Note: Descriptions are shown in the official language in which they were submitted.
~ 3~
1 UD 13928
HETEROGENEOUS_ALKOXYLATION USING
ANION-BOUND METAL OXIDES
BACKGROUND OF THE INVENTION
~ 1. Field Of The Inventlon
: 5 The invention relates to a catalytic process of
alkoxylating active-hydrogen compounds, to the starting
compositions and to the alkoxylation catalysts.
:;
2. Background Art
Hino, ~akoto, and Kazushi Arata, "Synthesis of
Solld Superacid Catalyst with Acid 3trength of Ho <
-16.04", J.C.S. Chem. Comm., (1980) pages 851 and 852,
discloses a solid superacid catalyst with an acid
strength of Ho < -16.04. The catalyst was obtained by
exposing Zr(OH)4, prepared by the hydrolysis of ZrOC12,
: 15 to lN H2S04 and then calcinlng it ln air at 575 to
6500C.
Hino, Makoto, and Kazushi Arata, "Synthesis Of
Esters From Acetic Acid With Methanol, Ethanol,
Propanol, Bu~anol, And Isobutyl Alcohol Catalyzed By
Solid Superacid", Chemical Letters, Chem. Soc. Jap.,
(1981), pages 1671 and 1672, discloses catalytically
esterlYying acetic acid with lower alkanols, such as,
.. ~
:~ .
:,.
. .
.,........ ~.~,
:. :
5!33~
2 UD 13928
ethanol. A solid superacid catalyst, which was obtained
by exposing Zr(OH)4 to lN H2SO4 and then calcining in
~ir at 500 to 750C " was stated to be highly active
for the heterogeneous esterification reactions at 30 to
45C. The reactions with used catalysts gave identical
results with those using freshly activated catalysts.
(Esterificatlon reactlons are known to be catalyzed by
aclds.) Solid superacld catalysts were also prepared
from ( )3 4 4
Hino, M., and K. Arata, "Conversion Of Pentane To
Isopentane And Isopentane To Isobutane Catalyzed By A
Solid Superacid In The Vapor Phase"~ React. Kinct,
Catal. Lett., Vol. 19, No. 1-2, (1982), pages 101 to
104, dlscloses converting pentane and isopentane,
respectlvely, into isopentane and isobutane using a
solid superacid, which was prepared by exposing Zr(OH)4
to lN H2S04, followed by calcination at 650C. ln air.
The selectivities were 84 percent under short contact
conditlons at 80C. The reactions involved the
isomerlzatlon and hydrocrack~ng o~ lower hydrocarbons.
The paper states that Takahashi et al. prepared solld
superacids by supporting SbF5 on metal oxides and
studied reactions o~ pentane and isopentane. [R.
Ohnishi T., Morikawa, Y. Hira~a and K. Tanabe,
` 25 Zeitschrif`t fur Physikalische Chemic Nue Folg, Vol. 130,
~:~3309;2
UD 13928
pp. 205-209, (1982)]
The above-dlscussed Hino and Arata articles are
~nconsistent and teach away from the invention which is
the subJect o~ thls application.
Chukhlantsev, V.G., and Yu. M. Galkin, "Thermal
Decomposition Of Baslc Zirconium Sulphate", Russian
Journal of Inorganic Chemistry, 18 (6), (1973), pages
770 and 771, earlier disclosed that when basic zlrconlum
sulphate ls heated to 500 to 650C. (even above 400 to
420C.) only dehydration, accompanied by the formation
of an anhydrous product amorphous to X-rays, took place.
Starting from 600C. the latter decomposed with the
formation of ZrO2 and release of SO3. Basic zirconium
sulfate was obtained by boiling a solution of zirconium
oxide chlorlde containing 50 g of ZrO2 per llter, 15 g
of ~ree HCl per liter, and sulfuric acid to give SO3:
Zr2 = 0.56 (molar). The product was washed and then
dried at 100C.
