CA2031212A1 - 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

Info

Publication number
CA2031212A1
CA2031212A1 CA002031212A CA2031212A CA2031212A1 CA 2031212 A1 CA2031212 A1 CA 2031212A1 CA 002031212 A CA002031212 A CA 002031212A CA 2031212 A CA2031212 A CA 2031212A CA 2031212 A1 CA2031212 A1 CA 2031212A1
Authority
CA
Canada
Prior art keywords
hydrocarbon
liquid
alcohol
methanol
reactor
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.)
Abandoned
Application number
CA002031212A
Other languages
French (fr)
Inventor
Mohsen N. 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.)
ExxonMobil Oil Corp
Original Assignee
Individual
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
Priority claimed from US07/358,097 external-priority patent/US5047070A/en
Application filed by Individual filed Critical Individual
Publication of CA2031212A1 publication Critical patent/CA2031212A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/05Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS 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
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/02Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1088Olefins
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081Recycling aspects
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02Gasoline
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock

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)

Abstract

INTEGRATED PROCESS FOR PRODUCTION OF GASOLINE AND
ETHER FROM ALCOHOL WITH FEEDSTOCK EXTRACTION

ABSTRACT

Alcohol feedstock containing water is extracted with olefinic liquid and reacted catalytically to produce tertiary ether. Unreacted alcohol and olefin vapor separated from etherification effluent is converted along with aqueous alcoholic raffinate in a zeolite catalysis step to produce gasoline and paraffinic intermediate. By dehydrogenating the C3-C5 paraffins, an olefinic liquid rich in isoalkenes is obtained for recycle to the extractor as solvent for alcohol feedstock.

Description

2~1212 INTEGRATED PROCES FOR PRODUCTION OF GASOLINE AND ETHE~3 FROM ALCOHOL WITH FEEDSTOCK EXTRACTION

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. In particular, 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 ol fins, such as C4-C5 normally liquid iso-olefins.
Technical progress of the commercial methanol-to-gasoline MTG process has provided an important synthetic fuel source. Also, there has been considerable development of processes synthetic alkyl tertiary-alkyl ethers as octane boosters in place of conventional lead additives in gasoline. The etherification processes for the produc ion of methyl tertiary alkyl ethers, in particular methyl t-butyl ether (MTBE) and t-amyl methyl ether (TAME) have been the focus of considerable research attention to resolve certain limitations in the etherification process with respect to the opportunity to drive the equilibrium dependent etherification reaction to completion by conducting etherification in the presence of excess methanol. It is known that recovering unreacted methanol by conventional separation and extraction techniques imposes severe economic burdens on the etherification process.
Recognizing the common feedstock (e.g. - methanol) for the synthetic production of gasoline as well as the production of methyl tertiary alkyl octane boosting ethers, research workers have endeavored to combine 2~3~21 2 these processes in a manner to provide a synergistically bene~icial integrated process.
It is known that isobutylene and other isoalkenes producPd by hydrocarbon cracking may be reacted with methanol, ethanol, isopropanol and other lower aliphatic primary and secondary alcohols over an acidic catalyst to provide tertiary ethers. Methanol is considered the most important Cl-C4 oxygenate feedstock because of its widespread availability and low cost.
Therefore, primary emphasis herein is placed on MTBE
and TAME. ~ethanol may be readily obtained from coal by gasiflcation to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial prooesses. 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. %; howeverr the present invention is useful for removing water in lesser amounts or greater.
It is an object of the present invention to provide a novel and economic technique for removing excess water from crude methanol feedstocks, including novel reactor systems and equipment for treating oxygenate feedstocks prior to etherification and disposing of raffinate containing methanol. It has been discovered that aqueous methanol streams, such as etherification feedstock extraction raffinate can be economically upgraded to valuable gasoline product by catalytic conversion concurrently with hydrocarbons.
A continuous process has been provided for converting crude lower aliphatic alcohol to alkyl tertiary-alkyl ethers and gasoline comprising the st~ps of:
(a) contacting a crude alcohol feedstock containing a minor amount of water with a liquid 2~3~212 olefinic hydrocarbon extraction solvent stream rich in C4 iso-alkene hydroc~rbon under extraction conditions favorable to selective extraction of the alcohol, there~y providing a non-aqueous organic extract liquid str~am rich in alcohol and an aqueous raffinate stream containing unextracted alcohol;
(b) charging liquid hydrocarbon extractant and extracted alcohol substantially free of water to a first etherification catalytic reaction zone for contact with acid etherification catalyst under etherification process conditions for converting alcohol and iso-alkene hydrocarbon to predominantly tertiary-alkyl ether;
(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;
(d) catalytically con~erting aqueous raffinate from step (a) in contact with medium pore acid zeolite catalyst in a second oxygenate conversion reaction ~one concurrently with catalytic upgrading of unreacted alcohol the olefinic overhead stream of step (c) to provide predominantly liquid C6 ~ hydrocarbon product along with C3-C5 alkane intermediate product, water, and light gas;
(e) separating water and light gas from step (d) to recover C3-C5 alkane-rich intermediate and C6 +
hydrocarbon product;
(f) dehydrogenating alkane intermediate from step (e) to provide an olefinic hydrocarbon liquid rich in iso-alkenes; and (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.

