EP0424511A1 - Procede integre pour ameliorer la production d'ether a indice d'octane eleve et la conversion d'olefines dans l'essence - Google Patents

Procede integre pour ameliorer la production d'ether a indice d'octane eleve et la conversion d'olefines dans l'essence

Info

Publication number
EP0424511A1
EP0424511A1 EP90907833A EP90907833A EP0424511A1 EP 0424511 A1 EP0424511 A1 EP 0424511A1 EP 90907833 A EP90907833 A EP 90907833A EP 90907833 A EP90907833 A EP 90907833A EP 0424511 A1 EP0424511 A1 EP 0424511A1
Authority
EP
European Patent Office
Prior art keywords
olefins
gasoline
hydrocarbons
etherification
olefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90907833A
Other languages
German (de)
English (en)
Inventor
Mohsen Nadimi Harandi
Hartley Owen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mobil Oil AS
ExxonMobil Oil Corp
Original Assignee
Mobil Oil AS
Mobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mobil Oil AS, Mobil Oil Corp filed Critical Mobil Oil AS
Publication of EP0424511A1 publication Critical patent/EP0424511A1/fr
Withdrawn legal-status Critical Current

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C10G2300/1092—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
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/30—Aromatics
    • 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 process for the conversion of light olefins to ethers including methyl tertiary butyl ether and high octane gasoline. More particularly, the invention relates to the catalytic hydration and etherification of light olefins to produce mixed ethers followed by unreacted olefins aromatization or conversion to gasoline.
  • the mixed ether products of the integrated process are useful as high octane blending stocks for gasoline.
  • isobutylene 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
  • the feedstock for the etherification reaction may be taken from a variety of refinery process streams such as the unsaturated gas plant of a fluidized bed catalytic cracking operation containing mixed light olefins, preferably rich in isobutylene.
  • Light olefins such as propylene and isomers of butene other than isobutylene in the feedstock are essentially unreactive toward alcohols under the mild, acid catalyzed etherification reaction conditions employed to produce lower alkyl tertiary butyl ether.
  • the further utilization, without recycle, of these unreacted olefins and alcohols to meet the overall product goals of the process would be a welcomed improvement.
  • IPA isopropyl alcohol
  • DIPE diisopropyl ether
  • the petrochemicals industry also produces mixtures of light olefin streams in the C_ and 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 blending stocks for gasoline.
  • the catalytic hydration of olefins to provide alcohols and ethers is a well-established art and is of significant commercial importance. Representative olefin hydration processes are disclosed in U. S. Patents Nos. 2,262,913; 2,477,380; 2,797,247;
  • Olefin hydration employing zeolite catalysts is known.
  • lower olefins, in particular propylene are catalytically hydrated over a crystalline aluminosilicate zeolite catalyst having a silica to alumina ratio of at least 12 and a Constraint Index of from 1 to 12, e.g., acidic ZSM-5 type zeolite, to provide the corresponding alcohol, essentially free of ether and hydrocarbon by-product.
  • ether from secondary alcohols such as isopropanol and light olefins is known.
  • DIPE is produced from IPA and propylene in a series of operations employing a strongly acidic cation exchange resin as catalyst.
  • the surprising discovery has been made that conversion of the light alkenes component of a hydrocarbon feedstream for high octane ether production can be substantially increased by serially integrating the initial iso-olefins etherification step with processes capable of converting unreacted light olefins to alcohols and ethers by hydration and etherification, followed by aromatization or oligomerization of remaining unreacted olefins to higher hydrocarbons such as gasoline and distillate.
  • the process enhances the production of both the desirable tertiary alkyl ethers as well as iso-ethers.
  • the process comprises the following steps: (a) reacting a fresh mixture of excess lower alkanol and said hydrocarbon feedstock in the presence of acidic etherification catalyst under etherification conditions whereby an etherification effluent stream containing lower alkyl tertiary alkyl ethers, unreacted lower alkanol and linear C.+ olefinic hydrocarbons is produced;
  • step (d) separating step (c) effluent stream and recovering said oxygenates containing high octane ethers and a stream containing unreacted linear C - olefins and alkanol by-product;
  • step (e) contacting said unreacted linear olefins stream with an acidic metallosilicate catalyst in a conversion zone under olefins conversion conditions at elevated temperature whereby higher molecular weight gasoline boiling range hydrocarbons are produced.
  • step (d) unreacted olefins stream containing alkanol by-product is separated and the olefins portion is passed to step (e) .
