EP0416095A1 - Nouvelle methode de separation integree pour procedes de production de di-isopropyle ether et de methyle tertiaire alkyle ether - Google Patents

Nouvelle methode de separation integree pour procedes de production de di-isopropyle ether et de methyle tertiaire alkyle ether

Info

Publication number
EP0416095A1
EP0416095A1 EP19900906008 EP90906008A EP0416095A1 EP 0416095 A1 EP0416095 A1 EP 0416095A1 EP 19900906008 EP19900906008 EP 19900906008 EP 90906008 A EP90906008 A EP 90906008A EP 0416095 A1 EP0416095 A1 EP 0416095A1
Authority
EP
European Patent Office
Prior art keywords
zsm
etherification
ether
zone
ethers
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Withdrawn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
EP19900906008
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.)
ExxonMobil Oil Corp
Original Assignee
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 Corp filed Critical Mobil Oil Corp
Publication of EP0416095A1 publication Critical patent/EP0416095A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/38—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

Definitions

  • This invention relates to an integrated process and means for the production of high octane gasoline rich in methyl tertiary alkyl ether and di-isopropyl ether. More particularly, the invention relates to a novel method for cxinbining the separation of the independent product streams from the
  • 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 iscmers of butene other than isobutylene in the feedstock are essentially unreactive toward primary alcohols under the mild, acid catalyzed etherification reaction conditions employed to produce lower alkyl tertiary butyl ether.
  • IPA isopropyl alcohol
  • DUE diiscprcpyl ether
  • IPA isopropyl alcohol
  • MTBE and TAME are useful octane enhancers.
  • by-product propylene from which IPA and DUE can be made is usually available in a fuels refinery.
  • the petrochemicals industry also produces mixtures of light olefin streams in the C 2 and C 7 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.
  • Olefin hydration employing zeolite catalysts is also kncwn.
  • lower olefins, in particular prcpylene 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 frcro secondary alcohols such as isopropanol and light olefins
  • DIPE is produced from IPA and propylene in a series of operations employing a strongly acidic cation exchange resin as catalyst.
  • processes for the hydration of olefins to provide alcohols and ethers using zeolite catalyst have been disclosed in U. S. patent applications Serial Nos. 139,570, 139,567, 139,565, 139,569, 139,543 arxi 139,566.
  • Adapting available refinery feedstock to simultaneously produce the above oxygenates as octane enhancers can involve two different etherification processes, i.e., iso-olefin
  • the aqueous phase from the water wash tower which contains methanol and isopropanol is recycled to the DUE etherification zone while the organic phase is debutanized to produce high octane gasoline rich in ethers and an overhead ccmprising C 4 -hydrocarbons.
  • the water wash step allows large excess quantities of methanol to be used in the MTBE
  • the invention advantageously employs a cannon water washing step and common debutanizing step in the manufacture of tertiary alkyl ethers and DUE.
  • the common water washing zone utilizes the DUE
  • the present invention provides an integrated continuous process for the production of C 4 + ether rich gasoline, the process comprising the steps of: contacting a fresh mixture of excess methanol and C 4 + hydrocarbon feedstock rich in tertiary olefins with an acidic etherification catalyst in a first etherification zone under tertiary olefin
  • the process further comprises separating the DIPE effluent stream prior to water washing and recycling a major portion of the unreacted C 3 olefinic hydrocarbon, water and isoprcpanol components thereof to the DUE etherification zone while passing the oxygenates components thereof to the washing zone.
  • Another embodiment of the present invention comprises an integrated continuous process for the production of C 5 + ether rich gasoline comprising the steps of: contacting a fresh mixture of excess lower alkanol, a first C 4 + hydrocarbon feedstream rich in tertiary olefins and a second feedstream ccnprising
  • etherification effluent stream containing C 5+ ethers and unreacted alkanol is produced; separating the effluent stream in a water wash tower in contact with water feedstream to provide an organic fraction containing C 4 + hydrocarbons and C 5 + ethers and an aqueous phase comprising water and unreacted lower alkanol; separating said aqueous phase by distillation in cxxnbination with a distillation feedstream ccnprising di-isopropyl ether whereby an overhead stream ccnprising the second feedstream and a bottom stream containing water is produced; introducing the bottom stream and C 3 olefinic hydrocarbons into a second etherification zone in contact with acidic olefin hydration catalyst under olefins hydration and etherification conditions whereby an effluent stream containing di-isoprcpyl ether comprising said distillate feedstream is produced.
  • Figure 1 is a general block flow schematic of the present process.
  • Figure 2 is a flew schematic of a preferred embodiment of the process of this invention.
  • Figure 3 is a flow schematic of an embodiment of the present invention without methanol feed to the DUE
  • 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.
  • Known processes are combined in a unique configuration that provides enhancement of the performance of component processes as well as achieving surprising advantages for the integrated process.
  • the processes integrated include etherification to produce lower alkyl tertiary alkyl ethers such as MTBE (methyl tertiary butyl ether) and TKME (tertiary amyl methyl ether) and C 3 olefins hydration and etherification to produce alcohols and ethers such as DUE, IPA and methyl isopropyl ether.
  • lower alkyl in the present invention refers to C 1 -C 3 altyl derived from etherification using lower alkanol such as methanol, ethanol or isoprcpanol.
  • Tertiary alkyl refers to C 4 -C 5 tertiary alkyl groups derived from the etherification of tertiary olefins.
  • oxygenates or oxygenate as used herein comprises singularly or in combination C 1 -C 8 lower aliphatic, acyclic alcohols or alkanol and symmetrical or unsymmetrical C 2 -C 9 ethers.
  • the process of the present invention is directed to maximizing the utilization of C 3 + refinery streams for the production of those gasoline range oxygenated species, or oxygenates, kncwn to exhibit high octane numbers which are useful for gasoline product blending.
  • Table 1 lists those oxygenated species of particular interest as products of the present
  • methanol is reacted with C 4 + olefinic hydrocarbon feedstock such as FCC unsaturated gas plant containing olefins, particularly iso-olefins, to produce methyl tertiary butyl ether.
  • C 4 + olefinic hydrocarbon feedstock such as FCC unsaturated gas plant containing olefins, particularly iso-olefins, to produce methyl tertiary butyl ether.
  • olefins particularly iso-olefins
  • Methanol may be readily detained from coal by gasification to synthesis gas and conversion of the synthesis gas to methanol by well-established industrial processes.
  • the methanol may be obtained from natural gas by other conventional processes, such as steam reforming or partial oxidation to make the intermediate syngas. Crude methanol from such processes usually contains a significant amount of water, usually in the range of 4 to 20 wt%.
  • the etherification catalyst employed is preferably an ion
  • acidic catalyst in the hydrogen form; however, any suitable acidic catalyst may be employed. Varying degrees of success are obtained with acidic solid catalysts; such as, sulfonic acid resins, phosphoric acid modified kieselguhr, silica alumina and acid zeolites.
  • acidic solid catalysts such as, sulfonic acid resins, phosphoric acid modified kieselguhr, silica alumina and acid zeolites.
