ETHERIFICATION PROCESS

Abstract: A method is disclosed combining the process for the hydration or etherification of light linear olefins, such as the production of diisopropyl ether (DIPE), with the process for the etherification of C4+ or C4 hydrocarbons containing isobutylene to produce alkyl tertiary butyl ether or ether-rich gasoline in a manner which effectively dewaters alkanol using the iso-olefin hydrocarbon feedstream as extractant. The combined process leads to the production of isopropyl tert-alkyl ethers. In the integrated process the high octane ethers produced may include methyl tert-butyl ether, methyl tert-amyl ether, isopropyl tert-butyl ether and diisopropyl ether. The process also results in the production of a gasoline stream rich in high octane ethers.

Description: ETHERIFICATION PROCESS This invention relates to the production of high octane ethers by etherification of iso-olefins. in a particular embodiment the invention relates to a process integration wherein wet alkanol from linear olefin hydration is dewatered using the hydrocarbon feedstream to an alkyl tert-alkyl ether etherification zone and combined therewith for tert-alkyl ether production. Lower molecular weight alcohols and ethers such as isopropanol (IPA) and diisopropyl ether (DIPE) boil in the gasoline boiling range and are known to have high blending octane numbers.. In addition, by-product propylene from which IPA and DIPE can be made is usually available in a fuels refinery. One important focus of research in the petroleum industry is processes to produce high octane gasolines blended with lower aliphatic alkyl ethers as octane boosters and supplementary fuels. Generally, it is known that asymmetrical C5-C7 alkyl tertiary alkyl ethers and diisopropyl ether (DIPE) are particularly useful as octane improvers for liquid fuels, especially gasoline. MTBE, ethyl tert-butyl ether (ETBE) , isopropyl tert-butyl ether (IPTBE) and TAME are known to be high octane ethers. J.D. Chase, et al, Qil_and J Sas Journal/ April 9, 1979, discuss the advantages one can achieve by using such materials to enhance gasoline octane. The octane blending number of MTBE when 10% is added to a base fuel (R+O = 91) is about 120. For a fuel with a low motor rating (M+O = 83) octane, the blending value of MTBE at the 10% level is about 103. On the other hand, for an (R+0) of 95 octane fuel, the blending value of 10% MTBE is about 114. Increasing demand for high octane gasolines blended with high octane ethers as octane boosters and supplementary fuels has created a significant demand for these ethers, especially MTBE and TAME. Improvements to the processes related to the production of these ethers are matters of high importance and substantial challenge to research workers in the petroleum refining arts. 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 US-A-2,262,913, 3,798,097, 3,198,752, 3,810,848 and 3,989,762. The production of ether from secondary alcohols such as isopropanol and light olefins is also known. US-A-4,182,914 discloses production of DIPE from IPA and propylene in a series of operations employing a strongly acidic cation exchange resin as catalyst. Processes for producing and recovering MTBE and other methyl tertiary alkyl ethers from iso-olefins are known to those skilled in the art, for instance from ϋS-A- 4,544,776 and 4,603,225. Various suitable extraction and distillation techniques are known for recovering ether and hydrocarbon streams from etherification effluent. It is well known that 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) . The reaction of methanol with isobutylene and isoamylenes at moderate conditions with a resin catalyst is discussed by R.W. Reynolds, et al, Tke_o.l_and_gas J≤JiEail, June 16, 1975, and by S. Pecci and T. Floris, HydFQcaς h. . .Processing, December 1977. 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. The reaction is a useful preparation for these valuable gasoline octane enhancers and is typical of the reaction of the addition of lower alkanol to the more reactive tertiary alkenes, or iso-olefins, of the type R2C=CH2 under mild conditions to form the corresponding tertiary alkyl ethers. 