WO1990008120A1

WO1990008120A1 - Process for the conversion of olefins to alcohols and/or ethers

Info

Publication number: WO1990008120A1
Application number: PCT/US1990/000135
Authority: WO
Inventors: David Owen Marler; Charles Mitchel Sorensen, Jr.; Philip Varghese
Original assignee: Mobil Oil Corporation
Priority date: 1989-01-12
Filing date: 1990-01-10
Publication date: 1990-07-26
Also published as: AU4840290A; CA2025016A1; JPH03503175A; EP0403639A1

Abstract

Olefins are converted to alcohols and/or ethers employing, as catalyst, an acidic zeolite which has been bound with an essentially non-acidic refractory oxide of at least one metal of Group IVA and/or IVB of the Periodic Table of Elements, e.g., silica, titania, zirconia and/or germania.

Description

PROCESS FOR THE CONVERSION OF OLEFINS TO ALCOHOLS AND/OR ETHERS

This invention relates to a process for the catalytic conversion of olefins to provide alcohols, ethers and their mixtures useful, inter alia , as high octane blending stocks for gasoline. There is a need for an efficient catalytic process to manufacture alcohols and ethers from light olefins thereby augmenting the supply of high octane blending stocks for gasoline. Lower molecular weight alcohols and ethers such as isopropyl alcohol (IPA) and diisopropyl ether (DIPE) are in the gasoline boiling range and are known to have a high blending octane number. In addition, by-product propylene from which IPA and DIPE can be made is usually available in a fuels refinery. The petrochemicals industry also produces mixtures of light olefin streams in the C_ to C_ molecular weight range and the conversion of such streams or fractions thereof to alcohols and/or ethers can also provide products useful as solvents and as blending stocks for gasoline.

The catalytic hydration of olefins to provide alcohols and/or ethers is a well-established art and is of significant commercial importance. Representative olefin hydration processes are disclosed in U.S. Patent Nos. 2162913, 2477380, 2797247, 3798097, 2805260, 2830090, 2861045, 2891999, 3006970, 3198752, 3810849 and 3989762. Olefin hydration employing zeolite catalysts is known. As disclosed in U.S. Patent No. 4214107, lower olefins, in particular, propylene, can be catalytically hydrated over a zeolite catalyst having a silica to alumina molar ratio of at least 12 and a Constraint Index of 1-12, e.g. ZSM-5, to provide the corresponding alcohol, essentially free of ether and hydrocarbon by-product.

According to U.S. Patent No. 4499313, an olefin is hydrated to the corresponding alcohol in the presence of hydrogen ordenite or hydrogen zeolite Y having a molar ratio of 20-500. The use of such a catalyst is said to result in higher yields of alcohol than olefin hydation processes which employ conventional solid acid catalysts. Use of the catalyst is also said to offer the advantage over ion-exchange type olefin hydration catalysts of nc . being restricted by the hydration temperature.

U.S. Patent No 4783S55 describes an olefin hydra ion process employing a medium pore zeolite as hydration catalyst. Specific cataysts mentioned are theta-1, ferrierite, ZSM-22, ZSM-23 and Nu-10

The catalyzed reaction of olefins with alcohols to provide ethers is a well known process. For example, U.S. Patent No. 4,042,633 discloses the preparation of diisopropyl ether (DIPE) from iεopropyl alcohol (IPA) employing a montmorillonite clay catalyst, optionally in the presence of added propylene. U.S. Patent No. 4,182,914 dϊc;clQS£s the production_*.of- DIPE- from IPA and propylene in a series of operations employing a^" strongly acidic cation exchange resin as catalyst. In U.S. Patent No. 4,334,890, a mixed C stream containing isobutylene is reacted with . aqueous ethanol to form a mixture of ethyl tertiary butyl ether (ETBE) and tertiary butyl alcohol (TBA) .

