CA2025016A1 - Process for the conversion of olefins to alcohols and/or ethers - Google Patents
Process for the conversion of olefins to alcohols and/or ethersInfo
- Publication number
- CA2025016A1 CA2025016A1 CA 2025016 CA2025016A CA2025016A1 CA 2025016 A1 CA2025016 A1 CA 2025016A1 CA 2025016 CA2025016 CA 2025016 CA 2025016 A CA2025016 A CA 2025016A CA 2025016 A1 CA2025016 A1 CA 2025016A1
- Authority
- CA
- Canada
- Prior art keywords
- zeolite
- olefin
- zsm
- alcohol
- water
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
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.
and/or IVB of the Periodic Table of Elements, e.g., silica, titania, zirconia and/or germania.
Description
~ 090/0~12~ PcT/~s9o/(~ol~' 2 ~ v' PROCESS FOR THE CONVERSION OF OLEFINS
TO ~.LCOHOLS AND/OR ~THERS
This invention relates to a process for the catalytic conversion of olefins to provide alcohols, ethers and their mixtures useful, nter alia, as high octane blending stocks for gasoline.
There is a need for an e~ficient catalyt1c process to manufacture alcohols and ethers from light olefins thereby augmenting the supply of high octane blending stocks fo~ gasoline. Lower mclecular weight alcohols and ethers suoh as isopropyl alcohol (IPA) and diisoprop~l et~er (DIPE) are in the gasoline boiling range and are known to have a high blending octane number. In addition, ~y-product propylene from which IPA and DIPE can ~e ma~e is usually available in a fuels refinery. The petrochemicals industry also produces mixtures of light olefin streams in the C2 to C7 molecular weight range and the conversion of such s'reams 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 alcohois 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 ole~ins, 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 Inde~
~O90/0817~ PCT/~9()/()01 of 1-12, e.g. ZSM-5, to provide the corresponding alcohc`, essentially free of ether and hydrocarbo~ by-produ~t.
According to U.S. Patent No. 4499313, an olefin is hydrated to the corresponding alcohol in the presence Or j hydrogen mordenite 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 alsa said to offer the advantag-i over ion-exchange type olefin h~dra~icn catalysts of n -- being restricted by the hydration te~erature.
U.S. Patent No 47835~5 describes an olefin hydra~
process employing a mediu~ pore zeolite as hydration catalyst. Specific catays~s mentioned are theta-l, l; ferrierite, ZSM-22, ZSM-23 an~ Nu-10 The catalyzed reaction of olefins with alcohols to provide ethers is a well known process. For example, ~.S.
Patent No. 4,042,633 discloses the preparation of diisopropyl ether (DIPE~ from isopropyl alcohol (IPA) employing a montmorillonite clay catalyst, optionally in the presence of added propylene. U.S. Patent No. 4,182,914 discloses t~e produ~tion of ~IPE 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 C4 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 isobuty-ene and methanol in the presence of boron phosphate, blue tungsten oxide or a crystalline aluminosilicate zeolite having a silica to alumina mole UO90/~812~) _ 3 _ PCT/~S~0/001~ -ratio of at least 12:1 and a Constraint Index of fro~ 1 to 12 as catalyst.
As disclosed in ~.S. Pate~t No. 4,605,787, al~
tert- alkyl ethers such as MTBE and tertiary amyl ~e~hyl ether (TAME) are prepared by the reaction of a primary alcohol with an olefin having a double bon~ 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-ll, ZSM-12, ZSM-23 dealuminized zeolite Y and rare earth-exchanged zeolite Y.
U.S. Patent No. ~,714"87 discloses th~ preparatior of ethers by the catalytic reaction of linear ~onoolefinc with primary or secondary alcohols employing, as a catalyst, a zeolite ha~ing a pore size greater than 5 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, 2~ 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 2~ to provide an ether, e.g., isobutene and methanol are reacted to provide MTBE, in the presence of an acidic zeollte such as zeolite Beta, ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35 and ZSM-48, as a catalyst.
It is a common practice in zeolite catalyst 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 O90/08120 PC~/~
possessing good mechanical strength. In many cases, the binder component contributes little to the observed catalytic activity and can be regarded as an inert diluen~
for the catalytically active zeolite component. Howeve~, it has now been discovered tha~ the activity and selectivity of zeolite catalys~s used in olefin hydration/etherification may be significantly influenced by the nature of the binders with which the zeolitcs are composited.
Accordingly, the inventior resides in a process fc~-converting an olefin to an alcohol and/or an ether co~.prisinc reacting the olef in ~ith water and/or an alcohol in the presence of a catalyst comprising a zeolite and a refractory binde~ comprising a metal of Group IV~
1- and/or IVB of the Periodic Table of Elements.
The present invention is applicable to the conversion of individual light olefins and mixtures of ole~ins of various structures, preferably within the C2 7 range. Accordingly, the invention is applicable to the conversion of ethylene, propylene, butenes, pentenes, hexenes, heptenes, mixtures of these and other olefins such as gas pl2nt off-gas containing ethylene ~nd, . -propylene, naphtha cracker off-gas containing light olefins, fluidized catalytic cracked (FCC) light gasoline 2~ containing pentenes, hexenes and heptenes, and refinery FCC propane/propylene streams. For example, a typical FCC
light olefin stream possesses the following composition:
O9~/0~120 ~ PCT/~S9~ 013 TY~ical RefinerY FCC Lia~ Olefin Compositio~
Wt.% Mole~
Ethane 3.3 ~.l Ethylene 0.7 l.2 Propane 14.5 ~5.3 Propylene42.5 46.8 Isobutanel2.9 lO.3 n-Butane 3.~ 2. t Butenes 22.l 18.3 Pentanes 0.7 0.~
The process of the invention is especially applicable to the conversion of propylene an~
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 '0 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 derydration 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 l 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.