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 butenes 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 crude methanol source for methanol for the MTBE reaction typically contains a significant amount of water. For the etherification reaction to proceed effectively it is important that water in the crude methanol be reduced. In the DIPE process, the reaction of water with propylene to produce DIPE also produces a by¬ product stream consisting of isopropanol and water. To maintain high conversion it is required in the prior art that this stream be recycled to the DIPE unit. According to the present invention a process for the production of lower alkyl tert-alkyl ethers comprises extracting an aqueous alkanol stream from a linear C2-C4 olefin hydration and/or etherification zone with a hydrocarbon stream rich in iso-olefin and separating an organic stream containing dewatered alkanol, and introducing said organic stream into an iso-olefin etherification zone under iso-olefin etherification conditions in contact with acidic catalyst whereby lower alkyl tert-alkyl ether is produced. Said hydrocarbon stream preferably contains isobutylene and/or isoamylene, and may take the form of a C4+ hydrocarbon whereby lower alkyl tert-butyl and lower alkyl tert-amyl ethers are produced. The alkanol includes ethanol, 1-propanol, isopropanol, 1-butanol and 2-butanol; in a preferred manner of operation the aqueous alkanol comprises aqueous isopropanol and the tert-alkyl ethers comprise isopropyl tert-butyl ether and isopropyl tert-amyl ether. The aqueous alkanol stream can, moreover, further include wet methanol? alternatively dry methanol may be introduced directly into said etherification zone, whereby methyl tert-butyl ether and methyl tert-amyl ether are produced. The raffinate stream resulting from said extraction, containing water and unextracted alkanol and methanol, is in an advantageous embodiment passed together with a fresh water feedstream and a hydrocarbon feedstream comprising linear C2-C4 olefin to said olefin hydration and/or etherification zone in contact with acidic olefin hydration and etherification catalyst under olefin hydration and etherification conditions to produce effluent streams comprising an ether stream, said aqueous alkanol stream and an unreacted linear C2-C4 olefin containing hydrocarbons stream. The C2-C4 hydrocarbon feedstream is preferably a C3 hydrocarbon stream containing propene, whereby the effluent streams comprise diisopropyl ether, methyl isopropyl ether and aqueous isopropanol. The iso-olefin etherification zone effluent may be separated to produce a stream comprising high octane ether rich gasoline and a stream comprising unreacted iso- olefin-rich hydrocarbons. The acidic olefin hydration and etherification catalyst and acidic iso-olefin etherification catalyst may be the same or different and selected from acidic zeolites, acidic resins, phosphoric acid modified kieselguhr and silica-alumina. As zeolites, zeolite ZSM-5 and zeolite Beta are preferred, whilst sulfonated polystyrene resins are preferred acidic resins. The operating conditions in the linear olefin hydration and/or etherification zone include a temperature of 60 to 450°C, a pressure of 6.9 to 241 bar and a water/olefin mole ratio of 0.1 to 30. In the iso-olefin etherification zone alkanol is preferably present in stoichiometric excess, and may include methanol, and the operating temperature is preferably 40 to 100°C, more preferably 60 to 80°C, the operating pressure preferably 1 to 20 bar, more preferably 10 to 15 bar. An integrated process for the manufacture of alkyl tertiary alkyl ethers, using dewatered alkanol byproduct from linear olefins hydration as feedstream to iso-olefins etherification, can provide for the manufacture of methyl or isopropyl tert-alkyl ether and diisopropyl ether in a design integrated with DIPE production; an integrated MTBE and DIPE process which additionally produces isopropyl tert-butyl ether; and an integrated process for the manufacture of high octane ethers containing methyl tert-alkyl ethers, DIPE and including high octane gasoline. Processes for the hydration of light olefins and production of ethers such as DIPE, and for the alkanol etherification of C4+ iso-olefinic hydrocarbons to produce ether-rich gasoline, can be combined in a manner which effectively dewaters alkanol feedstock using the C4+ hydrocarbon feedstream as extractant. The combined process leads to the production of ethers such as methyl tert-butyl ether, methyl tert-amyl ether and isopropyl tert-butyl ether. The process also results in the production of a gasoline stream rich in high octane ethers. In the integrated process the light, linear olefin hydration product, or by-product, comprising C2-C4 alkanol is dewatered with C4+, or C4, iso-olefin-rich feedstock and converted to tert-ethers. Typical hydrocarbon feedstock materials for iso-olefin etherification reactions include C4+ olefinic streams, such as FCC light naphtha and C4 butenes rich in isobutene. These aliphatic streams are produced in petroleum refineries by catalytic cracking of gas oil or the like. A