1 WO 1990012778A1 US 9002203 W US9002203 W US 9002203W WO 9012778 A1 WO9012778 A1 WO 9012778A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrocarbon
- liquid
- alcohol
- methanol
- reactor
- Prior art date
Links
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
- C10G2400/02—Gasoline
-
- 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 an integrated reactor and extraction process and operating techniques for converting crude methanol or similar lower aliphatic alcohols to high octane gasoline and methyl tertiary-alkyl ethers, such as MTBE.
- this invention relates to an improvement in utilizing methanol-to-gasoline (MTG) processes and operating systems for converting crude methanol to valuable products by etherifying lower branched olefins, such as C.-C- normally liquid iso-olefins.
- MMG methanol-to-gasoline
- Methanol is considered the most important C 1 -C. oxygenate feedstock because of its widespread availability and low cost. Therefore, primary emphasis herein is placed on MTBE and TAME. 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. As an alternative, 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.
- a continuous process has been provided for converting crude lower aliphatic alcohol to alkyl tertiary-alkyl ethers and gasoline comprising the steps of:
- step (c) fractionating the etherification effluent from step (b) to recover an overhead stream containing unreacted alcohol and light olefinic hydrocarbon and to recover liquid product containing tertiary-alkyl ether;
- step (d) catalytically converting aqueous raffinate from step (a) in contact with medium pore acid zeolite catalyst in a second oxygenate conversion reaction zone concurrently with catalytic upgrading of unreacted alcohol the olefinic overhead stream of step (c) to provide predominantly liquid C_ hydrocarbon product along with C 3 ⁇ C g alkane intermediate product, water, and light gas;
- step (e) separating water and light gas from step (d) to recover C 3_-C5_ alkane-rich intermediate and C6- hydrocarbon product;
- step (f) dehydrogenating alkane intermediate from step (e) to provide an olefinic hydrocarbon liquid rich in iso-alkenes;
- step (g) recycling olefinic liquid from step (f) to step (a) as extraction solvent liquid for dewatering alcohol feedstock.
- the drawing is a schematic methanol extraction and etherification system flowsheet depicting the present invention.
- Typical feedstock materials for etherification reactions include olefinic streams, such as FCC light naphtha and butenes rich in iso-olefins. Typically, these aliphatic streams are produced in petroleum refineries by catalytic cracking of gas oil or the like.
- the crude methanol commercially available from syngas processes may contain, for instance 4 to 17 wt. % water, which must be removed, preferably to a methanol purity of 99.8 wt. %.
- Improved yield of high octane gasoline may be obtained by providing an etherification unit in conjunction with a large-scale MTG (methanol to gasoline) reaction zone.
- MTG methanol to gasoline
- isobutane-rich C_-C 5 paraffins from the MTG process may be converted to iso-alkenes.
- the overall yield of high octane gasoline from oxygenate conversion is significantly increased.
- the olefinic methanol-containing vapors are separated from the ether products and coreacted in the MTG reaction zone.
- the feedstock for a typical MTG process is lower molecular weight oxygenated organic compound(s) .
- examples of such compounds are C.-C. aliphatic alcohols and their ethers. It is known in the art to partially convert methanol by dehydration, as in the catalytic reaction over gamma-alumina to produce DME intermediate.
- a mixture (CH-OH + CH_-0-CH_
- the MTG process unit may be a fixed bed type, as disclosed in U.S. Patents 3,894,107; 3,928,483; 3,931,349; 4,048,250; etc.
- isobutane In a typical fixed-bed MTG process relatively large amounts of isobutane are produced, e.g., 8% by weight of hydrocarbons product. In the past, it has been the practice to recover the isobutane fraction without an immediate upgrading step.
- isobutane production may be optimized in the range of 5-10 wt. % of hydrocarbon effluent.
- MTG gasoline plus ethers will increase blended gasoline pool octane because of their high component octanes.
- the desired MTG products are C. and C_ iso-alkanes, which will ordinarily comprise at least 5% of the recovered product.
- a continuous stream of crude methanol (MeOH) feedstock is introduced via conduit 10 with a stream of olefinic hydrocarbon liquid extractant introduced via conduit 12 to extraction separation unit 14, operated at 35-40*C.
- aqueous raffinate phase 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 reactor 20.
- Supplemental reactants such as dry alcohol or iso-alkenes may be added via line 19 to the etherification reaction zone to maintain stoichiometric ratio of reactants as desired.
- Flow control means can be employed to measure streams 12 and 18 and provide increased or decreased fresh feed through line 10 in response to a predetermined ratio, as understood by those skilled in the chemical process instrumentation.
- the bypassed portion of fresh feed can be mixed with the raffinate stream 16 and upgraded in reactor 40.
- the effluent stream 22 passes to a debutanizer fractionation tower 30.
- debutanizer separation unit 30 the C 5 tert-alkyl ether product (MTBE and/or TAME) is recovered as a liquid product stream 32, along with unreacted C 5 (or optionally heavier C g ) hydrocarbons in the extractant.