090/0~120 PC~/~S9(~ 01~' -- 6 -- .
They include a temperature ranging from am~ient (20 c) tc 300C, preferably from 50 to 220C and more prefer2biy from 100 to 200C, a total system pressure of at least 5 atm (500kPa), preferably at least 20 atm (2000kPa)and mor~
preferably at least 40 atm (4000kPa), a total water and/or alcohol to olefin mole ratio of from 0.1 to 30, preferabl~-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 wai~r to total olefin mole ratios as disclosed in E~-A-323270, e.g., at water to total olefin ~ole ratios of less than about 1.
It will also be appreciated that the precise conditions selected should, to some extent, reflect th~
nature of the olefin feed. For example, isoolefins generally re~lire milder process conditions than straight chain olefins. Thus, in the case of isobutylene, CH2=CH(CH3)2, good conversions to ether can be obtained with process conditions of from 30C to 100C, 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;fro~
~.1 to 30, preferably from 0.2 to i5-and mo~~p~ `a`~
from 0.3 to 5 and an LHSV of from 0;1 to 25.
The olefin conversion process of this invent~on car 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.
TO ~.LCOHOLS AND/OR ~THERS
This invention relates to a process for the catalytic conversion of olefins to provide alcohols, ethers and their mixtures useful, nter alia, as high octane blending stocks for gasoline.
There is a need for an e~ficient catalyt1c process to manufacture alcohols and ethers from light olefins thereby augmenting the supply of high octane blending stocks fo~ gasoline. Lower mclecular weight alcohols and ethers suoh as isopropyl alcohol (IPA) and diisoprop~l et~er (DIPE) are in the gasoline boiling range and are known to have a high blending octane number. In addition, ~y-product propylene from which IPA and DIPE can ~e ma~e is usually available in a fuels refinery. The petrochemicals industry also produces mixtures of light olefin streams in the C2 to C7 molecular weight range and the conversion of such s'reams 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 alcohois 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 ole~ins, 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 Inde~
~O90/0817~ PCT/~9()/()01 of 1-12, e.g. ZSM-5, to provide the corresponding alcohc`, essentially free of ether and hydrocarbo~ by-produ~t.
According to U.S. Patent No. 4499313, an olefin is hydrated to the corresponding alcohol in the presence Or j hydrogen mordenite 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 alsa said to offer the advantag-i over ion-exchange type olefin h~dra~icn catalysts of n -- being restricted by the hydration te~erature.
U.S. Patent No 47835~5 describes an olefin hydra~
process employing a mediu~ pore zeolite as hydration catalyst. Specific catays~s mentioned are theta-l, l; ferrierite, ZSM-22, ZSM-23 an~ Nu-10 The catalyzed reaction of olefins with alcohols to provide ethers is a well known process. For example, ~.S.
Patent No. 4,042,633 discloses the preparation of diisopropyl ether (DIPE~ from isopropyl alcohol (IPA) employing a montmorillonite clay catalyst, optionally in the presence of added propylene. U.S. Patent No. 4,182,914 discloses t~e produ~tion of ~IPE 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 C4 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 isobuty-ene and methanol in the presence of boron phosphate, blue tungsten oxide or a crystalline aluminosilicate zeolite having a silica to alumina mole UO90/~812~) _ 3 _ PCT/~S~0/001~ -ratio of at least 12:1 and a Constraint Index of fro~ 1 to 12 as catalyst.
As disclosed in ~.S. Pate~t No. 4,605,787, al~
tert- alkyl ethers such as MTBE and tertiary amyl ~e~hyl ether (TAME) are prepared by the reaction of a primary alcohol with an olefin having a double bon~ 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-ll, ZSM-12, ZSM-23 dealuminized zeolite Y and rare earth-exchanged zeolite Y.
U.S. Patent No. ~,714"87 discloses th~ preparatior of ethers by the catalytic reaction of linear ~onoolefinc with primary or secondary alcohols employing, as a catalyst, a zeolite ha~ing a pore size greater than 5 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, 2~ 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 2~ to provide an ether, e.g., isobutene and methanol are reacted to provide MTBE, in the presence of an acidic zeollte such as zeolite Beta, ZSM-5, ZSM-ll, ZSM-12, ZSM-23, ZSM-35 and ZSM-48, as a catalyst.
It is a common practice in zeolite catalyst 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 O90/08120 PC~/~
possessing good mechanical strength. In many cases, the binder component contributes little to the observed catalytic activity and can be regarded as an inert diluen~
for the catalytically active zeolite component. Howeve~, it has now been discovered tha~ the activity and selectivity of zeolite catalys~s used in olefin hydration/etherification may be significantly influenced by the nature of the binders with which the zeolitcs are composited.
Accordingly, the inventior resides in a process fc~-converting an olefin to an alcohol and/or an ether co~.prisinc reacting the olef in ~ith water and/or an alcohol in the presence of a catalyst comprising a zeolite and a refractory binde~ comprising a metal of Group IV~
1- and/or IVB of the Periodic Table of Elements.