  • Typical hydrocarbon feedstock materials for etherification reactions include olefinic streams, such as FOC 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 bifuncticaial ion exchange resin which etherifies and iscmerizes the reactant streams.
  • a typical acid catalyst is Amberlyst 15 sulfonic acid resin, a product of Rchm and Haas Corporation.
  • MTBE is kncwn to be a high octane ether.
  • M+O 83
  • the blending value of MTBE at the 10% level is about 103.
  • the blending value of 10% MTBE is about 114.
  • the olefins hydration and etherification process integrated in the present invention embodies the reaction of prcpylene with water catalyzed by strong acid to form
  • the operating conditions of the olefin hydration process herein are not especially critical and include a temperature of from 100 to 450°C, preferably frcm 130 to 220°C and most preferably from 160 to 200°C, a pressure of frcm 790 to 24230 kPa (100 to 3500 psi), preferably from 3550 to 13890 kPa (500 to 2000 psi), a water to olefin mole ratio of frcm 0.1 to 30, preferably from 0.2 to 15 and most preferably from 0.3 to 5.
  • the olefin hydration process of this invention can be carried out under supercritical dense phase, liquid phase, vapor phase or mixtures of these phases 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 IHSV of from 0.1 to 10 when cperating continuously are le. It is generally preferable to recover any unreacted olefin and recycle it to the reactor.
  • the catalyst employed in the olefin hydration and etherification operations is any lewis acid but preferably 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 about 2 and the large pore variety as represented, for example, by zeolites Y and Beta, which possess a Constraint index no greater than about 2.
  • Preferred catalysts include Zeolite Beta, Zeolite Y, ZSM-5, ZSM-35, and MCH-22. Both varieties of zeolites will possess a framework silica-to-alumina ratio of greater than about 7.
  • a convenient measure of the extent to which a zeolite provides controlled access to molecules of varying sizes to its internal strocture is the aforementioned Constraint Index of the zeolite.
  • a zeolite which provides relatively restricted access to, and egress frcm, its internal structure is characterized by a relatively high value for the Constrain Index, i.e., above about 2.
  • zeolites which provide relatively free access to the internal zeolitic structure have a relatively lew value for the Cutistraint Index, i.e., about 2 or less.
  • the method by which Constraint Index is determined is described fully in U.S. Patent No. 4,016,218, to which reference is made for details of the method.
  • the large pore zeolites which are useful as catalysts in the process of this invention are well known to the art.
  • Representative of these 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 about 2 or less, it should be noted that this zeolite does not behave exactly like other large pore zeolites. However, zeolite Beta does satisfy the requirements for a catalyst of the present invention.
  • Zeolite Beta is described in U.S. Reissue Patent No.
  • a hydrocarbon feedstock 110 containing propylene is passed to the DIPE etherification zone A while excess lower alcohol such as methanol is passed via conduit 115 to MTBE etherification zone B in conjunction with a hydrocarbon feedstock 120 rich in C4 + isoolefins.
  • Water for zone B olefins hydration is transferred via stream 125 to zone A as part of the aqueous phase from water wash tower C.
  • the water transfer system frcm zone B to zone A includes water purge line 126.
  • the etherification reactions in zones A and B are carried out under known conditions as previously described herein.
  • the effluents 130 and 135 from the etherification zones are passed to the common water wash tower C for extraction with water
  • the aqueous phase from C containing unreacted methanol frcm B and isoprcpanol from A is passed to A as noted.
  • the organic phase frcm C ccntaining DUE, C 4 + ethers and unreacted hydrocarbons from A and B is passed via stream 145 to debutanizer D for separation.
  • the gasoline stream may also contain methyl iscpropyl ether, TAME and other ethers of C 4 + isoolefins.
  • Methanol 210 and C 4 + hydrocarbon feedstock 215 are introduced into an etherification zone 220 containing a solid acidic catalyst such as Amberlyst 15. Methanol is in a stoichiometric excess amount compared to the isoolefin content of the C 4 + hydrocarbon feedstock but typically between 1 and 10% in excess.
  • the etherification is carried out vender kncwn etherification conditions between a temperature of 60°C and 125 C and the effluent 225 comprising MTBE, TAME, unreacted methanol and unreacted C 4 + hydrocarbons is fed to a water wash tower 230, preferably after cooling.
  • a hydrocarbon feedstock 235 rich in prcpylene is passed to an olefins hydration and etherification zone 240 which preferably contains zeolite Beta catalyst. Hydration and etherificaticai is carried out under kncwn conditions in contact with water introduced as a ecupenent of the aqueous phase 245 containing methanol and isoprcpanol separated from
  • the effluent from the DUE etherification zone 240 is separated in a high pressure separator 250 and water and isoprcpanol components of the effluent are recycled 255 to the etherification reactor.
  • unreacted C 3 hydrocarbons are fed via 260 to a high pressure flash evaporator 265 and separated at a pressure preferably less than about 350 kBa lower than the etherification zone 240 pressure.
  • a major portion of the unreacted C 3 hydrocarbcai component of the effluent stream is preferably re-compressed 275 and recycled 270 to the hydration and etherification zone 240.
  • the bottom fraction 280 of the flash evaporator which contains ethers frcm 240,
  • isoprcpanol and seme C 3 hydrocarbon is cooled and passed to the water wash tower 230.
  • aqueous phase 245 contains C 3 + hydrocarbons and ethers frcm both etherificaticai zones 220 and 240 ccnprising DIPE, MTBE and TAME.
  • organic phase 290 contains C 3 + hydrocarbons and ethers frcm both etherificaticai zones 220 and 240 ccnprising DIPE, MTBE and TAME.
  • excess methanol from the MTBE reactor is mostly converted to methyl iscpropyl ether.
  • the organic phase is separated in debutanizer 295 to produce C 4 -hydrocarbons 296 and high octane gasoline 297 rich in C 4 + ethers.
  • the process of the present inventicn uniquely uses only one debutanizer to stabilize DUE products and methyl tertiary alkyl ether products. Also, the process uniquely uses one water wash tower to absorb etherification excess methanol and DUE process iscpropyl alcohol byproduct into the DUE water feed.
  • Feedstream 310 containing lower alkanol such as methanol and C 4 + hydrocarbon is fed to MTBE etherification zone 320 in contact with acidic etherificaticai catalyst as described hereinbefore.
  • the effluent stream 330 from the MTBE zone is passed to water wash column or separator 340 and separated in contact with water wash feedstream 350.
  • This feedstream serves to provide both water for the physical separation of the components as required in the process and as the required reactant in the DUE etherification zone.
  • the organic phase 360 is fed to debutanizer distillation fracti ⁇ nator 370 where an overhead stream 380 containing C 3 and C 4
  • the bottom effluent stream 390 from the debutanizer comprises ether-rich gasoline.
  • the aqueous phase 305 from water wash column 340 containing water and unreacted methanol from the etherification zone 320 is passed to
  • distillation separator 315 A bottom stream 325 containing water and isopropyl alcohol (IPA) is separated from separator 315 and transferred to DUE etherification zone 335 via conduits 336 and 337 and pump 338.
  • C 3 hydrocarbon feedstream 345 is passed to etherification zone 335 in contact with acidic catalyst as described herein before.
  • the effluent 355 from zone 335 is passed to separator 365 for separation of a bottom stream 339 containing water and isopropyl alcohol which is transferred to zone 335 by pump 341.
  • the overhead stream 375 cxartaining water,