- Fractionation tower overhead vapor comprising unreacted c. "" hydrocarbons and methanol is removed via conduit 34, and is sent to catalytic zeolite conversion unit 40, where it is contacted concurrently with aqueous raffinate from line 16.
- the aqueous raffinate stream 16 consists essentially of water, partitioned methanol (e.g. -
- 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 fluidized bed MTG reaction zone to produce predominantly gasoline range liquid hydrocarbons, along with a saturated hydrocarbon intermediate to be treated as herein described.
- an acid zeolite catalyst such as medium pore shape selective zeolite, such as, ZSM-5, etc.
- Effluent stream 42 is condensed and separated by phase and/or fractionation in unit 50 to provide a liquid gasoline product stream 52, byproduct water, light offgas 54, and a C--C 5 paraffinic intermediate hydrocarbon stream 56, rich in isobutane and isopentane.
- Dehydrogenation unit 60 converts the intermediate hydrocarbons to an iso-alkene containing liquid suitable for use as an extraction solvent. The dehydrogenation may be achieved catalytically by known unit operations to produce a hydrogen byproduct gas and an olefinic product consisting essentially of C 2 ⁇ C 5 olefins.
- dehydrogenated aliphatics from unit 60 may be employed as extractant via line 12; however, it is within the inventive concept to separate a portion of these olefins for feeding to conversion unit 40 via line 12A.
- Paraffinic feed to the deydrogenation unit 60 may be supplemented by various refinery streams via line 62, such as LPG containing propane and butanes.
- the aqueous methanol raffinate stream may be coreacted with olefinic light gas and/or other reactive hydrocarbon feedstreams in a conventional MTG reaction section, as described by Tabak in U.S. Patent 4,654,453 and Owen et al in U.S. Patent No. 4,788,365.
- the aqueous methanol may be introduced as a liquid directly to a fluidized bed reaction zone (bottom or middle secton) or vaporized and mixed with effluent vapor from the etherification unit.
- etherification effluent overhead and/or 2 -C 5 olefinic light hydrocarbon gas containing ethene, propene, unreacted butylenes, etc. may be injected at the bottom of the fluidized bed reaction zone and converted along with the raffinate stream.
- the typical preferred crude feedstock material is methanol containing 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.
- 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.
- the crude aqueous feedstock containing 4% water is contacted with olefinic liquid hydrocarbons in a liquid-liquid contact and separation unit at 38*C (100'F) .
- the extractor unit is operated at 35-65"C (100-150*F) and 0-2000 kPa.
- a preferred catalyst is a sulfonic acid ion exchange resin which etherifies and isomerizes the reactants.
- a typical acid catalyst is Amberlyst 15 sulfonic acid resin.
- Zeolite catalysis technology for upgrading lower aliphatic hydrocarbons and oxygenates to liquid hydrocarbon products are well known.
- Commerial Methanol-to-Gasoline (MTG) methanol-to olefins (MTO) , aromatization (M2-Forming) 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 liquid aliphatic and aromatics in the C_-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. In the fluidized bed reactor 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;
- zeolites having a coordinated metal oxide to silica molar ratio of 20:1 to 200:1 or higher may be used, it is advantageous to employ a standard ZSM-5 having a silica alumina molar ratio of 25:1 to 70:1, suitably modified if desired to adjust acidity and oligomerization/aromatization characteristics.
- a typical zeolite catalyst component having Bronsted acid sites may consist essentially of aluminosilicate ZSM-5 zeolite with 5 to 95 wt. % silica and/or alumina binder.
- 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.
- Particle size distribution can be a significant factor in achieving overall homogeneity in turbulent regime fluidization. It is desired to operate the process with particles that will mix well throughout the bed. Large particles having a particle size greater than 250 microns should be avoided, and it is advantageous to employ a particle size range consisting essentially of l to 150 microns. Average particle size is usually 20 to 100 microns, preferably 40 to 80 microns. Particle distribution may be enhanced by having a mixture of larger and smaller particles within the operative range, and it is particularly desirable to have a significant amount of fines. Close control of distribution can be maintained to keep 10 to 25 wt. % of the total catalyst in the reaction zone in the size range less than 32 microns. Accordingly, the fluidization regime is controlled to assure operation between the transition velocity and transport velocity.
- olefinic supplemental feedstreams may be added to the preferred MTG reactor unit.
- Non-deleterious components such as lower paraffins and inert gases, may be present.
- the reaction severity conditions can be controlled to optimize yield of C -C_ paraffins, olefinic gasoline or Cg"C 8 BTX hydrocarbons, according to product demand. It is understood that aromatic hydrocarbon and light paraffin production is promoted by those zeolite catalysts having a high concentration of Bronsted acid reaction sites. Accordingly, an important criterion is selecting and maintaining catalyst inventory to provide 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.
- a turbulent fluidized catalyst bed the conversion reactions are conducted in a vertical reactor column by passing hot reactant vapor or lift gas 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.
- reaction temperature can be carefully controlled in the usual operating range of about 250*C. to 650 * C, preferably at average reactor temperature of 350'C to 500'C.