wet methanol feedstream, containing about 4 to 20 wt% water, may be included in the integrated dewatering step to produce MTBE and TAME. More particularly, in an integrated process for the production of high octane ethers an aqueous alkanol effluent stream from a light olefins hydration zone is extracted with a hydrocarbon feedstream to a lower alkyl tert-alkyl ether production zone. The feedstream to the tert-alkyl etherification zone typically contains isobutylene and/or isoamylene. The aqueous raffinate stream is separated after extraction, and contains some residual alkanol, while the organic extract stream comprising the tert-alkyl ether hydrocarbon feedstream contains a major portion of dewatered alkanol. The organic stream is passed to the tert-alkyl ether production zone in contact with acidic iso-olefin etherification catalyst under etherification conditions to produce an etherification effluent stream comprising tert- alkyl ethers of alkanol and unreacted hydrocarbons. The aqueous raffinate stream, a fresh water feedstream and light, linear olefin hydrocarbon feedstream is in one embodiment passed to an ether production zone in contact with acidic olefin hydration and etherification catalyst under olefin hydration and etherification conditions to produce linear ethers and alkanol, such as diisopropyl ether, dibutyl ether, isopropanol, 1-butanol, 2-butanol and the like. The single Figure is a schematic diagram of a preferred manner of operation of the process of the present invention. The Figure shows an etherification unit 110 for the conversion of C1-C4 alkanol to lower alkyl tert-alkyl ethers; and olefins hydration and/or etherification unit 120 for the etherification and/or hydration of C3 hydrocarbons containing propylene to produce high octane diisopropyl ether, with isopropanol as by-product. These units, 110 and 120, are integrated into a combined process through separator 130. According to the illustrated embodiment a C4+ hydrocarbon feedstock, rich in iso-olefins and particularly isobutylene and isoamylene, is employed as feedstock and introduced through conduit 105 for eventual mixing with a C2-C4 alkanol feedstream. A C4 feedstream containing isobutylene may also be used, rather than C4+ feedstream. Wet methanol may be combined with the C2-C4 alkanol feedstream, via conduit 115. The mixture of C4+ hydrocarbon feedstock and alkanol is passed to a separator 130 where it comes in contact with a by-product stream 125 comprising aqueous isopropanol. In the separator isopropanol and methanol are extracted into the hydrocarbon feedstream and an aqueous raffinate stream 135 is separated which contains some methanol and isopropanol. The major portion of methanol and isopropanol is separated from the separator/extractor unit 130 as an organic stream 145. In this process the methanol feedstream as well as the aqueous isopropanol DIPE by-product stream are effectively dewatered. The organic stream 145 is passed to the iso-olefins unit 110 where etherification is carried out in contact with acidic catalyst. The iso- olefins etherification effluent stream is separated, typically by fractionation and/or extraction, to produce an ether-rich gasoline stream 155 and an unreacted C4 stream 165. When the alkanol includes methanol the ether- rich gasoline contains MTBE, TAME, isopropyl tert-butyl ether, isopropyl tert-amyl ether. When the hydrocarbon feedstream is C4, the hydrocarbon effluent stream 155 comprises MTBE and isopropyl tert-butyl ether. From separator 130 the aqueous raffinate 135 is combined with water 175 and introduced into a DIPE etherification zone in conjunction with C3's hydrocarbon feedstream 185. Hydration and etherification of C3 ! s is carried out in contact with acidic catalyst. The product of the hydration and etherification, after separation, is diisopropyl ether, stream 190 and unreacted C3 hydrocarbon stream 195. To the extent that a minor portion of alkanol such as methanol is contained in the raffinate from separator 130 a minor portion of methyl isopropyl ether may also be produced in the DIPE etherification unit. The separation also produces the by-product aqueous isopropanol stream 125 which, conventionally, would be recycled to the DIPE unit, but in the illustrated embodiment is integrated with the iso-olefins etherification process. Separation of the effluent from the DIPE unit 120 can be achieved by a variety of means known to those skilled in the art. Certain variations of the illustrated embodiment may conveniently be adopted. In particular, the methanol feedstream 115 may be eliminated and the dewatered alkanol from the hydration and/or etherification