U.S. Patent No. 4,418,219 discloses a process for preparing methyl tertiary butyl ether (MTBE) by reacting isobutylene and methanol in the presence of boron phosphate, blue tungsten oxide or a crystalline aluminosilicate zeolite having a silica to alumina mole ratio of at least 12:1 and a Constraint Index of from 1 to 12 as catalyst.

As disclosed in U.S. Patent No. 4,605,787, alkyl tert- alkyl ethers such as MTBE and tertiary a yl methyl 5 ether (TAME) are prepared by the reaction of a primary alcohol with an olefin having a double bond on a tertiary carbon atom employing as catalyst an acidic zeolite having a Constraint Index of from 1 to 12, e.g., ZSM-5, ZSM-11, ZSM-12, ZSM-23 dealuminized zeolite Y and rare 10 earth-exchanged zeolite Y.

U.S. Patent No. 4,714,787 discloses the preparation of ethers by the catalytic reaction of linear monoolefins with primary or secondary alcohols employing, as a catalyst, a zeolite having a pore size greater than 5 15 Angstroms, e.g., ZSM-5, zeolite Beta, zeolite X and zeolite Y. Specifically, in connection with the reaction of propylene with methanol to provide methyl isoopropyl ether (MIPE) , effluent from the reactor is separated into a MIPE fraction, useful as a gasoline blending component, ^2C with unreacted propylene, methanol, by-product dimethyl ether (DME) and water at up to one mole per mole of by-product DME, either individually or in combination, being recycled to the reactor.

In EP-A-55,045, an olefin is reacted with an alcohol -^~ to provide an ether, e.g., isobutene and methanol are reacted to provide MTBE, in the presence of an acidic zeolite such as zeolite Beta, ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-48, as a catalyst.

It is a common practice in zeolite catalyst 30 manufacture to extrude the active zeolite component with an inorganic oxide binder component such as alumina. The binder serves as a matrix for the zeolite and facilitates the extrusion process resulting in a composite product possessing good mechanical strength. In many cases, the binder component contributes little to the observed catalytic activity and can be regarded as an inert diluent for the catalytically active zeolite component. However, it has now been discovered that the activity and selectivity of zeolite catalysts used in olefin hydration/etherification may be significantly influenced by the nature of the binders with which the zeolites are composited. Accordingly, the invention resides in a process for converting an olefin to an alcohol and/or an ether comprising reacting the olefin with water and/or an alcohol in the presence of a catalyst comprising a zeolire and a refractory binder comprising a metal of Group IVA and/or IVB of the Periodic Table of Elements.

The present invention is applicable to the conversion of individual light olefins and mixtures of olefins of various structures, preferably within the C_. range. Accordingly, the invention is applicable to the conversion of ethylene, propylene, buteneε, pentenes, hexenes, heptenes, mixtures of these and other olefins such as gas plant, off-gas containing ethylene and • -. -_*. propylene, naphtha cracker off-gas containing light olefins, fluidized catalytic cracked (FCC) light gasoline containing pentenes, hexenes and heptenes, and refinery- FCC propane/propylene streams. For example, a typical FCC light olefin stream possesses the following composition:

Typical Refinery FCC Light Olefin Composition

The process of the invention is especially applicable to the conversion of propylene and propylene-containing streams to mixtures of IPA and DIPE. When an olefin is reacted with water to provide an alcohol, the reaction can be regarded as one of hydration although, of course, some product alcohol can, and does, react with the olefin feed to co-produce ether. When an olefin is reacted solely with an alcohol to provide an ether, the reaction can be regarded as one of etherification. When an olefin is reacted with both water and an alcohol to provide a mixture of an alcohol and an ether, the resulting conversion involves both hydration and etherification reactions. In addition, other reactions such as the chemical dehydration of alcohol to ether may occur to some extent.

Lower alcohols which are suitable for reaction with light olefins herein, optionally together with water, include alcohols having from 1 to 6 carbon atoms, i.e., methanol, ethanol, propanol, isopropyl alcohol, n-butanol, tert-butanol, the pentanols and the hexanols.