The present invention is applicable to the conversion of individual light olefins and mixtures of ole~ins of various structures, preferably within the C2 7 range. Accordingly, the invention is applicable to the conversion of ethylene, propylene, butenes, pentenes, hexenes, heptenes, mixtures of these and other olefins such as gas pl2nt off-gas containing ethylene ~nd, . -propylene, naphtha cracker off-gas containing light olefins, fluidized catalytic cracked (FCC) light gasoline 2~ containing pentenes, hexenes and heptenes, and refinery FCC propane/propylene streams. For example, a typical FCC
light olefin stream possesses the following composition:
O9~/0~120 ~ PCT/~S9~ 013 TY~ical RefinerY FCC Lia~ Olefin Compositio~
Wt.% Mole~
Ethane 3.3 ~.l Ethylene 0.7 l.2 Propane 14.5 ~5.3 Propylene42.5 46.8 Isobutanel2.9 lO.3 n-Butane 3.~ 2. t Butenes 22.l 18.3 Pentanes 0.7 0.~
The process of the invention is especially applicable to the conversion of propylene an~
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 '0 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 derydration 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 l 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.
090/0~120 PC~/~S9(~ 01~' -- 6 -- .
They include a temperature ranging from am~ient (20 c) tc 300C, preferably from 50 to 220C and more prefer2biy from 100 to 200C, a total system pressure of at least 5 atm (500kPa), preferably at least 20 atm (2000kPa)and mor~
preferably at least 40 atm (4000kPa), a total water and/or alcohol to olefin mole ratio of from 0.1 to 30, preferabl~-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 wai~r to total olefin mole ratios as disclosed in E~-A-323270, e.g., at water to total olefin ~ole ratios of less than about 1.
It will also be appreciated that the precise conditions selected should, to some extent, reflect th~
nature of the olefin feed. For example, isoolefins generally re~lire milder process conditions than straight chain olefins. Thus, in the case of isobutylene, CH2=CH(CH3)2, good conversions to ether can be obtained with process conditions of from 30C to 100C, 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;fro~
~.1 to 30, preferably from 0.2 to i5-and mo~~p~ `a`~
from 0.3 to 5 and an LHSV of from 0;1 to 25.
The olefin conversion process of this invent~on car 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.
3~ Reaction times of from 20 minutes to 20 hours when operating in batch and an LHSV of from 0.1 to 2S when operating continuously are generally suitable. It may, UO 90/0812() ~ ~ r~ PC~/~S90/()Ol~i~
.
of course, be advantageous to recover any unreacted olefir and recycle it to the reactor.
When seeking to maximize the production of ether b.
the hydration of olefin, the aqueous product effluent fro~
the olefin hydration reactor containing alcohol and ether can be introduced into a separator, e.g., a cistillation column, for recovery of ether. The dilutle aqueous solution of alcohol ma~ be then introduced into a second separator, e.g., another distillation colu~n, where a water/alcohol azeotrope is recovered. A f ~ction of th2 azeotrope may be fed into a conYentional dehydra=ion reactor to provid^ a further quantity of ether which can be combined with the ether previously recovered from the olefin hydration reactor. By blending various product 1~ 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 CU;`..s~:it:~.lte nt' ~OC` abou_ 20 weit7ht percent of the gasoline to which they are added.
A particularly advantageous procedure for producing 2~- 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/3IPE
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, ~090/~12n PcT/~9o/l)ol3 together with recycled ~nreacted 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 ; 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 C6 olefin) is distilled off an~, following cooling is introduced into a decanter i~ ~hich phas~ sepa-ation ta~ec place. The upper layer contain~ mostly DIP~, ~.g., so weight percent or more, cnd relatively little water, e.g., l weight percent or so. The lower layer is largely water 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 overheads to provide the final IPA/DIPE mixture.
Where it is desired to separate out the alcohol from an alcohol/etherimixture~and thus ~ro~ D'~S -ether, one can advantageously-practIce th~ ~rocedure of EP-A-323l38. According to this process as applied to the 2; 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 below the olefin hydration reaction temperature. There, two liguid phases form, the aqueous phase being removed and recycled to the hydration reactor. The ~090/081~ P~r/~S~0/(~01 hydro~arbon-rich phase i5 flashed to a lower pressur~ tc effect separation of the unreacted C3 components. Tne flashed product, now containing a substantial amount of IPA product, is introduced to a distillation unit operate~
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 pro~ides a DIPE product containing at most negligible amounts of IPA and water, e.g., 1.0 weight percent and 0.
weight percent of these materials, respectivel~. The remaining aqLeous phase can ~e recycled to the reactor.
The catalyst employed in the olefin conversion 1; process of this invention can include any zeolite which is effective for the catalysis of the reaction of olefin(s) with water and/or alcohol(s) to produce alcohol(s), ether(s) or their mixtures. Representative of the zeolites which are useful herein are zeolite Beta, zeolite X, zeolite L, zeolite Y, ultrastable zeolite Y (USY), dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-5, ZSM-12, ZSM-20, ZS~ 3~ 7.SM-50, and ~;;.xtures of any of the foregoing.
Zeolite Beta is described in U.S. Reissue Patent No.