  • step (c) hydration zone may be a common hydration zone for C- and C. hydrocarbons or a two reactor system to upgrade C- and C hydrocarbons separately under different conditions.
  • the C 3 hydrocarbon feedstream to the hydration and etherificaton step is omitted and only unreacted olefins from the iso-olefin etherificaton step are reacted in the hydration and etherification zone.
  • the Figure is a flow schematic of the process of the present invention.
  • the principal components of known processes are integrated in a manner providing a highly advantageous and surprising advancement in refinery technology leading to the production of high octane gasoline blending components as well gasoline distillate and/or aro atics.
  • Known processes are combined in a unique configuration that provides enhancement of the performance of component processes, achieving surprising advantages for the integrated process.
  • the processes integrated include the etherification of tertiary olefins to produce lower alkyl tertiary alkyl ethers such as MTBE (methyl tertiary butyl ether) and TAME (methyl tertiary amyl ether) , olefins hydration to produce alcohols and ethers and olefins conversion over zeolite catalyst to produce gasoline (MOG-Mobil Olefins to Gasoline process) , distillate (MOGD-Mobil Olefin to Gasoline and Distillate process) or aromatics (M-2 Forming-Mobil Aromatization process) .
  • Olefin feedstock may be produced, in entirety or in part, by including a paraffins dehydrogenation step in the process.
  • Lower alkyl in the present invention refers to C 1 -C 4 al yl derived from etherification using methanol, ethanol, 1-propanol, isopropanol, 2-butanol and 1-butanol.
  • Tertiary alkyl refers to C . -C ⁇ tertiary alkyl groups derived from the etherification of tertiary olefins such as isobutene and isoamylene.
  • oxygenates or oxygenate as used herein comprises, individually or in combination, C.-C- lower aliphatic, acyclic alcohols or alkanol and symmetrical or unsymmetrical C 2 ⁇ ethers.
  • the process of the present invention is directed to maximizing the utilization of C_-C. refinery streams for the production of those gasoline range oxygenated species, or oxygenates, known to exhibit high octane numbers which are useful for gasoline product blending.
  • Table 1 lists some of those oxygenated species of particular interest as products of the present invention.
  • Methyl Tertiary Butyl Ether 120 100 Di-isopropyl ether (DIPE) 109 99
  • IPTBE Isopropyl Tertiary Butyl Ether
  • Isobutylene etherification conditions are known in the art and, in the instant invention, comprise mild conditions of low temperature and high liquid hourly space velocity (LHSV) .
  • Isobutylene etherification temperature can range from 20°C to 150°C and preferably between 60 and 125°C.
  • methanol is reacted with C_-C. olefinic hydrocarbon feedstock such as FCC unsaturated gas containing olefins, particularly iso-olefins, to produce methyl tertiary butyl ether.
  • olefinic hydrocarbon feedstock such as FCC unsaturated gas containing olefins, particularly iso-olefins
  • methanol is generally present in a stoichiometric excess amount between 1 and 100 percent, based upon isobutylene.
  • Unreacted alkanol such as methanol largely will end up in the MTBE product as a result of azeotrope formation during fractionation. Typically, this would present problems of an aqueous phase formation in gasoline.
  • isopropyl alcohol (IPA) and sec-butyl alcohol (SEC) formed in subsequent olefin hydration steps of the overall process mitigates against two phase formation by solubilizing methanol in the gasoline pool.
  • 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 ay 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%.
  • the etherification catalyst employed is preferably an ion exchange resin in the hydrogen form; however, any suitable acidic catalyst may be employed.
  • acidic solid catalysts such as, sulfonic acid resins, phosphoric acid modified kieselguhr, silica alumina and acid zeolites such as zeolite beta and ZSM-5.
  • Typical hydrocarbon feedstock materials for etherification reactions include olefinic streams, such as FCC light naphtha and butenes rich in iso-olefins. These aliphatic streams are produced in petroleum refineries by catalytic cracking of gas oil or the like.
  • a preferred catalyst is a bifunctional ion exchange resin which etherifies and isomerizes the reactant streams.
  • a typical acid catalyst is Amberlyst 15 sulfonic acid resin, a product of Rohm and Haas Corporation.
  • MTBE is known to be a high octane ether.
  • the blending value of MTBE at the 10% level is 103.
  • the blending value of 10% MTBE is 114.
  • the operating conditions of the olefin hydration process herein are not especially critical and include a temperature of from 60 to 450°C, preferably from 90 to 220°C and most preferably from 120 to 200°C, a pressure of from 120 to 200'C, a pressure of from 690 to 16.6X10 kPa (100 to 3500 psi) , preferably from 3.45X10 3 to 13.8X10 3 kPa (500 to 2000 psi) , a water to olefin mole ratio of from 0.1 to 30, preferably from 0.2 to 15 and most preferably from 0.3 to 3.