step 190 used as the sole alkanol feed to etherification zone 110, after extraction with the iso-olefin etherification feedstream 105. Implementation of this variation of the described embodiment produces isopropyl tert-butyl ether and, when the feedstream is C4+ iso-olefins, isopropyl tert-amyl ether. Optionally, dry methanol may be passed directly to etherification zone 110. Also, the hydration and/or etherification zone 120 can effect hydration and/or etherification of other linear olefins, such as butene. Conditions can be adjusted to control the linear olefins hydration step to produce predominantly alkanol as the product to be subjected to dewatering in separator 130. Lower alkyl in the present invention refers to C1-C4 alkyl derived from etherification using lower alkanol such as methanol, ethanol, 1-propanol, isopropanol, 2-butanol and l-butanol. Tertiary alkyl refers to C4-C5 tertiary alkyl groups derived from the etherification of iso-olefins such as isobutene and isoamylene. Light, linear olefins include ethene, propene, butene-1 and butene-2. The etherification catalyst employed is preferably an ion exchange resin 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 such as zeolite beta and ZSM-5. Lower alkanol, including optional methanol, may be present in the iso-olefin etherification zone in stoichiometric excess. Methanol may itself be up to 100% mole percent in excess. In the absence of a methanol feedstream the sole alkanol reactant to the iso-olefin etherification zone is, in the preferred embodiment, isopropanol and the reaction products are tertiary alkyl ethers of isopropanol, i.e., isopropyl tertiary butyl ether and isopropyl tertiary amyl ether. The operating conditions of the olefin hydration and etherification process include a temperature of from about 60 to 450°C, preferably from about 90 to about 220°C and most preferably from about 120 to about 200°C, a pressure of from about 100 (6.9 bar) to about 3500 psi (241 bar), preferably from about 500 (34.5 bar) to about 2000 psi (138 bar) a water to olefin mole ratio of from about 0.1 to about 30, preferably from about 0.2 to about 15 and most preferably from about 0.3 to about 3. The olefin hydration and etherification process 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 about 20 minutes to about 20 hours when operating in batch and an olefin WHSV of from about 0.1 to about 20, preferably about 0.1-2, when operating continuously are suitable. A portion of unreacted olefin may be recovered and recycled to the reactor. For DIPE, the DIPE per pass selectivity of isopropanol in this invention may be 10-99%, preferably about 50%. The catalysts employed in the olefin hydration and etherification and iso-olefin etherification operations may be any acidic catalyst, although a shape- selective acidic zeolite is advantageously used. In general, the useful catalysts embrace two categories of zeolite, namely those of intermediate pore size, for example ZSM-5, which possess a Constraint Index of greater than about 2; and those of large pore size, for example zeolite Y, Beta and ZSM-12, which possess a Constraint Index no greater than about 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 about 7. In addition, acid resin catalysts are useful, such as Amberlyst 15 (Rohm, & Hass) and other sulfonated vinyl aromatic resins. The method by which Constraint Index is determined is described fully in US-A-4,016,218. Constraint Index (CI) values for some zeolites which can be used in the process of this invention are described in the following table together with the temperature at which the test was made: Constraint Index Zl m Qlite lΔ£_I.§≤i_I≤m ≤I3£ϋ£e^.__-2£l ZSM-11, ZSM-23, ZSM-35 and ZSM-38 are defined by the x-ray data set forth in US-A-3,702,886, 3,709,979, 4,076,842, 4,016,245 and 4,046,859 respectively. Although ZSM-38 possesses a Constraint Index of 2.0, it is often classified with the intermediate pore size zeolites and will therefore be 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 about 2, 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. Although 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. X, L and Y are defined by the x-ray data set forth in ϋS-A-3,308,069, 2,882,244, 3,216,789 and 3,130,007 respectively. Low sodium ultrastable zeolite Y (USY) is described in US-A-3,293,192, 3,354,077, 3,375,065, 3,402,996, 3,449,070 and 3,595,611. Dealuminized zeolite Y (Deal Y) can be prepared by the method disclosed in US-A-3,442,795. Zeolites ZSM-3, ZSM-4, ZSM-12, ZSM-20 and ZSM-50 are defined by the x-ray data set forth in ϋS-A-3,415,736, 3,923,639, 3,832,449, 3,972,983 and 4,640,829 respectively.