2j 28,341 (of original U.S. Patent No. 3,308,069). Zeolite X
is described in U.S. Patent No. 2,882,244. Zeolite L is described in U.S. Patent No. 3,216,789. Zeolite Y is described i~ U.S. Patent No. 3,130,007. Low sodium ultr~stable zeolite Y (USY) is described in U.S. Patent Nos. 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. 3,442,79S. Zeolite ZSM-3 is described in U.S. Patent No. 3,415,736. Zeolite ~'O 9()/OXl~l PCr/~91~/()(~1~' -- 10 -- , ZSM-5 is described in U.S. Patent Re. 29,948 (of original U.S. Patent No. 3,702,886). Zeolite ZSM-12 is 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 describe~ in U.s. Patent No. 4,076,842. Zeolite ZSM-35 is described ln U.S. Patent No. 4,016,245. Zeolite ZSM-50 is described i~
U.S. Patent No. 4,640,829.
The zeolite olefin hydration/etherification catalysts selected for use herein will generally ~ ossess an alpha value of at least about 1. "Alpha value", cr "alpha number", is a measure of zeolite acidic functionality and is more fully described together ~i h details of its measurement in J. CatalYsis, 6l, pp.
390-396 (1980). Zeolites of relatively low acidity (e.g., 1~ zeolites possessing alpha values of less than about 200) can be prepared by a variety of techniques including (a) synthesizing a zeolite with a high silica/alumina ratio, (b) steaming, (c) steaming followed by dealuminization and (d) substituting framework aluminum with other trivalent 20 metal species. For example, in the case of steaming, the zeolite can bç expo~ed to stea~ at elevated temperatures rangi~gSf~m 26~ o-~0U~a(~ ~ m~o .~ 2 nd-pref~ra~ly from 400 to 540C (750 to lOC~F~.~ri~his treatment can be accomplished in an atmosphere of 100% steam or an 25 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 7~0'F) and from lO00 to 20000kPa (lO to 200 atmospheres).
30 Specific details of several steaming procedures may be gained from the disclosures of U.S. Patent Nos. 4,325,994, 4,374,296 and 4,418,235. Aside from, or in addition to any of the foregoing procedures, the surface acidity of the ~O90/08~2t) r~ C,; ~ ^ ;;3 PC'r/~S90/()()1~' zeolite can be elimi~ated or reduced by treatment with bulky reagents as described in U.S. Patent No. 4,520,2~1.
Prior to their use as olefin hydration/etherification catalysts, the as-synthesized zeolite crystals should be subjected to thermal traatment to remove part or all of any organic constituent present therein. In addition, the zeolites should be at least partially dried prior to use. This can be done by heatin~
the crystals to a temperature in the range of fro~ 200 to ]~ 595DC in an inert atmosphere, such as air or ritrogen an~
atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes to 48 h~urs. Dehydratio~ can also be performed at room temperature merely by placing the crystalline material in a vacuum, but a longer time is 1~ required to obtain a sufficient amount of de~ydration.
The original cations associated 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, alkyi ammonium and metal cations, and their mixtures. Metal cations can also ~e introduced intc he zeolite. In the case o.. .i~.;.?.t.z i. catioris, partLcuiar preference is given to metals Gf Groups IB to VIII of the Periodic Table including, by way of example, ircn, nickel, cobalt, copper, zinc, platinum, palladium, calcium, chro~ium, 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 sul~ates. ~epresentative ion-exchange techniques are ~'090/08t2(l PCT/~'~9~)/(1013 - 12 ~
disclosed i~ a number of patents including U.S. Patent Nos. 3,140,2~9i 3,140,251 and 3,140,253. Following con~act with a solution of the desired replacing cation, the zeolite is then preferably washed with water and dried at a temperature ranging from 65 to 315C (150 to 600F) and thereafter calcined in air or other inert gas at temperatures ranging from 2~0 to 820C (500 to 1500F) for periods of time ranginq from 1 to 48 hours or more.
The catalyst empioyed in the process of the invention als~ includes a binder ma~erial in the form of at least one essentially non-acidic refractory o~ide of .
metal of Groups IVA or IVB of the Periodic Table of the Elements. Particularly useful are the oxides of silicon, germanium, titanium and zirconium. Combinations of such 1~ 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 is one or a combination of the aforesaid Group IVA and/or Group IVB metal oxides. Thus, mixtures of oxides which can be used to provide the.binder material herein include titania-alumina, titania-magnesic, titani,a-z,i.r.coni.,~, titania-thoria, titania-beryllia, titan~ R.,-.,~ a~ iF~.-;,.,.s,'.,`.i~a-alu~ina-z.rcon~a,,.~.
silica-alumina-magnesia ~na s;lica-titania-zirconia, zirconia-alumina and silica-zirconia.
In preparing the refractory oxide-bound zeolite catalyst, it is generally advantageous to provide at least a part of the binder in colloidal form as 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 ~90/OX12() ~ 5~ PCT/~S90/()013 silica ranging from 2 to 60 weight percent of the total binder generally provide good results. ~he relative proportions of zeolite and refractory oxide binder on an anhydrous basis can vary widely with the zeolite content ranging from between l to 99 weight percent, and more ~sually in the range of from 20 to 80 weight percen., of the dry composite.
In the examples which follow in which ail parts are by weight, Examples l and 2 are illustrative of the preparation of zeolite catalysts which are useful as catalysts herein and Examples 3 to 5 are illustrative c-the olefin conversior, process of this inventio...
This example illustrates the preparation of 35 wt%
Tio2/65 wt% zeolite Beta and 35 Wt% ZrO2/65 wt% zeolite Beta olefin hydration/etherification catalyst compositions.