  • the olefin hydration process of this invention can be carried out under dense phase, liquid phase, vapor phase or mixed vapor-liquid phase conditions in batch or continuous manner using a stirred tank reactor or fixed bed flow reactor, e.g., trickle-bed, liquid-up- flow, liquid-down-flow, counter-current, co-current, etc. Reaction times of from 20 minutes to 20 hours when operating in batch and an LHSV of from 0.1 to 20, preferably 0.1-2, when operating continuously are suitable. A portion of unreacted olefin may be recovered and recycled to the reactor.
  • the catalyst employed in the olefin hydration and etherification operations which are connected sequentially downstream of isobutylene etherification operations is shape-selective acidic zeolite.
  • the useful catalysts embrace two categories of zeolite, namely, the intermediate pore size variety as represented, for example, by ZSM-5, which possess a Constraint Index of greater than 2 and the large pore variety as represented, for example, by zeolites Y, Beta and ZSM-12, which possess a Constraint index no greater than 2.
  • Preferred catalysts include Zeolite Beta, Zeolite Y, ZSM-12, ZSM-5 and ZSM-35. Both varieties of zeolites will possess a framework silica-to-alumina ratio of greater than 7.
  • zeolite is meant to include the class of porotectosilicates, i.e., porous crystalline silicates, which contain silicon and oxygen atoms as the major components.
  • Other components can be present in minor amounts, usually less than 14 mole %, and preferably less than 4 mole %. These components include aluminum, gallium, iron, boron, and the like, with aluminum being preferred.
  • the minor components can be present separately or in mixtures in the catalyst. They can also be present intrinsically in the framework structure of the catalyst.
  • the framework silica-to-alumina mole ratio referred to can be determined by conventional analysis.
  • This ratio is meant to represent, as closely as possible, the mole ratio of silica to alumina in the rigid anionic framework of the zeolite crystal and to exclude any alumina which may be present in a binder material optionally associated with the zeolite or present in cationic or other form within the channels of the zeolite.
  • zeolites as otherwise characterized herein but which are substantially free of aluminum, i.e., having silica-to-alumina mole ratios up to and including infinity, are useful and can even be preferable in some cases.
  • a convenient measure of the extent to which a zeolite provides controlled access to molecules of varying sizes to its internal structure is the afore entioned Constraint Index of the zeolite.
  • a zeolite which provides relatively restricted access to, and egress from, its internal structure is characterized by a relatively high value for the Constraint Index, i.e., above 2.
  • zeolites which provide relatively free access to the internal zeolitic structure have a relatively low value for the Constraint Index, i.e., 2 or less.
  • the method by which Constraint Index is determined is described fully in U.S. Patent No. 4,016,218.
  • Useful zeolite catalysts of the intermediate pore size variety, and possessing a Constraint Index of greater than 2 up to 12, include such materials as ZSM-5, ZSM-11, ZSM-23, ZSM-35, and ZSM-38.
  • ZSM-5 is more particularly described in U.S. Reissue Patent No. 28,341 (of original Patent No. 3,702,886);
  • ZSM-11 is more particularly described in U.S. Patent No. 3,709,979;
  • ZSM-23 is more particularly described in U.S. Patent No. 4,076,842;
  • ZSM-35 is more particularly described in U.S. Patent No. 4,016,245; and
  • ZSM-38 is more particularly described in U.S. Patent No. 4,046,859.
  • ZSM-38 possesses a Constraint Index of 2.0, it is often classified with the intermediate pore size zeolites and will therefore e regarded as such for purposes of this invention.
  • the large pore zeolites which are useful as catalysts in the process of this invention, i.e., those zeolites having a Constraint Index of no greater than 2, are well known to the art.
  • zeolites are zeolite Beta, zeolite X, zeolite L, zeolite Y, ultrastable zeolite Y (USY) , dealuminized Y (Deal Y) , rare earth-exchanged zeolite Y (REY) , rare earth-exchanged dealuminized Y (RE Deal Y) , mordenite, ZSM-3, ZSM-4, ZSM-12, ZSM-20, and ZSM-50 and mixtures of any of the foregoing.
  • zeolite Beta has a Constraint Index of 2 or less, it should be noted that this zeolite does not behave exactly like other large pore zeolites.
  • zeolite Beta does satisfy the requirements for a catalyst of the present invention.
  • Zeolite Beta is described in U.S. Reissue 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 is described in U.S. Patent No. 3,216,789;
  • Zeolite Y is described in U.S. Patent No. 3,130,007.
  • Dealuminized zeolite Y (Deal Y) can be prepared by the method found in U.S. Patent No. 3,442,795.
  • Zeolite ZSM-3 is described in U.S.Patent No. 3,415,736; Zeolite ZSM-4 is described in U.S. Patent No. 3,923,639; Zeolite ZSM-12 is described in ⁇ .S.Patent No.3,832,449, Zeolite ZSM-20 is described in U.S.Patent No.3,972,983; and Zeolite ZSM-50 is described in U.S. Patent No. 4,640,829.