- the present invention is particularly advantageous in the economic dewatering of crude methanol, thus avoiding expensive and energy-intensive prefracti ⁇ nation by distillation.
- By extracting methanol from the crude feedstock with olefinic hydrocarbon reactant liquid substantial utilitites and equipment savings are realized.
- Various modifications can be made to the system, especially in the choice of equipment and non-critical processing steps.
- Another advantage is increased C_+ gasoline yield, especially by converting a C_-C. fraction to MTG gasoline and MTBE.
Abstract
Description
Claims
Applications Claiming Priority (6)
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 | ||
US358,097 | 1989-05-30 | ||
US07/358,097 US5047070A (en) | 1988-04-11 | 1989-05-30 | Integrated process for production of gasoline and ether from alcohol with feedstock extraction |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990012778A1 true WO1990012778A1 (en) | 1990-11-01 |
Family
ID=27407495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1990/002203 WO1990012778A1 (en) | 1989-04-24 | 1990-04-23 | Integrated process for production of gasoline and ether from alcohol with feedstock extraction |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0422188A1 (en) |
JP (1) | JPH03505603A (en) |
AU (1) | AU5529890A (en) |
CA (1) | CA2031212A1 (en) |
WO (1) | WO1990012778A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6179786B1 (en) | 1998-10-02 | 2001-01-30 | Profemme Ltd. | System for thermometry-based breast cancer risk-assessment |
US6419636B1 (en) | 1998-10-02 | 2002-07-16 | David Ernest Young | System for thermometry-based breast assessment including cancer risk |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4191846A (en) * | 1973-11-15 | 1980-03-04 | Phillips Petroleum Company | Catalytic dehydrogenation process |
US4423251A (en) * | 1982-09-09 | 1983-12-27 | Uop Inc. | Process employing sequential isobutylene hydration and etherification |
US4827045A (en) * | 1988-04-11 | 1989-05-02 | Mobil Oil Corporation | Etherification of extracted crude methanol and conversion of raffinate |
US4826662A (en) * | 1984-12-19 | 1989-05-02 | Mobil Oil Corporation | Apparatus for feeding an MTG conversion reactor |
US4826507A (en) * | 1987-12-08 | 1989-05-02 | Mobil Oil Corporation | Integrated etherification and oxygenates to gasoline process |
US4827046A (en) * | 1988-04-11 | 1989-05-02 | Mobil Oil Corporation | Extraction of crude methanol and conversion of raffinate |
US4830635A (en) * | 1987-12-08 | 1989-05-16 | Mobil Oil Corporation | Production of liquid hydrocarbon and ether mixtures |
US4886925A (en) * | 1988-05-02 | 1989-12-12 | Mobil Oil Corp | Olefins interconversion and etherification process |
-
1990
- 1990-04-23 AU AU55298/90A patent/AU5529890A/en not_active Abandoned
- 1990-04-23 CA CA002031212A patent/CA2031212A1/en not_active Abandoned
- 1990-04-23 EP EP90906693A patent/EP0422188A1/en not_active Withdrawn
- 1990-04-23 WO PCT/US1990/002203 patent/WO1990012778A1/en not_active Application Discontinuation
- 1990-04-23 JP JP2506505A patent/JPH03505603A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4191846A (en) * | 1973-11-15 | 1980-03-04 | Phillips Petroleum Company | Catalytic dehydrogenation process |
US4423251A (en) * | 1982-09-09 | 1983-12-27 | Uop Inc. | Process employing sequential isobutylene hydration and etherification |
US4826662A (en) * | 1984-12-19 | 1989-05-02 | Mobil Oil Corporation | Apparatus for feeding an MTG conversion reactor |
US4826507A (en) * | 1987-12-08 | 1989-05-02 | Mobil Oil Corporation | Integrated etherification and oxygenates to gasoline process |
US4830635A (en) * | 1987-12-08 | 1989-05-16 | Mobil Oil Corporation | Production of liquid hydrocarbon and ether mixtures |
US4827045A (en) * | 1988-04-11 | 1989-05-02 | Mobil Oil Corporation | Etherification of extracted crude methanol and conversion of raffinate |
US4827046A (en) * | 1988-04-11 | 1989-05-02 | Mobil Oil Corporation | Extraction of crude methanol and conversion of raffinate |
US4886925A (en) * | 1988-05-02 | 1989-12-12 | Mobil Oil Corp | Olefins interconversion and etherification process |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6179786B1 (en) | 1998-10-02 | 2001-01-30 | Profemme Ltd. | System for thermometry-based breast cancer risk-assessment |
US6419636B1 (en) | 1998-10-02 | 2002-07-16 | David Ernest Young | System for thermometry-based breast assessment including cancer risk |
Also Published As
Publication number | Publication date |
---|---|
CA2031212A1 (en) | 1990-10-25 |
JPH03505603A (en) | 1991-12-05 |
EP0422188A1 (en) | 1991-04-17 |
AU5529890A (en) | 1990-11-16 |
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