2~3:12~2 Typical feedstock materials for etherification reactions include olefinic streams, such as FCC light naphtha and butenes rich in iso~olefins. Typically, these aliphatic strea~s are produced in petroleum refineries by catalytic cracking of gas oil or the like. The crude methanol commercially available from syngas processes may con~Ain, ~or instance 4 to 17 wt.
% water, which mus~ be removed, preferably to a methanol purity o~ 99.8 wt. %. It has been found that more than 75% of crude feedstock methanol can be recovexed by liquid extraction with light olefinic liquid extraction solvent, such as propylene, iso-butylenes, iso-amylene~ and other C3-C5 light hydrocarbons. The typical feed ratio range is 2 to 8 parts hydrocarbon extractant per part by volume of methanol.
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. In the present reactor system, isobutane-rich C3-C5 parafins from the MTG
process may be converted to iso-alkenes. The overall yield o~ high octane gasoline from oxygenate conversion is significantly increased. In a further improvement, 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 C1-C4 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 DM~
intermediate. Typically, a mixture (CH30H ~ CH3-0-CH3 + H20) is produced by partial dehydration. This reaction can take place in direct conversion of methanol to gasoline (MTG).

2~312~2 F-5262 -5~

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. In a typical fixed-bed MTG
process relatively large amounts of isobutane are produced, e.g., 8% by weight of hydrocarbons productO
In the past, it has been the practice to recover the isobutane fraction without an immediate upgrading step.
In fluidized bed MTG operations, isobutane pro~uction may be optimized in the range of 5-I0 wt. % of hydrocarbon effluent.
Overall the production of MTG gasoline plus ethers will increase blended gasoline pool octane because of their high component octanes. Ethene-containing gas from dehydxogenation can be routed directly or indirectly to the ~rG unit to react C2= to gasoline.
This will eliminate the need for cryogenic separation required to separate ethene. The desired MTG products are C4 and C5 iso-alkanes, which will ordinarily comprise at least 5% of the recovered product.
Referring to the drawing, a continuous stream of crude methanol (MeOH) feedstock is introduced via conduit 10 with a s~ream of olefinic hydrocarbon liquid extractant introduced via conduit 12 to extraction separation unit 14, operated at 35-40C. These streams are contacted under liquid extraction conditions to provide an aqueous raffinate phase. An aqueous stream containing a major amount of the wa~er present in the crude feedstock is withdrawn via conduit 16. The lighter organic extract phase containing hydrocarbon ~xtraction solvent and the major amount of feadstock 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 2~ 2~2 F--52 62 -6~