  • crystalline porous silicoaluminophosphates such as those disclosed in U.S. Patent No. 4,440,871, the catalytic behavior of which is similar to that of the aluminosilicate zeolites.
  • the zeolite(s) selected for use herein will generally possess an alpha value of at least 1 and preferably at least 10.
  • alpha value of at least 1 and preferably at least 10.
  • the most preferred alpha value for fresh catalyst is at least 400.
  • "Alpha value”, or "alpha number” is a measure of zeolite acidic functionality and is more fully described together with details of its measurement in U.S. Patent No. 4,016,218, J. Catalysis, 6., pp. 278-287 (1966) and J. Catalysis, 61, pp. 390-396 (1980) .
  • Zeolites of low acidity can be achieved by a variety of techniques including (a) synthesizing a zeolite with a high silica/alumina ration, (b) steaming, (c) steaming followed by dealu inization and (d) substituting framework aluminum with other species.
  • the zeolite(s) can be exposed to steam at elevated temperatures ranging from 260 to 650 ⁇ C and preferably from 400 to 540°C.
  • This treatment can be accomplished in an atmosphere of 100% steam or an atmosphere consisting of steam and a gas which is substantially inert to the zeolite.
  • a similar treatment can be accomplished at lower temperatures employing elevated pressure, e.g., at from about 177 to 370 ⁇ C with from 10 to 200 atmospheres (1013.0 to 20260 kPa) .
  • Specific details of several steaming procedures may be gained from the disclosures of U.S. Patent Nos. 4,325,994; 4,374,296; and 4,418,235.
  • the surface acidity of the zeolite(s) can be eliminated or reduced by treatment with bulky reagents as described in U.S. Patent No. 4,520,221.
  • zeolite(s) In practicing the olefin hydration and etherification process of the present invention, it can be advantageous to incorporate the zeolite(s) into some other material, i.e., a matrix or binder, which is resistant to the temperature and other conditions employed in the process.
  • a matrix or binder which is resistant to the temperature and other conditions employed in the process.
  • Useful matrix materials include both synthetic and naturally-occurring substances, e.g., inorganic materials such as clay, silica and/or metal oxides. Such materials can be either naturally-occurring or can be obtained as gelatinous precipitates or gels including mixtures of silica and metal oxides.
  • Naturally-occurring clays which can be composited with the zeolite include those of the montmorillonite and kaolin families, which families include the sub-bentonites and the kaolins commonly known as Dixie, McNa ee-Georgia and Florida clays or others in which the main mineral constituent is haloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.
  • c + hydrocarbons feedstock are passed 310 to etherification zone 320 containing an acidic catalyst under tertiary olefin etherification conditions as previously described herein in conjunction with methanol feedstream 315.
  • methanol may be in excess of the stoichiometric amount to etherify tertiary olefins in the hydrocarbon feedstock to assure essentially complete conversion to the corresponding lower alkyl tertiary alkyl ether.
  • the excess can be between 1-100%, but preferably 30%.
  • the etherification effluent stream is separated by distillation to yield C 5 + ether rich gasoline 330 containing MTBE and a portion of unreacted methanol.
  • the remaining unreacted methanol and linear C.- olefins are passed 340 to the hydration and etherification zone 350 in contact with catalyst and under such condition as described previously herein.
  • Water and C. hydrocarbon feedstock 360 containing propylene are also introduced to the hydration zone 350 wherein olefins are hydrated to alcohols and alcohols etherified.
  • C_ feedstream to the hydration zone
  • C_ hydration can be carried out in a separate reaction vessel as part of hydration zone 350.
  • the products are separated 365 as primarily acyclic lower aliphatic oxygenates including mixed ethers.
  • the oxygenates comprise isopropyl alcohol, 2-butanol, di-isopropyl ether, di-butyl ether, methyl sec-butyl ether, methyl isopropyl ether.
  • An unreacted C.- hydrocarbon stream 370 is passed to conversion zone 380 under olefins to gasoline conversion conditions at elevated temperature in contact with zeolite catalyst such as ZSM-5. C g + gasoline 385 is produced. Other effluents from the conversion zone may include LPG 390 and C 2 ⁇ hydrocarbon 395.
  • the C.-hydrocarbon stream 370 may be converted to gasoline and distillate, or aromatics, in contact with zeolite catalyst under conditions well known in the art and described in the referenced patents herein before.
  • all or a portion of effluent stream 340 may be passed to unit 380 through conduit 305.
  • acidic zeolite such as ZSM-5 in each of the individual process steps: iso-olefin etherification, linear olefin hydration and etherification, and olefin conversion to higher molecular weight product. Accordingly, when the same catalyst is used a common catalyst regeneration system may be used. This feature of the invention provides a significant occasion for cost savings.

