Note: Descriptions are shown in the official language in which they were submitted.
~ 090/0~12~ PcT/~s9o/(~ol~'
2 ~ v'
- 1 -
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.
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
8 --
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
- 13 -
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...
EXAMPLE 1
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
- 14 -
ln nitrogen at 540C (1000F) followed by aqueo~s
exchanges with 1.0 N ammonium nitrate solution and
calcining in air at 540C (1000DF).
EXAMPLE 2
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)
EXAMPLE 3
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
- 15 -
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
- 16 -
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
- 17 -
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.
. . . .
. , .