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Le procédé de production d'alkyle éther tertiaire tel que MTBE, TAME et d'isopropyle tertiaire alkyle éther, et le procédé de production de di-isopropyle éther (DIPE) sont intégrés en un seul procédé global pour produire de l'essence à haute teneur en octane riche en ces éthers. L'intégration s'effectue de préférence dans une étape de séparation combinée dans laquelle les effluents provenant des deux procédés d'éthérification sont amenés dans une tour de lavage à l'eau pour les séparer en une phase organique contenant des hydrocarbures C3+ et des oxygénats comprenant des éthers C4+ et une phase aqueuse qui contient du méthanol et de l'isopropanol. La phase aqueuse est recyclée vers la zone d'éthérification de DIPE tandis que la phase organique est débutanisée pour produire un courant de fond comprenant de l'essence à haute teneur en octane riche en éthers et un courant supérieur comprenant des C4- hydrocarbures. L'étape de lavage à l'eau permet l'utilisation de grandes quantités excédentaires de méthanol dans l'étape d'éthérification de MTBE sans recyclage. L'invention utilise avantageusement une étape commune de lavage à l'eau et une étape commune de débutanisation dans la production d'éthers alkyle tertiaires et DIPE.
EP19900906008 1989-03-23 1990-03-19 Nouvelle methode de separation integree pour procedes de production de di-isopropyle ether et de methyle tertiaire alkyle ether Withdrawn EP0416095A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32786689A 1989-03-23 1989-03-23
US327866 1999-06-08