The operating conditions of the improved olefin conversion process herein are not especially critical. They include a temperature ranging from ambient (20°C) to 300°C, preferably from 50 to 220°C and more preferably from 100 to 200°C, a total system pressure of at least 5 atm (500kPa) , preferably at least 20 atm (2000kPa)and more preferably at least 40 atm (4000kPa) , a total water and/or alcohol to olefin mole ratio of from 0.1 to 30, preferably from 0.2 to 15 and most preferably from 0.3 to 5. When the conversion is primarily one of hydration, it may be preferable to operate at low water to total olefin mole ratios as disclosed in EP-A-323270, e.g., at water to total olefin mole ratios of less than about 1.

It will also be appreciated that the precise conditions selected should, to some extent, reflect the nature of the olefin feed. For example, isoolefins generally require milder process conditions than straight chain olefins. Thus, in the case of isobutylene, CH =CH(CH_) , good conversions to ether can be obtained with process conditions of from 30°C to 100°C, a pressure which is at least sufficient to maintain the isobutylene in the liquid phase, e.g., about 3 atm (300kPa) or higher, a water and/or alcohol to isobutylene mole ratio of from 0.1 to -30, preferably from 0.2 to 15 and

^{■ ■}_ from 0.3 to 5 and an LHSV of from 0.1 to 25. ^'

The olefin conversion process of this invention can be carried out under liquid phase, vapor phase or mixed vapor-liquid phase conditions in batch or in a continuous manner using a stirred tank reactor or fixed bed flow reactor, e.g. , of the trickle-bed, liquid-up-flow, liquid-down-flow, counter-current and co-current type. Reaction times of from 20 minutes to 20 hours when operating in batch and an LHSV of from 0.1 to 25 when operating continuously are generally suitable. It may, of course, be advantageous to recover any unreacted olefin and recycle it to the reactor.

When seeking to maximize the production of ether by the hydration of olefin, the aqueous product effluent from the olefin hydration reactor containing alcohol and ether can be introduced into a separator, e.g., a distillation column, for recovery of ether. The dilute aqueous solution of alcohol may be then introduced into a second separator, e.g., another distillation column, where a water/alcohol azeotrope is recovered. A fraction of the azeotrope may be fed into a conventional dehydra^tion reactor to provide a further quantity of ether which can be combined with the ether previously recovered from the olefin hydration reactor. By blending various product streams, almost any ratio of alcohol/ ether can be obtained. When alcohol/ether mixtures are to be used as gasoline blending stocks, this capability for adjusting the ratios of alcohol to ether offers great flexibility in meeting the octane requirements for given gasoline compositions. Regulatory considerations aside, alcohol/ether mixtures, e.g., IPA/DIPE mixtures, can cons itxαte up tc about 20 weight percent of the gasoline to which they are added.

A particularly advantageous procedure for producing mixtures of alcohol and ether, and in particular IPA and DIPE, from the hydration of an olefin-containing feed (a propylene-containing feed in the case of IPA/DIPE mixtures) employing a large pore zeolite such as zeolite Y or zeolite Beta is described in EP-A-323137. In accordance with this procedure as applied, e.g., to the production of IPA/DIPE mixtures, a fresh propane/propylene-containing feed (readily available in many petroleum refineries) and fresh water are cofed, together with recycled unreacted propylene and recycled water from a decanter, into a hydration reactor. The reactor effluent is passed to a separator unit with propane and unconverted propylene being recycled to the 5 reactor, part of the gaseous mixture being purged in order to avoid build-up of propane in the recycle loop. The liquid products from the separator unit are introduced into a distillation unit where an azeotropic mixture of IPA, DIPE, water and propylene oligomers (mostly C__

10 olefin) is distilled off and, following cooling, is introduced into a decanter in which phase separation takes place. The upper layer contains mostly DIPE, e.g., 90 weight percent or more, end relatively little water, e.g., 1 weight percent or so. The lower layer is largely water

15 containing negligible quantities of IPA and DIPE. The quantity of the decanter overheads which is recycled can be regulated so as to control the water content in the final product. The bottom fraction of the distillation unit, mainly IPA, is combined with DIPE in the decanter

20 overheads to provide the final IPA/DIPE mixture.