Claims: QLi.Il.-. 1. A process for the production of lower alkyl tert-alkyl ethers, comprising extracting an aqueous alkanol stream from a linear C2-C4 olefin hydration and/or etherification zone with a hydrocarbon stream rich in iso-olefin and separating an organic stream containing dewatered alkanol, and introducing said organic stream into an iso-olefin etherification zone under iso-olefin etherification conditions in contact with acidic catalyst whereby lower alkyl tert-alkyl ether is produced. 2. A process according to claim 1 wherein said hydrocarbon stream contains isobutylene and/or isoamylene. 3. A process according to claim 1 or claim 2 wherein said hydrocarbon stream comprises C4+ hydrocarbon whereby lower alkyl tert-butyl and lower alkyl tert-amyl ethers are produced. 4. A process according to any preceding claim wherein said alkanol includes ethanol, 1-propanol, isopropanol, 1-butanol and 2-butanol. 5. A process according to any preceding claim wherein said aqueous alkanol comprises aqueous isopropanol and said tert-alkyl ethers comprise isopropyl tert-butyl ether and isopropyl tert-amyl ether. 6. A process according to any preceding claim wherein said aqueous alkanol stream further includes wet methanol, together with the aqueous alkanol from olefin hydration. 7. A process according to any preceding claim further comprising introducing dry methanol into said etherification zone whereby methyl tert-butyl ether and methyl tert-amyl ether are produced. 8. A process according to claim 6 or claim 7 wherein the raffinate stream resulting from said extraction, containing water and unextracted alkanol and methanol, is passed together with a fresh water feedstream and a hydrocarbon feedstream comprising linear C2-C4 olefin to said olefin hydration and/or etherification zone in contact with acidic olefin hydration and etherification catalyst under olefin hydration and etherification conditions to produce effluent streams comprising an ether stream, said aqueous alkanol stream and an unreacted linear C2-C4 olefin containing hydrocarbons stream. 9. A process according to claim 8 wherein said hydrocarbon feedstream is a C3 hydrocarbon stream containing propene and the effluent streams comprise diisopropyl ether, methyl isopropyl ether and aqueous isopropanol. 10. A process according to any preceding claim further comprising separating said iso-olefin etherification zone effluent to produce a stream comprising high octane ether rich gasoline and a stream comprising unreacted iso-olefin-rich hydrocarbons. 11. A process according to any preceding claim wherein said acidic olefin hydration and etherification catalyst and said acidic iso-olefin etherification catalyst are the same or different and are selected from acidic zeolites, acidic resins, phosphoric acid modified 4 kieselguhr and silica-alumina. 12. A process according to claim 11 wherein said catalyst is selected from zeolite ZSM-5, zeolite Beta and sulfonated polystyrene resins. 13. A process according to any preceding claim wherein the operating conditions in linear olefin hydration and/or etherification zone include a temperature of 60 to 450°C, a pressure of 6.9 to 241 bar and a water/olefin mole ratio of 0.1 to 30. 14. A process according to any preceding claim wherein alkanol is present in stoichiometric excess in the iso-olefin etherification zone. 15. A process according to claim 14 wherein said alkanol includes methanol. 16. A process according to any preceding claim wherein the iso-olefin etherification conditions include a temperature in the range 40 to 100°C and a pressure in the range 1 to 20 bar. 17 A process according to claim 16 wherein said temperature and pressure are 60-80°C and 10-15 bar respectively. 18. An integrated reactor system for the production of high octane ethers, comprising in combination; » first etherification reactor means for the etherification of iso-olefins; second etherification reactor means for the etherification of propene; extraction separator means operably connected to said first and second etherification means to dewater said second reactor aqueous isopropanol by-product stream and said first reactor wet methanol feedstream with said first reactor hydrocarbon feedstream.

Inventors: HARANDI MOHSEN NADIMI, OWEN HARTLEY, HARANDI, MOHSEN, NADIMI, OWEN, HARTLEY
Applicants: MOBIL OIL CORP, MOBIL OIL CORPORATION
Application year: 1990
Main classification: C07C41
IPC codes: C07C29, C07C41, C07C43, C10L1