ratio o~ reactants as desired. Flow control means can be employed to measure streams 12 and 18 and provide increased or decreas~d fresh feed through line 10 in response to a predetermined ratio, as understood by S 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.
From reactor 30, the effluent stream 22 passes to a debutanizer fractionation tower 30. In debutanizer separation unit 30 the C5 + tert-alkyl ether product (~BE and/or TAME) is recovered as a liquid product stream 32, along with unreacted C5 (or optionally heavier C6) hydrocarbons in the extractant.
Fractionation tower overhead vapor comprising unreacted c4 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. -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 , etcO, 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.
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 C3-C5 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 2 0 ~ 2 unit operations to produce a hydrogen byproduct gas and an ol~finic product consisting essentially of C2-C5 olefins. All or a portion of the 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 ra~finate stream may be coreacted with olefinic light gas and/or other reactive hydrocar~on feedstreams in a conventional MTG reaction section, as described by Tabak in U.S. Patant 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 e~fluent vapor from the etherification unit. Optionally, etherification effluent ovarhead and/or C2-C5 olefinic light hydrocarbon gas containing ethene, propene, unreacted butylenes, etc., may be injected at the bottam 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 ~eedstock is intimately contacted with a substantially immiscible liquid hydrocarbon solvent, which may be a mixture of C4 + aliphatic components including lower alkanes, n-alkenes or relatively pure isoalkenes, such as isobutylene~ etc.
This unit operation is described in Kirk-Othmer 2~3~2~2 Encyclopedia of Chemical Technology (Third Ed.), 1980, pp.672-721. Other equipment ~or extraction is disclosed in US Patents 4,349,415 (DeFilipi et al), 4,626,415 (Tabak), and 4,665,237 (Arakawa et al). Unit operation de~ails are also disclosed by Harandi and Owen in U.S. Patent 4,777,321. 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.
In a typical methanol extraction the crude aqueous feedstock containing 4% water is contacted with olefinic liquid hydrocarbons in a liquid-liquid contact and separation unit at 38C (100F). The extractor unit is operated at 35-65C (100-150F) and 0-2000 kPa.
The reaction of methanol with isobutylene and isoamylenes at moderate conditions with a resin catalyst is known technology, as provided by R. W~
Reynolds, et al., The Oil and Gas Journal, June 16, 1975, and S. Pecci and T. Floris, Hydrocarbon Processinq, December 1977. An article entitled "MTBE
and TAME - A Good Octane Boosting Combo", by J. D.
Chase, et al., The Oil and Gas Journal, April 9, 1979, pages 149-152, discusses the technology. A preferred catalyst is a sulfonic acid ion exchange resin which etherifies and isomerizes the reactants. A typical acid catalyst is Amberlyst lS sulfonic acid resin.
Processes for producing and recovering MTBE and other methyl tert-alkyl ethers for C4-C7 isoolefins are known to those skilled in the art, such as disclosed in U.S. Patent 4,788,365 (Harandi and Owen). Various suitable extraction and distillation techniques are known for recovering ether and hydrocarbon streams from etherication effluent.
Zeolite catalysis technology for upgrading lower aliphatic hydrocarbons and oxygenates to liquid 2~3.~2:L2 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 C5-Cg gasoline range.
Recent developments in zeolite technology have provided a group of medium pore siliceous materials having similar pore geometry. Most prominent among these intermediate pore size zeolites is ZSM-5, which is usually synthssized 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-selecti~e 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 sev~rity.
Representative of the ZS~-5 type medium pore shape ~31~2 selective zeolites are ZSM-5, ZSM-ll, 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,~76,8~2; 4,016,245; 4,414,423; 4,417,086;
4,517,396 and 4,542,251. While suitable 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:~ 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.
Usually the zeolite crystals have a crystal size from 0.01 to 2 microns or more. In order to obtain the desired particle size for fluidization in the turbulent regime, 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. %.
It is advantageou~ to employ a standard ZSM-5 having a silica:alumina molar ratio of 25:1 or greater in a once-through ~luidized bed unit to convert 60 to 100 percent, preferably at least 75 wt. %, o~ the monoalkenes and methanol in a single pass. I~ the preferred embodiment 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 2~2~ 2 advantageous to employ a particle size range consisting essentially of 1 to 150 microns. Average particle size is usually 20 to lO0 micronsl preferably 40 to 80 microns. Particle distribu~ion 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 o~ fines. Close control of distribution can be maintain~d to keep 10 to 25 wt.
~ of the total catalyst in t~e 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.
In addition to the aqeuous methanol an olefinic components of the reactor feed, suitable oxygenate and or 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 C3-C5 paraffins, olefinic gasoline or C6-C8 BTX hydrocarbons, according to product demand. It is understood that aromatic hydrocarbon and ligh~ paraffin production is promoted by those zeolite catalysts havinq 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 ~he reaction severity is maintained within the limits which yield a desired weight ratio of propane to propene in the reaction effluent.
In a turhulent fluidized catalyst bed the conversion reactions are conducted in a vertical reactor column by passing hot reactan~ vapor or lift 2~312~2 F-5262 -l2-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 ~atalyst activity and reaction severity to effect feedstock conversion.
Upgrading of olefins by such hydrogen contributors in co-conversion reactors is taught by Owen et al in U. S. Patents 4,788,365, 4,090,949, and 4,827,046. In a typical process, the methanol and olefinic feedstreams are converted in a catalytic reactor under elevated temperature conditions and moderate pressure (i.e. - l00 to 2500 kPa) to produce a predominantly liquid product consisting essentially of C6 hydrocarbons rich in gasoline-range paraffins and aromatics. The reaction temperature can be carefully controlled in the usual operating range of about 250~C.
to 650C., preferably at average reactor temp~rature of 350C to 500C.
An important unit operation in the conversion of iso-paraffins to their corresponding iso-olefins is dehydrogenation. Conventionally this can be achieved by high temperature cracking using hydrogenation-dehydrogenation catalyst; however, it is within the inventive concept to employ transhydrogenation in this process step to ef~ect removal of hydrogen ~rom the C3-C5 intermediate alkanes. Various processes are known for producing isoalkene-rich by dehydrogenation (including isomerization processes), such as disclosed in U.S.
Patent 4,393,250 (Gottlieb et al~. Typical processes are operated at elevated temperature (530-700OC) and moderate pressure using an active alumina solid catalyst impregnated with Pt or Cr oxide. Other 2~3~2~2 dehydrogenation techniques are disclosed in Oil ~ Gas Journal, 8 Dec 1980, pp 96-101; ~ydrocarbon Processing, April 1982, pp 171-4; U.S. Patent Application Serial No. 179,729, filed 11 April 1988, and in U.S. Patent ~,216,346 (Antos).
The present invention is particularly advantageous in the economic dewatering of crude methanol, thus avoiding expensive and ener~y-intensive prefractionation by di.stillation. 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 procPssing steps. Another advantage is increased C5+ gasoline yield, especially by converting a C3-C4 fraction to MTG gasoline and MTBE.