Landscapes

  • 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)
  • Catalysts (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé intégré de conversion d'oléfines C3+ et/ou C4+ pour en faire des éthers, des alcools et des hydrocarbures, dont la limite d'ébullition est celle de l'essence, à indice d'octane élevé. L'invention concerne l'éthérification d'oléfines tertiaires C4+ (310) avec de l'alcanol inférieur (315) pour obtenir de l'alcoyl-éther tertiaire d'alcoyle inférieur (330) dans un premier étage d'éthérification (320), dans des conditions douces, ainsi que l'hydratation d'oléfines linéaires (340) et leur éthérification à l'aide d'un catalyseur acide dans un second étage subséquent (350) pour obtenir des produits oxygénés à indice d'octane élevé supplémentaires (365). On fait passer les oléfines qui n'ont pas réagi dans une zone de conversion d'oléfines en contact avec un catalyseur à zéolite pour les transformer en essence (385), en distillat ou en aromatiques. L'invention porte en particulier sur un procédé intégré pur convertir un substrat d'hydrocarbures comprenant des oléfines C3-C4 contenant de l'isobutylène pour en faire de l'alcool et des éthers à indice d'octane élevé, y compris MTBE et TAME (éther de butyle tertiaire de méthyle et éther de méthyle d'amyle tertiaire).
EP90907833A 1989-04-24 1990-04-23 Procede integre pour ameliorer la production d'ether a indice d'octane eleve et la conversion d'olefines dans l'essence Withdrawn EP0424511A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US34213389A 1989-04-24 1989-04-24
US342133 1989-04-24

Publications (1)

Publication Number Publication Date
EP0424511A1 true EP0424511A1 (fr) 1991-05-02

Family

ID=23340491

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90907833A Withdrawn EP0424511A1 (fr) 1989-04-24 1990-04-23 Procede integre pour ameliorer la production d'ether a indice d'octane eleve et la conversion d'olefines dans l'essence

Country Status (5)