48.5 Parts of 50% tertiary am~onium bromide were added to a mixture containing 5.5 parts NaO~, 5.45 par_s Al2(S04)3.14H20, 29.5 parts HiSil 233, 1.0 parts zeolite beta se?ds and 116.8~ parts deiDnized water. ~ile r.-:ac~ "
mixture was then heated to 140C (280-F) and scirred 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 parts 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 U'O90/0812() PCT/~;S90/(~()13 ln nitrogen at 540C (1000F) followed by aqueo~s exchanges with 1.0 N ammonium nitrate solution and calcining in air at 540C (1000DF).
This example illustrates the preparacion of 3~ ~t%
Tio2/65 wt% ZSM-35 and 35 wt% ZrO2/65 wt% ZSM-35 olefin hydration/etherification catalyst compositions.
3.2 Parts of pyrrolidine were added to a rixture containing 1.3~ parts 50% NaOH, 1.18 parts A12(SO~)~.14H20, 3.2 parts Hisil 233 and 7.5 parts deionized water. The react-ion mixture was then heate~ to 104C (220F) and stirred in an autociave at that temperature for crystallization. After full crystallinity was achieved, the resulting ZSM-35 crystals were separated from the remaining liquid by filtration, washed with w~ater and dried.
Portions of the ZSM-35 crystals were separately combined with titania and zirconia to form mixtures, each containing 65 parts zeolite and 35 parts metal oxide binder. Enough water was added to the mixture so tha~ the -:es~ a~ _~'alyst could be formed into an extrudate. The catalyst was activated by calcining first in nitrogen at 540C (1000F), followed by aqueous exchanges with 1.0 ammonium nitrate solution and calcining in air at 540'C
(1000'F) This example illustrates the improved results obtained when conducting olefin hydration/etherification with non-acidic metal oxide-bound z201ite Beta olefin hydration catalysts, i.e., the titania- and zirconia-bound zeolite Beta catalyst compositions of Example 1, compared with an acidic metal oxide-bound zeolite Beta, e.g., zeolite bound with 35 parts of alumina.
~O90/OX12() ~ 0 2 s ~ P~r/~ X~0/~)013 The hydratiQn conditions included the use of essentially pure propylene as the feed, a total syste~
pressure of 7000kPa (1000 psig), a temperature of 166C
(330F), 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 as follows:
~ TABLE I
IG Propylene Hydration/Etherification Usina various Meta Oxide-Bc-~nd Zeolite Beta Catalysts _ Zeolite Olefin Hydration/
Etherification Catalyst A12 3/ TiO2/Beta ~ ZrO2/Beta Propylene Conversion, % 44.9 69.0 65.-Water Conversion, %53.7 78.4 75.3 DIPE Selecti~ity, %57.3 58.9 61.5 IPA Selectivity, ~ 39.7 37.0 3~. 5 Oligomer Selectivity3.0 4.1 ~._ 2~l As these data show, propylene conversion activit~
is much higher for the titania- and zirconia-bound zeolite catalysts. In addition, DIPE selectivit~ is also higher compared to the alumina-bound zeolite catalyst.
. EXAM E 4 The propylene hydration/etherification operations of Example 3 were substantially 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 was 2.
The results of the hydration reactions are set forth in Table II as follows:
~'090/08120 PCT/~S9~iO013 TABLE II
Propylene Hydratlon Using Various Metal Oxide-Bound ZSM-35 Ca~alysts _ Zeolite Olefin Hydration/
5Etherification Catalyst -Al2o~/zs}~-35 TiO2/Zsl~-35 Propylene Conversion, ~ 55.l 72.7 Water Conversion, % 25.3 37.5 IPA Selectivity, % 99.5 98.
lOAs these data show, the titania-bound zeolite catalyst provided much higher propylene conversion compared to the alumina-bound zeolite.
EX~MPLE 5 A zeolite Beta catalyst composition was prepared 15much as described in Example l, supra, except that the binder was 17 weight parts of silica.
~090/0812~ PCr/~`~9()/~)l3 The reaction conditions were as follows:
Pressure : 200 psig (1480};-~) Temperature : 200'F (93'C) Water:Isobutylene Mole Ratio : 3.2 Time on Stream : 116.~ hr.
Weight Hourly Space Velocity (WHSV), based on isobutyl-ene ~.9 Liquid Hourly Space Velocity (LHSV) : 9.3 The feed possessed the followirg wt.% composi~ion:
Water : 2~.8 Isopropanol : 39.6 Isobutylene : 35.6 The percent conversions and product selectivities are set forth in Table III as follows:
TABLE III
Total Conversion Water IsoPropanol Isobutvlene Conversion, % 42.4 40.0 3.6 87.3 T-Butyl Isopropyl Product Selectivity Alcohol t-ButYl Ether Oliqomers 90.1 8.2 l.
. . . .
. , .
.
of course, be advantageous to recover any unreacted olefir and recycle it to the reactor.
When seeking to maximize the production of ether b.
the hydration of olefin, the aqueous product effluent fro~
the olefin hydration reactor containing alcohol and ether can be introduced into a separator, e.g., a cistillation column, for recovery of ether. The dilutle aqueous solution of alcohol ma~ be then introduced into a second separator, e.g., another distillation colu~n, where a water/alcohol azeotrope is recovered. A f ~ction of th2 azeotrope may be fed into a conYentional dehydra=ion reactor to provid^ a further quantity of ether which can be combined with the ether previously recovered from the olefin hydration reactor. By blending various product 1~ 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 CU;`..s~:it:~.lte nt' ~OC` abou_ 20 weit7ht percent of the gasoline to which they are added.