Claims (18)

CLAIMS:
1. A continuous process for converting crude methanol to methyl tertiary-alkyl ethers and gasoline comprising the steps of:
(a) contacting a crude methanolic feedstock containing a minor amount of water with a liquid olefinic hydrocarbon extraction solvent stream rich in C4 + iso-alkene hydrocarbon under extraction conditions favorable to selective extraction of the methanol, thereby providing a non-aqueous organic extract liquid stream rich in methanol and an aqueous raffinate stream containing unextracted methanol;
(b) charging liquid hydrocarbon extractant and extracted methanol substantially free of water to a first etherification catalytic reaction zone for contact with acid etherification catalyst under etherification process conditions for converting methanol and iso-alkene hydrocarbon to predominantly methyl tertiary-alkyl ether;
(c) fractionating the etherification effluent from step lb) to recover overhead vapor containing unreacted methanol and light olefinic hydrocarbon and to recover liquid product containing methyl tertiary-alkyl ether:
(d) catalytically converting aqueous raffinate from step (a) in contact with medium pore acid zeolite catalyst in a second methanol-to-gasoline reaction zone concurrently with catalytic upgrading of unreacted methanol and olefinic overhead vapor from step (c) to provide predominantly liquid C6 + hydrocarbon product along with C3-C5 alkane intermediate product, water, and light gas;
(e) separating water and light gas from step (d) to recover C3-C5 alkane-rich intermediate and C6 +
hydrocarbon product;