Publications (1)

Publication Number Publication Date
EP0416095A1 true EP0416095A1 (fr) 1991-03-13

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EP19900906008 Withdrawn EP0416095A1 (fr) 1989-03-23 1990-03-19 Nouvelle methode de separation integree pour procedes de production de di-isopropyle ether et de methyle tertiaire alkyle ether

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Country Link
EP (1) EP0416095A1 (fr)
JP (1) JPH03504731A (fr)
AU (1) AU5405190A (fr)
CA (1) CA2027574A1 (fr)
WO (1) WO1990011267A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0423288A1 (fr) * 1989-04-24 1991-04-24 Mobil Oil Corporation Conversion d'alcools en essence riche en ether

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4182914A (en) * 1974-01-22 1980-01-08 Nippon Oil Company Limited Process for continuously producing diisopropyl ether
US4042633A (en) * 1976-06-07 1977-08-16 Gulf Oil Canada Limited Process for preparing diisopropyl ether
DE3150755A1 (de) * 1981-12-22 1983-06-30 Deutsche Texaco Ag, 2000 Hamburg "verfahren zur abtrennung von methanol aus den bei der veraetherung von c(pfeil abwaerts)4(pfeil abwaerts) bis c(pfeil abwaerts)7(pfeil abwaerts)-isoolefinen mit methanol anfallenden reaktionsprodukten"
DE3614762A1 (de) * 1986-04-30 1987-11-05 Linde Ag Verfahren zur herstellung von t-amylmethylaether

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9011267A1 *

Also Published As

Publication number Publication date
AU5405190A (en) 1990-10-22
WO1990011267A1 (fr) 1990-10-04
CA2027574A1 (fr) 1990-09-24
JPH03504731A (ja) 1991-10-17

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