A particularly advantageous procedure for producing 2~- 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/3IPE
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, ~090/~12n PcT/~9o/l)ol3 together with recycled ~nreacted 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 ; 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 C6 olefin) is distilled off an~, following cooling is introduced into a decanter i~ ~hich phas~ sepa-ation ta~ec place. The upper layer contain~ mostly DIP~, ~.g., so weight percent or more, cnd relatively little water, e.g., l weight percent or so. The lower layer is largely water 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 overheads to provide the final IPA/DIPE mixture.
Where it is desired to separate out the alcohol from an alcohol/etherimixture~and thus ~ro~ D'~S -ether, one can advantageously-practIce th~ ~rocedure of EP-A-323l38. According to this process as applied to the 2; 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 below the olefin hydration reaction temperature. There, two liguid phases form, the aqueous phase being removed and recycled to the hydration reactor. The ~090/081~ P~r/~S~0/(~01 hydro~arbon-rich phase i5 flashed to a lower pressur~ tc effect separation of the unreacted C3 components. Tne flashed product, now containing a substantial amount of IPA product, is introduced to a distillation unit operate~
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 pro~ides a DIPE product containing at most negligible amounts of IPA and water, e.g., 1.0 weight percent and 0.
weight percent of these materials, respectivel~. The remaining aqLeous phase can ~e recycled to the reactor.
The catalyst employed in the olefin conversion 1; process of this invention can include any zeolite which is effective for the catalysis of the reaction of olefin(s) with water and/or alcohol(s) to produce alcohol(s), ether(s) or their mixtures. Representative of the zeolites which are useful herein are zeolite Beta, zeolite X, zeolite L, zeolite Y, ultrastable zeolite Y (USY), dealuminized Y (Deal Y), mordenite, ZSM-3, ZSM-5, ZSM-12, ZSM-20, ZS~ 3~ 7.SM-50, and ~;;.xtures of any of the foregoing.
Zeolite Beta is described in U.S. Reissue Patent No.
2j 28,341 (of original U.S. Patent No. 3,308,069). Zeolite X
is described in U.S. Patent No. 2,882,244. Zeolite L is described in U.S. Patent No. 3,216,789. Zeolite Y is described i~ U.S. Patent No. 3,130,007. Low sodium ultr~stable zeolite Y (USY) is described in U.S. Patent Nos. 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. 3,442,79S. Zeolite ZSM-3 is described in U.S. Patent No. 3,415,736. Zeolite ~'O 9()/OXl~l PCr/~91~/()(~1~' -- 10 -- , ZSM-5 is described in U.S. Patent Re. 29,948 (of original U.S. Patent No. 3,702,886). Zeolite ZSM-12 is 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 describe~ in U.s. Patent No. 4,076,842. Zeolite ZSM-35 is described ln U.S. Patent No. 4,016,245. Zeolite ZSM-50 is described i~
U.S. Patent No. 4,640,829.
The zeolite olefin hydration/etherification catalysts selected for use herein will generally ~ ossess an alpha value of at least about 1. "Alpha value", cr "alpha number", is a measure of zeolite acidic functionality and is more fully described together ~i h details of its measurement in J. CatalYsis, 6l, pp.
390-396 (1980). Zeolites of relatively low acidity (e.g., 1~ zeolites possessing alpha values of less than about 200) can be prepared by a variety of techniques including (a) synthesizing a zeolite with a high silica/alumina ratio, (b) steaming, (c) steaming followed by dealuminization and (d) substituting framework aluminum with other trivalent 20 metal species. For example, in the case of steaming, the zeolite can bç expo~ed to stea~ at elevated temperatures rangi~gSf~m 26~ o-~0U~a(~ ~ m~o .~ 2 nd-pref~ra~ly from 400 to 540C (750 to lOC~F~.~ri~his treatment can be accomplished in an atmosphere of 100% steam or an 25 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 7~0'F) and from lO00 to 20000kPa (lO to 200 atmospheres).
30 Specific details of several steaming procedures may be gained from the disclosures of U.S. Patent Nos. 4,325,994, 4,374,296 and 4,418,235. Aside from, or in addition to any of the foregoing procedures, the surface acidity of the ~O90/08~2t) r~ C,; ~ ^ ;;3 PC'r/~S90/()()1~' zeolite can be elimi~ated or reduced by treatment with bulky reagents as described in U.S. Patent No. 4,520,2~1.
Prior to their use as olefin hydration/etherification catalysts, the as-synthesized zeolite crystals should be subjected to thermal traatment to remove part or all of any organic constituent present therein. In addition, the zeolites should be at least partially dried prior to use. This can be done by heatin~
the crystals to a temperature in the range of fro~ 200 to ]~ 595DC in an inert atmosphere, such as air or ritrogen an~
atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes to 48 h~urs. Dehydratio~ can also be performed at room temperature merely by placing the crystalline material in a vacuum, but a longer time is 1~ required to obtain a sufficient amount of de~ydration.