Where it is desired to separate out the alcohol from an alcohol/ether mixture and ^"trius^'"provide^Ss ^'en -ir^:i'pu e^j ether, one can advantageously practice the procedure^{" '}of '^'r EP-A-323138. According to this process as applied to the

-^~~ production of DIPE, the propylene component of a mixed propane/propylene feed undergoes hydration in the presence of a large pore zeolite olefin hydration catalyst, e.g., zeolite Y or zeolite Beta, in a hydration reactor with the effluent therefrom being passed to a separator operating

30 below the olefin hydration reaction temperature. There, two liquid phases form, the aqueous phase being removed and recycled to the hydration reactor. The hydrocarbon-rich phase is flashed to a lower pressure to effect separation of the unreacted C components. The flashed product, now containing a substantial amount of IPA product, is introduced to a distillation unit operated at or below atmospheric pressure to effect further purification of the DIPE. The azeotropic IPA, DIPE and water overhead product containing a small amount of propylene oligomer is condensed and thereafter contacted with reactor feed water. The resulting phase separation provides a DIPE product containing at most negligible amounts of IPA and water, e.g., 1.0 weight percent and 0.5 weight percent of these materials, respectively. The remaining aqueous phase can be recycled to the reactor. The catalyst employed in the olefin conversion process of this invention can include any zeolite which is effective for the catalysis of the reaction of olefin (ε) with water and/or alcohol(s) to produce alcohol (ε) , ether(ε) or their mixtures. Representative of the zeolites which are uεeful herein are zeolite Beta, zeolite X, zeolite L, zeolite Y, ultraεtable zeolite Y (USY) , dealuminized Y (Deal Y) , ordenite, ZSM-3 , ZSM-5, ZSM-12, ZSM-20, Z-5M~23_r ZSM-35, ZSM-50, and ixtureε of any of the foregoing.

Zeolite Beta iε described in U.S. Reiεεue Patent No. 28,341 (of original U.S. Patent No. 3,308,069) . Zeolite X is described in U.S. Patent No. 2,882,244. Zeolite L iε described in U.S. Patent No. 3,216,789. Zeolite Y is described in U.S. Patent No. 3,130,007. Low sodium ultrastable zeolite Y (USY) is described in U.S. Patent Noε. 3,293,192, 3,354,077, 3,375,065, 3,402,996, 3,449,070 and 3,595,611. Dealuminized zeolite Y can be prepared by the method disclosed in U.S. Patent No. 3,442,795. Zeolite ZSM-3 iε described in U.S. Patent No. 3,415,736. Zeolite ZSM-5 iε deεcribed in U.S. Patent Re. 29,948 (of original U.S. Patent No. 3,702,886). Zeolite ZSM-12 iε described in U.S. Patent No. 3,832,449. Zeolite ZSM-20 is described in U.S. Patent No. 3,972,983. Zeolite ZSM-23 is described in U.S. Patent No. 4,076,842. Zeolite ZSM-35 is described in U.S. Patent No. 4,016,245. Zeolite ZSM-50 is described in U.S. Patent No. 4,640,829.