(f) dehydrogenating alkane intermediate from step (e) to provide an olefinic hydrocarbon liquid rich in iso-alkenes; and (g) recycling olefinic liquid from step (f) to step (a) as extraction solvent liquid for dewatering methanol feedstock.
2. The process of claim 1 wherein the acid etherification catalyst comprises ion exchange resin or acid medium pore zeolite, wherein the methanolic feedstock consists essentially of methanol and 4 to 20 wt. % water, and wherein the extraction liquid comprises a major amount of C4-C5 tertiary-alkenes.
3. The process of claim 1 wherein additional methanol is introduced with extracted methanol in step (b) to provide a stoichiometric excess of methanol over iso-alkene.
4. A continuous reactor system for converting crude lower alkyl alcohol to lower alkyl t-alkyl ethers comprising the steps of:
(a) extraction means for contacting crude aqueous alcohol feedstock containing with a liquid hydrocarbon extraction solvent rich in C4 + iso-alkene hydrocarbon under extraction conditions favorable to selective extraction of the alcohol, thereby providing an extract liquid stream rich in alcohol and an aqueous raffinate stream lean in alcohol;
(b) primary etherification reactor means operatively connected to receive the extract liquid stream for charging liquid hydrocarbon extractant and extracted methanol substantially free of water to a first catalytic reaction zone containing acid etherification catalyst for converting alcohol and iso-alkene hydrocarbon to predominantly lower alkyl t-alkyl ether;

(c) fractionation means for separating etherification effluent from reactor (b) to recover unreacted alcohol and light olefinic hydrocarbon overhead stream and to recover liquid product containing ether product;
(d) secondary catalytic reactor means for upgrading olefinic overhead vapor from fractionator (c) to provide liquid hydrocarbon product; and (e) means for charging at least a portion of said aqueous raffinate stream from extraction means (a) for conversion of alcohol to hydrocarbons concurrently with olefin upgrading in reactor (d).
5. The reactor system of claim 4 wherein the acid etherification catalyst comprises ion exchange resin.
6. The reactor system of claim 4 the secondary reactor means contains acid medium pore zeolite catalyst.
7. A continuous process for converting crude lower aliphatic alcohol to alkyl tertiary-alkyl ethers and gasoline comprising the steps of:
(a) contacting a crude alcohol feedstock containing a minor amount of water with a liquid olefinic hydrocarbon extraction solvent stream rich in C4 + iso-alkene hydrocarbon under extraction conditions favorable to selective extraction of the alcohol, thereby providing a non-aqueous organic extract liquid stream rich in alcohol and an aqueous raffinate stream containing unextracted alcohol;
(b) charging liquid hydrocarbon extractant and extracted alcohol substantially free of water to a first etherification catalytic reaction zone for contact with acid etherification catalyst under etherification process conditions for converting alcohol and iso-alkene hydrocarbon to predominantly tertiary-alkyl ether;
(c) fractionating the etherification effluent from step (b) to recover overhead stream containing unreacted alcohol and light olefinic hydrocarbon and to recover liquid product containing tertiary-alkyl ether;
(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 and olefinic overhead stream from step (c) to provide predominantly liquid C6 + hydrocarbon product along with C3-C5 alkane intermediate product, water, and light gas;
(e) separating water and light gas from step (d) to recover C3-C5 alkane-rich intermediate and C6 +
hydrocarbon product;
(f) dehydrogenating at least a fraction of alkane intermediate from step (e) to provide an olefinic hydrocarbon liquid rich in iso-alkenes; and (g) recycling olefinic liquid from step (f) to step (a) as extraction solvent liquid for dewatering alcohol feedstock.
8. A continuous process for converting lower aliphatic alcohol to alkyl tertiary-alkyl ethers and gasoline comprising the steps of:
reacting lower aliphatic alcohol with a liquid olefinic hydrocarbon stream rich in C4 + iso-alkene hydrocarbon in a first etherification catalytic reaction zone containing acid etherification catalyst under etherification process conditions for converting alcohol and iso-alkene hydrocarbon to predominantly tertiary-alkyl ether;
fractionating the etherification effluent to recover overhead vapor containing unreacted alcohol and light olefinic hydrocarbon and to recover liquid product containing tertiary-alkyl ether;
catalytically converting unreacted alcohol and olefinic overhead vapor from etherification concurrently with crude aqueous oxygenated hydrocarbon feedstock in contact with medium pore acid zeolite catalyst in a second catalytic reaction zone to provide predominantly liquid C6 + hydrocarbon product along with C3-C5 alkane intermediate product, water, and light gas;
separating water and light gas from the second reaction zone to recover C3-C5 alkane-rich intermediate and C6 + hydrocarbon product;
dehydrogenating alkane intermediate to provide an olefinic hydrocarbon rich in iso-alkenes; and recycling dehydrogenated olefinic hydrocarbon directly or indirectly to the etherification reaction zone.
9. The process of claim 8 wherein the alkane intermediate includes 5 to 10% isobutane, based on total hydrocarbon effluent from the second reacton zone.
10. The process of claim 8 wherein the etherificaton catalyst comprises sulfonic acid resin and the medium pore zeolite comprises acid ZSM-5.
11. A continuous feedstock separation and etherification reactor system for converting crude methanol feedstock to methyl t-alkyl ether comprising:
extractor means for contacting crude feedstock liquid containing a minor amount of water with a liquid olefinic hydrocarbon extraction solvent stream under extraction conditions favorable to selective extraction of methanol, thereby providing an extract liquid stream rich in methanol 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;
effluent separation means for recovering ether product from unconverted olefinic hydrocarbon and methanol; and second catalytic reactor means operatively connected for contacting said raffinate stream with conversion catalyst in the presence of said unconverted olefinic hydrocarbon and methanol to produce normally liquid C6 + gasoline product along with saturated C5 -intermediate hydrocarbon;
means for recovering a gasoline product stream and saturated intermediate hydrocarbon stream from second reactor effluent;
third reactor means for dehydrogenating at least a fraction of said C5 - intermediate hydrocarbon to produce an olefinic liquid stream rich in iso-alkene;
and means for recovering and recycling at least a fraction of the olefinic liquid stream from the third reactor means to the extractor means for use as extraction solvent.
12. A catalytic reactor system for converting oxygenate feedstock to liquid hydrocarbons comprising:
zeolite catalysis reactor means for converting oxygenate feedstock predominantly to gasoline range hydrocarbons in a MTG reactor zone in contact with acid shape selective, medium pore zeolite catalyst thereby producing a minor amount of isobutane;