The original cations associated 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, alkyi ammonium and metal cations, and their mixtures. Metal cations can also ~e introduced intc he zeolite. In the case o.. .i~.;.?.t.z i. catioris, partLcuiar preference is given to metals Gf Groups IB to VIII of the Periodic Table including, by way of example, ircn, nickel, cobalt, copper, zinc, platinum, palladium, calcium, chro~ium, 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 sul~ates. ~epresentative ion-exchange techniques are ~'090/08t2(l PCT/~'~9~)/(1013 - 12 ~
disclosed i~ a number of patents including U.S. Patent Nos. 3,140,2~9i 3,140,251 and 3,140,253. Following con~act with a solution of the desired replacing cation, the zeolite is then preferably washed with water and dried at a temperature ranging from 65 to 315C (150 to 600F) and thereafter calcined in air or other inert gas at temperatures ranging from 2~0 to 820C (500 to 1500F) for periods of time ranginq from 1 to 48 hours or more.
The catalyst empioyed in the process of the invention als~ includes a binder ma~erial in the form of at least one essentially non-acidic refractory o~ide of .
metal of Groups IVA or IVB of the Periodic Table of the Elements. Particularly useful are the oxides of silicon, germanium, titanium and zirconium. Combinations of such 1~ 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 is one or a combination of the aforesaid Group IVA and/or Group IVB metal oxides. Thus, mixtures of oxides which can be used to provide the.binder material herein include titania-alumina, titania-magnesic, titani,a-z,i.r.coni.,~, titania-thoria, titania-beryllia, titan~ R.,-.,~ a~ iF~.-;,.,.s,'.,`.i~a-alu~ina-z.rcon~a,,.~.
silica-alumina-magnesia ~na s;lica-titania-zirconia, zirconia-alumina and silica-zirconia.
In preparing the refractory oxide-bound zeolite catalyst, it is generally advantageous to provide at least a part of the binder in colloidal form as 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 ~90/OX12() ~ 5~ PCT/~S90/()013 silica ranging from 2 to 60 weight percent of the total binder generally provide good results. ~he relative proportions of zeolite and refractory oxide binder on an anhydrous basis can vary widely with the zeolite content ranging from between l to 99 weight percent, and more ~sually in the range of from 20 to 80 weight percen., of the dry composite.
In the examples which follow in which ail parts are by weight, Examples l and 2 are illustrative of the preparation of zeolite catalysts which are useful as catalysts herein and Examples 3 to 5 are illustrative c-the olefin conversior, process of this inventio...
This example illustrates the preparation of 35 wt%
Tio2/65 wt% zeolite Beta and 35 Wt% ZrO2/65 wt% zeolite Beta olefin hydration/etherification catalyst compositions.
48.5 Parts of 50% tertiary am~onium bromide were added to a mixture containing 5.5 parts NaO~, 5.45 par_s Al2(S04)3.14H20, 29.5 parts HiSil 233, 1.0 parts zeolite beta se?ds and 116.8~ parts deiDnized water. ~ile r.-:ac~ "
mixture was then heated to 140C (280-F) and scirred 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 parts 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 U'O90/0812() PCT/~;S90/(~()13 ln nitrogen at 540C (1000F) followed by aqueo~s exchanges with 1.0 N ammonium nitrate solution and calcining in air at 540C (1000DF).
This example illustrates the preparacion of 3~ ~t%
Tio2/65 wt% ZSM-35 and 35 wt% ZrO2/65 wt% ZSM-35 olefin hydration/etherification catalyst compositions.
3.2 Parts of pyrrolidine were added to a rixture containing 1.3~ parts 50% NaOH, 1.18 parts A12(SO~)~.14H20, 3.2 parts Hisil 233 and 7.5 parts deionized water. The react-ion mixture was then heate~ to 104C (220F) and stirred in an autociave at that temperature for crystallization. After full crystallinity was achieved, the resulting ZSM-35 crystals were separated from the remaining liquid by filtration, washed with w~ater and dried.
Portions of the ZSM-35 crystals were separately combined with titania and zirconia to form mixtures, each containing 65 parts zeolite and 35 parts metal oxide binder. Enough water was added to the mixture so tha~ the -:es~ a~ _~'alyst could be formed into an extrudate. The catalyst was activated by calcining first in nitrogen at 540C (1000F), followed by aqueous exchanges with 1.0 ammonium nitrate solution and calcining in air at 540'C
(1000'F) This example illustrates the improved results obtained when conducting olefin hydration/etherification with non-acidic metal oxide-bound z201ite Beta olefin hydration catalysts, i.e., the titania- and zirconia-bound zeolite Beta catalyst compositions of Example 1, compared with an acidic metal oxide-bound zeolite Beta, e.g., zeolite bound with 35 parts of alumina.
~O90/OX12() ~ 0 2 s ~ P~r/~ X~0/~)013 The hydratiQn conditions included the use of essentially pure propylene as the feed, a total syste~
pressure of 7000kPa (1000 psig), a temperature of 166C
(330F), 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 as follows:
~ TABLE I
IG Propylene Hydration/Etherification Usina various Meta Oxide-Bc-~nd Zeolite Beta Catalysts _ Zeolite Olefin Hydration/
Etherification Catalyst A12 3/ TiO2/Beta ~ ZrO2/Beta Propylene Conversion, % 44.9 69.0 65.-Water Conversion, %53.7 78.4 75.3 DIPE Selecti~ity, %57.3 58.9 61.5 IPA Selectivity, ~ 39.7 37.0 3~. 5 Oligomer Selectivity3.0 4.1 ~._ 2~l As these data show, propylene conversion activit~
is much higher for the titania- and zirconia-bound zeolite catalysts. In addition, DIPE selectivit~ is also higher compared to the alumina-bound zeolite catalyst.
. EXAM E 4 The propylene hydration/etherification operations of Example 3 were substantially 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 was 2.