The zeolite olefin hydration/etherification catalystε εelected for use herein will generally possess an alpha value of at least about 1. "Alpha value", or "alpha number", iε a measure of zeolite acidic functionality and is more fully described together with details of its measurement in J. Catalysis, 61, pp. 390-396 (1980) . Zeolites of relatively low acidity (e.g. , zeolites posεeεεing alpha valueε of less than about 200) can be prepared by a variety of techniques including (a) syntheεizing a zeolite with a high silica/alumina ratio, (b) steaming, (c) steaming followed by dealuminization and (d) substituting framework aluminum with other trivalent metal species. For example, in the case of steaming, the zeolite can be expoεed to steam at elevated temperatures ranging from 2-60 -.to_65Q ς_._ (,5QC p .l3£.Q_:'_τ )_r-.a.τϊά ^re erably from 400 to 540°C (750 to l-Q£Q-^β-E-. - This-.tEea-t ent can be accomplished in an atmosphere of 100% steam or an atmosphere consisting of steam and a gas which is substantially inert to the zeolite. A similar treatment can be accomplished at lower temperatures employing elevated pressure, e.g., at 175 to 370^*C (350 to 700^βF) and from 1000 to 20000kPa (10 to 200 atmospheres) . Specific details of several steaming procedures may be gained from the discloεureε of U.S. Patent Nos. 4,325,994, 4,374,296 and 4,418,235. Aside from, or in addition to any of the foregoing procedures, the surface acidity of the zeolite can be eliminated or reduced by treatment with bulky reagents as described in U.S. Patent No. 4,520,221.

Prior to their use as olefin hydration/etherification catalysts, the as-synthesized zeolite crystals εhould be subjected to thermal treatment to remove part or all of any organic constituent present therein. In addition, the zeolites εhould be at least partially dried prior to uεe. Thiε can be done by heating the crystals to a temperature in the range of from 200 to 595°C in an inert atmosphere, such as air or nitrogen and atmospheric, subat ospheric or superatmoεpheric pressures for between 30 minuteε to 48 hourε. Dehydration can also be performed at room temperature merely by placing the cryεtalline material in a vacuum, but a longer time is required to obtain a εufficient amount of dehydration. The original cations asεociated with the zeolites utilized herein can be replaced by a wide variety of other cations according to techniques well known in the art, e.g., by ion-exchange. Typical replacing cations include hydrogen, ammonium, alkyl ammonium and metal cationε, and their mixtureε. Metal cations can also be introduced into the zeolite. In the case of metal cations, particular preference is given to metals of Groups IB to VIII of the Periodic Table including, by way .of example, iron, nickel, cobalt, copper, zinc, platinum, palladium, calcium, chromium, tungsten, molybdenum, rare earth metals, etc. These metals can also be present in the form of their oxides.

A typical ion-exchange technique involves contacting a particular zeolite with a salt of the desired replacing cation. Although a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfateε. Repreεentative ion-exchange techniques are diεcloεed in a number of patentε including U.S. Patent Noε. 3,140,249; 3,140,251 and 3,140,253. Following contact with a εolution of the deεired replacing cation, the zeolite is then preferably waεhed with water and dried at a temperature ranging from 65 to 315°C (150 to 600°F) and thereafter calcined in air or other inert gas at temperatures ranging from 260 to 820*C (500 to 1500°F) for periods of time ranging from 1 to 48 hours or more. The catalyst employed in the procesε of the invention also includeε a binder material in the form of at leaεt one eεεentially non-acidic refractory oxide of a metal of Groupε IVA or IVB of the Periodic Table of the Elements. Particularly useful are the oxideε of silicon, germanium, titanium and zirconium. Combinations of such oxides with other oxides are also useful provided that at least 40 weight percent, and preferably at least 50 weight percent, of the total oxide iε one or a combination of the aforeεaid Group IVA and/or Group IVB metal oxideε. Thus, mixtures of oxideε which can be used to provide the binder material herein include titania-alumina, titania-magneεia, titania-zirconia, t_.ita.p,ia-thcria, titania-beryllia,