separation means for recovering C6 + gasoline product and isobutane-rich C5 - paraffinic intermediate hydrocarbons from the MTG reactor effluent;
dehydrogenation reactor means for converting at least a fraction of paraffinic intermediate predominantly to C2-C5 lower olefins comprising isobutylene:
means for recovering an olefinic stream from the second reactor olefinic effluent rich in isobutylene;
means for passing the isobutylene-rich stream and a lower aliphatic alcohol stream to an etherification reactor zone in contact with etherificaton catalyst for conversion of iso-alkene to tertiary-alkyl ether; and fractionator means for recovering liquid ether product and overhead stream containing unreacted alcohol and C4 + olefins from the etherification reactor zone: and means for feeding said overhead vapor to the MTG
reactor zone for coconversion with oxygenate feedstock.
13. The system of claim 12 wherein the catalyst in the MTG reactor zone comprises acid ZSM-5.
14. The system of claim 13 wherein the MTG
reactor comprises a fixed bed of catalyst whereby isobutane is produced in the amount of 5 to 10 weight percent of hydrocarbons therein.
15. The system of claim 12 wherein the MTG
reactor comprises a fluidized bed of fine catalyst particles maintained in a vertical reactor shell, and means for introducing fractionator overhead stream below the catalyst bed for upward flow therethrough.
16. The system of claim 15 further comprising means for introducing oxygenate feedstock to the MTG