Country Link
EP (1) EP0424511A1 (fr)
JP (1) JPH03505608A (fr)
AU (1) AU621486B2 (fr)
CA (1) CA2030797A1 (fr)
WO (1) WO1990012854A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE37142E1 (en) 1995-02-08 2001-04-24 Millennium Fuels Usa Llc Refining process and apparatus
USRE37089E1 (en) 1995-02-08 2001-03-13 Millennium Fuels Usa Llc Refining process and apparatus
CN102343279A (zh) * 2011-07-18 2012-02-08 天津市福生染料厂 用c4烯烃制备清洁汽油及催化剂制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2456084A1 (fr) * 1979-05-09 1980-12-05 Inst Francais Du Petrole Procede de preparation et d'isolement du methyl tertiobutyl ether
EP0123338B1 (fr) * 1983-04-01 1987-07-29 Stamicarbon B.V. Procédé pour la préparation d'éther méthyl-tert-butylique
US4906788A (en) * 1987-07-01 1990-03-06 Uop Combined dehydrogenation etherification process
US4826507A (en) * 1987-12-08 1989-05-02 Mobil Oil Corporation Integrated etherification and oxygenates to gasoline process
US4835329A (en) * 1987-12-08 1989-05-30 Mobil Oil Corporation Process for producing high octane gasoline
US4788365A (en) * 1987-12-08 1988-11-29 Mobil Oil Corporation High octane gasoline and distillates from oxygenates
US4830635A (en) * 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US4827046A (en) * 1988-04-11 1989-05-02 Mobil Oil Corporation Extraction of crude methanol and conversion of raffinate
US4827045A (en) * 1988-04-11 1989-05-02 Mobil Oil Corporation Etherification of extracted crude methanol and conversion of raffinate
US4886925A (en) * 1988-05-02 1989-12-12 Mobil Oil Corp Olefins interconversion and etherification process
US4925455A (en) * 1989-03-17 1990-05-15 Mobil Oil Corporation Process for the etherification of linear and branched olefins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9012854A1 *

Also Published As

Publication number Publication date
AU621486B2 (en) 1992-03-12
JPH03505608A (ja) 1991-12-05
CA2030797A1 (fr) 1990-10-25
WO1990012854A1 (fr) 1990-11-01
AU5556090A (en) 1990-11-16

Similar Documents

Publication Publication Date Title
US4886925A (en) Olefins interconversion and etherification process
EP0320180B1 (fr) Procédé intégré pour éthérification et la production de l'essence à partir de composés oxygénés
US4788365A (en) High octane gasoline and distillates from oxygenates
US5166455A (en) Process for the production of tertiary alkytl ethers from FCC light naphtha
US4835329A (en) Process for producing high octane gasoline
US5041690A (en) Conversion of alcohols to ether-rich gasoline
US4981491A (en) Production of ether-rich fuel
US5130101A (en) Reactor system for conversion of alcohols to ether-rich gasoline
EP0424154B1 (fr) Procédé intégré pour la production de l'éther di-isopropylique et de l'essence
US5047070A (en) Integrated process for production of gasoline and ether from alcohol with feedstock extraction
AU633080B2 (en) Conversion of alcohols to ether-rich gasoline
US4854939A (en) Aromatization and etherification process integration
US5024679A (en) Olefins etherification and conversion to liquid fuels with paraffins dehydrogenation
US5011506A (en) Integrated etherification and alkene hydration process
AU621486B2 (en) Integrated process for enhancing high octane ether production and olefin conversion in gasoline
JPH0395133A (ja) 軽質オレフィンの水和およびアルキルｔ―ブチルエーテルの製造方法
EP0556174B1 (fr) Procede d'etherification
US4957709A (en) Reactor system for olefin conversion and etherification
US5225609A (en) Production of tertiary alkyl ether using improved zeolite catalyst
JPH04233994A (ja) 第３級アルキルエーテルおよびガソリンの製造におけるｃ３〜ｃ４パラフィンの複合転化方法
WO1990011267A1 (fr) Nouvelle methode de separation integree pour procedes de production de di-isopropyle ether et de methyle tertiaire alkyle ether
WO1989009810A1 (fr) Etherification et transformation d'olefines en carburants liquides avec deshydrogenation de paraffines

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19901210

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE FR GB IT NL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Withdrawal date: 19920612

R18W Application withdrawn (corrected)

Effective date: 19920622