silica-alumina-magnesia- and '^•silica-titania-zirconia, zirconia-alumina and silica-zirconia. In preparing the refractory oxide-bound zeolite catalyst, it is generally advantageous to provide at leaεt a part of the binder in colloidal form aε this has been found to facilitate the extrusion of the bound zeolite which can otherwise be accomplished in accordance with known and conventional techniques. When a colloidal metal oxide binder is employed, it can represent anywhere from 1 to 100 weight percent of the total binder present. For example, in the case of silica, amounts of colloidal silica ranging from 2 to 60 weight percent of the total binder generally provide good resultε. The relative proportionε of zeolite and refractory oxide binder on an anhydrouε basis can vary widely with the zeolite content 5 ranging from between 1 to 99 weight percent, and more usually in the range of from 20 to 80 weight percent, of the dry compoεite.

In the exampleε which follow in which ail parts are by weight, Exampleε 1 and 2 are illuεtrative of the 0 preparation of zeolite catalysts which are useful as catalysts herein and Exampleε 3 to 5 are illustrative cf the olefin conversion procesε of this invention.

EXAMPLE 1

Thiε example illuεtrateε the preparation of 35 wt% 5^J

wt% zeolite Beta and 35 Wt% ZrO2_/65 wt% zeolit%e

Beta olefin hydration/etherification catalyst compoεitionε.

48.5 Partε of 50% tertiary ammonium bromide were added to a mixture containing 5.5 partε NaOH, 5.45 parts 0 Al₂ (S0₄) ₃.14H₂0, 29.5 partε HiSil 233, 1.0 parts zeolite beta seedε and 116.88 parts deionized water. The reaction mixture waε then heated to 140°C (280"F) and stirred in an autoclave at that temperature for crystallization. . After full crystallinity was achieved, the resulting zeolite Beta crystals were separated from the remaining liquid by filtration, washed with water and dried.

Portions of the zeolite Beta crystals were separately combined with titania and zirconia to form mixtures, each containing of 65 parts zeolite and 35 partε metal oxide binder. Enough water was added to the mixture so that the resulting catalyst could be formed into an extrudate. The catalyst was activated by calcining first in nitrogen at 540 ° C (1000°F) followed by aqueous exchanges .with 1.0 N ammonium nitrate solution and calcining in air at 540°C (1000'F) .

EXAMPLE 2 _ This example illustrates the preparation of 35 wt%

TiO /65 wt% ZSM-35 and 35 wt% Zr0₂/65 wt% ZSM-35 olefin hydration/etherification catalyst compositionε.

3.2 Parts of pyrrolidine were added to a mixture containing 1.38 parts 50% NaOH, 1.18 parts 0 Al (SO ) _, .14H O, 3.2 partε HiSil 233 and 7.5 partε deionized water. The reaction mixture was then heated to 104°C (220°F) and stirred in an autoclave at that temperature for crystallization. After full crystallinity was achieved, the resulting ZSM-35 crystalε were εeparated ₅ from the remaining liquid by filtration, waεhed with water and dried.

Portionε of the ZSM-35 cryεtalε were εeparately combined with titania and zirconia to form mixtureε, each containing 65 partε zeolite and 35 partε metal oxide ₀ binder. Enough water waε added to the mixture εo that the resulting ^ 'ca^yst .qc i . be formed into an extrudate. The catalyεt was activated by calcining first in nitrogen at 540°C (1000°F) , followed by aqueous exchangeε with -1.0 N ammonium nitrate solution and calcining in air at 540'C 5 (100Q-F).

EXAMPLE 3 This example illustrateε the improved results obtained when conducting olefin hydration/etherification with non-acidic metal oxide-bound zeolite Beta olefin 0 hydration catalysts, i.e., the titania- and zirconia-bound zeolite Beta catalyst compositions of Example l_r compared with an acidic metal oxide-bound zeolite Beta, e.g., zeolite bound with 35 parts of alumina. The hydration conditions included the use of eεεentially pure propylene aε the feed, a total system preεεure of 7000kPa (1000 pεig) , a temperature of 166°C (330°F) , a weight hourly space velocity (WHSV) based on propylene of 0.62 and a mole ratio of water to propylene of 0.5.