The results of the hydration reactions are set forth in Table II as follows:
~'090/08120 PCT/~S9~iO013 TABLE II
Propylene Hydratlon Using Various Metal Oxide-Bound ZSM-35 Ca~alysts _ Zeolite Olefin Hydration/
5Etherification Catalyst -Al2o~/zs}~-35 TiO2/Zsl~-35 Propylene Conversion, ~ 55.l 72.7 Water Conversion, % 25.3 37.5 IPA Selectivity, % 99.5 98.
lOAs these data show, the titania-bound zeolite catalyst provided much higher propylene conversion compared to the alumina-bound zeolite.
EX~MPLE 5 A zeolite Beta catalyst composition was prepared 15much as described in Example l, supra, except that the binder was 17 weight parts of silica.
~090/0812~ PCr/~`~9()/~)l3 The reaction conditions were as follows:
Pressure : 200 psig (1480};-~) Temperature : 200'F (93'C) Water:Isobutylene Mole Ratio : 3.2 Time on Stream : 116.~ hr.
Weight Hourly Space Velocity (WHSV), based on isobutyl-ene ~.9 Liquid Hourly Space Velocity (LHSV) : 9.3 The feed possessed the followirg wt.% composi~ion:
Water : 2~.8 Isopropanol : 39.6 Isobutylene : 35.6 The percent conversions and product selectivities are set forth in Table III as follows:
TABLE III
Total Conversion Water IsoPropanol Isobutvlene Conversion, % 42.4 40.0 3.6 87.3 T-Butyl Isopropyl Product Selectivity Alcohol t-ButYl Ether Oliqomers 90.1 8.2 l.
. . . .
. , .
Claims (9)
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 comprising a metal of Group IVA and/or IVB of the Periodic Table of Elements.
2. The process of Claim 1 wherein the olefin contains 2 to 7 carbon atoms.
3. The process of Claim 1 wherein the olefin is isobutylene.
4. The process of Claim 1 wherein the alcohol has 1 to 6 carbon atoms.
5. The process of Claim 1 wherein the zeolite is selected from mordenite, zeolite Beta, zeolite Y, USY, X, ZSM-5, ZSM-12, ZSM-20, ZSM-23, ZSM-35, and ZSM-50.
6. The process of Claim 1 wherein the metal oxide binder comprises silica, titania, zirconia and/or germania.
7. The process of Claim 1 wherein the 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°C, a pressure of at least 500kPa and a water and/or alcohol to olefin ratio of 0.1 to 30.
9. The process of Claim 1 wherein the reaction is conducted at a temperature of 100 to 200°C, a pressure of at least 2000KPa and a water and/or alcohol to olefin ratio of 0.2 to 15.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29611089A | 1989-01-12 | 1989-01-12 | |
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| JP (1) | JPH03503175A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532392A (en) * | 1994-01-13 | 1996-07-02 | Gheorghiu; Mihail | Process for the preparation of methyl fatty acid esters starting from natural oil or fat, methyl esters obtained in this way and use thereof |
| TW321634B (en) | 1994-07-05 | 1997-12-01 | Mitsui Toatsu Chemicals | |
| CN1060686C (en) * | 1998-01-12 | 2001-01-17 | 南开大学 | Compounded active carbon fibre solid catalyst |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| KR101740419B1 (en) | 2008-07-18 | 2017-05-26 | 지알티, 인코포레이티드 | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
| RU2507190C1 (en) * | 2012-11-09 | 2014-02-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" (ООО "НПО ЕВРОХИМ") | Method of obtaining tertiary butanol |
| WO2020081208A1 (en) * | 2018-10-17 | 2020-04-23 | Exxonmobil Chemical Patents Inc. | Oligomerization of olefins |
| EP3867213A4 (en) * | 2018-10-17 | 2022-08-24 | ExxonMobil Chemical Patents Inc. | Oligomerization of olefins |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0162475B1 (en) * | 1984-05-25 | 1991-08-21 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for producing cyclic alcohol |
| US4714787A (en) * | 1985-09-03 | 1987-12-22 | Mobil Oil Corporation | Production of ethers from linear olefins |
| ZA883091B (en) * | 1987-05-01 | 1989-12-27 | Mobil Oil Corp | Method for preparing a zeolite catalyst bound with a refractory oxide of low acidity |
| JP2593538B2 (en) * | 1987-12-30 | 1997-03-26 | モービル・オイル・コーポレイション | Preparation of isopropyl alcohol |
| CA1339382C (en) * | 1987-12-30 | 1997-08-26 | Tracy Jau-Hua Huang | Process for the catalytic hydration of olefins |
| JP2731203B2 (en) * | 1987-12-30 | 1998-03-25 | モービル・オイル・コーポレイション | Water addition method of olefin |
-
1990
- 1990-01-10 EP EP19900901716 patent/EP0403639A1/en not_active Withdrawn
- 1990-01-10 JP JP50228290A patent/JPH03503175A/en active Pending
- 1990-01-10 WO PCT/US1990/000135 patent/WO1990008120A1/en not_active Application Discontinuation
- 1990-01-10 AU AU48402/90A patent/AU4840290A/en not_active Abandoned
- 1990-01-10 CA CA 2025016 patent/CA2025016A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0403639A1 (en) | 1990-12-27 |
| WO1990008120A1 (en) | 1990-07-26 |
| JPH03503175A (en) | 1991-07-18 |
| AU4840290A (en) | 1990-08-13 |
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