reaction zone by pumping liquid feedstock for injection therein.
17. A continuous reactor system according to Claim 12 for converting crude lower alkyl alcohol to lower alkyl t-alkyl ethers further comprising:
extraction means for contacting crude aqueous alcohol feedstock containing water with a liquid hydrocarbon extraction solvent rich in C4 + iso-alkene hydrocarbon under extraction conditions favorable to selective extraction of the alcohol, thereby providing an extract liquid stream rich in alcohol and an aqueous raffinate stream lean in alcohol;
means for operatively connecting a primary etherification reactor to receive the extract liquid stream for charging liquid hydrocarbon extractant and extracted alcohol substantially free of water to the ethericiation reaction zone for converting dewatered alcohol and iso-alkene hydrocarbon to predominantly lower alkyl t-alkyl ether; and means for charging at least a portion of said aqueous raffinate stream from the extractor means for conversion of alcohol to hydrocarbons concurrently with olefin upgrading in the MTG reactor zone.
18. The reactor system of claim 17 wherein the acid etherification catalyst comprises ion exchange resin.
CA002031212A 1989-04-24 1990-04-23 Integrated process for production of gasoline and ether from alcohol with feedstock extraction Abandoned CA2031212A1 (en)

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
US07/358,097 US5047070A (en) 1988-04-11 1989-05-30 Integrated process for production of gasoline and ether from alcohol with feedstock extraction
US358,097 1989-05-30

Publications (1)

Publication Number Publication Date
CA2031212A1 true CA2031212A1 (en) 1990-10-25

Family

ID=27407495

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002031212A Abandoned CA2031212A1 (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)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6419636B1 (en) 1998-10-02 2002-07-16 David Ernest Young System for thermometry-based breast assessment including cancer risk
US6179786B1 (en) 1998-10-02 2001-01-30 Profemme Ltd. System for thermometry-based breast cancer risk-assessment

Family Cites Families (8)

* Cited by examiner, † Cited by third party
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
US4830635A (en) * 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US4826507A (en) * 1987-12-08 1989-05-02 Mobil Oil Corporation Integrated etherification and oxygenates to gasoline process
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

Also Published As

Publication number Publication date
AU5529890A (en) 1990-11-16
EP0422188A1 (en) 1991-04-17
JPH03505603A (en) 1991-12-05
WO1990012778A1 (en) 1990-11-01

Similar Documents

Publication Publication Date Title
CA2030000C (en) Integrated process for production of gasoline and ether
US4826507A (en) Integrated etherification and oxygenates to gasoline process
US4827046A (en) Extraction of crude methanol and conversion of raffinate
US4830635A (en) Production of liquid hydrocarbon and ether mixtures
US4981491A (en) Production of ether-rich fuel
US5041690A (en) Conversion of alcohols to ether-rich gasoline
US5001292A (en) Ether and hydrocarbon production
EP0414800A1 (en) Olefins interconversion and etherification process
US5130101A (en) Reactor system for conversion of alcohols to ether-rich gasoline
US5166455A (en) Process for the production of tertiary alkytl ethers from FCC light naphtha
US5047070A (en) Integrated process for production of gasoline and ether from alcohol with feedstock extraction
US4835329A (en) Process for producing high octane gasoline
US4831195A (en) Production of ethers from methanol
US5167937A (en) Production of gasoline and ether from methanol with feedstock extraction
US5064623A (en) Integrated system for extraction of crude alcohol and co-conversion raffinate with olefin
US4854939A (en) Aromatization and etherification process integration
AU633080B2 (en) Conversion of alcohols to ether-rich gasoline
US5095159A (en) Ether and hydrocarbon production
US5026529A (en) Production of ethers from methanol
US4975097A (en) Iso-olefin etherification, upgrading and paraffin transhydrogenation
US5024679A (en) Olefins etherification and conversion to liquid fuels with paraffins dehydrogenation
US5106389A (en) Process for conversion of light paraffins to alkylate in the production of tertiary alkyl ether rich gasoline
US5260493A (en) Effluent treatment for ether production
CA2031212A1 (en) Integrated process for production of gasoline and ether from alcohol with feedstock extraction
US4957709A (en) Reactor system for olefin conversion and etherification

Legal Events

Date Code Title Description
FZDE Dead