The results of the olefin hydration/etherification operations are set forth in Table I aε follows:

TABLE I

Propylene Hydration/Etherification Using Various Metal Oxide-Bound Zeolite Beta Catalysts

Zeolite Olefin Hydration/ Etherification Catalyst .

Propylene Conversion, % Water Conversion, % DIPE Selectivity, % IPA Selectivity, % Oligomer Selectivity

As theεe data εhow, propylene conversion activity iε much higher for the titania- and zirconia-bound zeolite catalyεtε. In addition, DIPE εelectivity iε also higher compared to the alumina-bound zeolite catalyst.

EXAMPLE 4 The propylene hydration/etherification operations of Example 3 were subεtantially repeated except that the catalysts were 35 weight percent alumina-bound ZSM-35 and 35 weight percent titania-bound ZSM-35 and the mole ratio of water to propylene waε 2. The reεults of the hydration reactions are set forth in Table II as follows: TABLE II

Propylene Hydration Uεing Variouε Metal Oxide-Bound

ZSM-35 Catalysts

Zeolite Olefin Hydration/ Etherification Catalyst

A1₂0. /ZSM-35 TiO /ZSM-35

Propylene Conversion, % 55.1 72.7 Water Conversion, % 25.3 37.5 IPA Selectivity, % 99.5 98.4

As these data show, the titania-bound zeolite catalyst provided much higher propylene conversion compared to the alumina-bound zeolite.

EXAMPLE 5 A zeolite Beta catalyst composition waε prepared much aε deεcribed in Example 1, εupr , except that the binder waε 17 weight partε of silica.

The reaction conditions were as follows:

Pressure : 200 psig (1480kPa)

Temperature : 200°F (93 °C)

Water:Isobutylene Mole Ratio : 3.2

Time on Stream : 116.5 hr. Weight Hourly Space

Velocity (WHSV) , based on isobutyl- ene : 4.9

Liquid Hourly Space

Velocity (LHSV) : 9.3

The feed posεeεεed the following wt.% compoεition: Water : 24.8 Iεopropanol : 39.6

Isobutylene : 35.6

The percent conversionε and product εelectivitieε are εet forth in Table III aε followε:

TABLE III

Total

Conversion Water Isopropanol Isobutylen

Conversion, % 42.4 40.0 3.6 87.3

T-Butyl Isopropyl

Product Selectivity Alcohol t-Butyl Ether Oligomer

90.1 8.2 1.8

Claims

CLAIMS :

1. A process for converting an olefin to an alcohol and/or an ether comprising reacting the olefin with water and/or an alcohol in the presence of a catalyst comprising a zeolite and a refractory oxide binder co priεing a metal of Group IVA and/or IVB of the Periodic Table of Elementε.

2. The proceεε of Claim 1 wherein the olefin containε 2 to 7 carbon atomε.

3. The proceεs of Claim 1 wherein the olefin is isobutylene.

4. The procesε of Claim 1 wherein the alcohol has 1 to 6 carbon atomε.

5. The proceεε of Claim 1 wherein the zeolite is εelected from mordenite, zeolite Beta, zeolite Y, USY, X, ZSM-5, ZSM-12, ZSM-20, ZSM-23, ZSM-35, and ZSM-50.

6. The proceεε of Claim 1 wherein the metal oxide binder comprises silica, titania, zirconia and/or germania.

7. The process of Claim 1 wherein tne metal oxide binder is titania and/or zirconia.

8. The process of Claim 1 wherein the reaction is conducted at a temperature of 20 to 300^βC, a pressure of at least 500kPa and a water and/or alcohol to olefin ratio of 0.1 to 30.

9. The procesε of Claim 1 wherein the reaction iε conducted at a temperature of 100 to 200°C, a presεure of at leaεt 2000kPa and a water and/or alcohol to olefin ratio of 0.2 to 15.