The Condensed Dictionary, 10th Ed., (1981) pages
1115 to 1117, dlscloses: Zr508(S04)2.xH2O, zirconyl
sulfate on zirconlum sulfate, basic; ZrOCO3.xH2O,
zirconyl carbonate or zirconium carbonate, basic;
ZrOC12.8H2O, zirconyl chloride or zlrconlum oxychloride;
ZrO(OH)Cl.nH20, zlrconyl hydroxychloride; and
ZrO(OH)NO3, zirconyl hydroxynitrate or zirconyl nitrate,
:, .
,
. :
~.2~3~92 ~D 13928
basic. 2irconium oxychloride can be prepared by the
action of hydrochloric acld on zlrconium oxide.
Z~rconyl sulfate can be prepared in a similar manner.
Zr(OH)4 can be prepared by the actlon of a solution o~
sod~ium hydroxide on a solutlon of a zlrconium salt.
Ethylene oxide, also termed oxirane, has been
reacted with C2H50H to produce C2H50CH2CH20H. The same
reaction with ethylene sulflde is known.
BROAD DESCRIPTION OF THE INVENTION
The invention involves the baslc and unexpected
discovery that anion-bound zirconium oxides and certain
other anion-bound metal oxides are heterogeneous
catalysts for alkoxylation, particularly ethoxylation.
The invention process ls broadly the use of anion-bound
metal oxide heterogeneous Gatalysts ~or the alkoxylation
o~ active-hydrogen compounds, such as, primary or
secondary alcohols and diols. Anion-bound zirconium
oxide heterogeneous catalysts are highly active.
The invention process for the alkoxylation of
ac~ive-hydrogen compounds includes reacting a liquid or
solid reactive epoxide compound having the ~ormula:
09~ UD 13928
- o ~
I
RlR2C CR3R4
wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3, and
whereln n is 0 to 3, with the proviso that Rl, R2, R3
and R4 can be the same or diff`erent, wlth an
active-hydrogen compound, the active hydrogen compound
belng in the llquid or gaseous state, in the presence of
a catalytlc amount of at least one solld anlon-bound
metal oxide catalyst. The anlon-bound metal oxlde
catalyst ls an amorphous or primarily amorphous
compound. The active-hydrogen compound ls one which
does not polson the catalyst. The pre~erred
active-hydrogen compound is preferably a primary
monohydric alcohol, a secondary monohydric alcohol, a
15 dihydric alcohol, a trihydric alcohol, a polyhydric
alcohol, an alkoxylated ethylene glycol or a glycol
ether. Water can be used as the active hydrogen
compound. The molar ratio o~ the cyclic epoxide
compound to the active-hydrogen compound ls usually
20 between 3:1 and 1:3. The process ls especlally
advantageous in the ethoxylation of ethylene glycol.
In the processes of the lnvent~on~ the preferred
',... .. , ''` -: .~,.. ...
-~2~330~3X
UD 13928
epoxide compound is ethylene oxide. Also preferably the
reactlon ls continuously conducted in a flxed-bed
r~actor or a fluidized reactor. Also in the processes
of the lnvention, preferably 0.5 to 50 weight percent,
bas~d on the total weight of the cycllc epoxide compound
and the other reactant, or reactants, of the solid
anlon-bound metal oxlde catalyst is used. Preferably
the anlon in the anion-bound metal oxlde catalyst ls
S0 BF4, C03, B03, HP04, SeO4, MoO4, B407 6
the metal oxlde in the anlon-bound metal oxide catalyst
ls zirconium oxide, nickel oxlde, alumlnum oxide, tin
oxide, magnesium oxlde, rubldium oxlde, tltanium oxide,
thorlum oxide, hafnium oxide or iron oxide. ZrO wlll
readlly blnd with anions other than S04; whereas the
other metal oxides wlll readily blnd with S04 but not as
~ readlly with the other anions. Preferably the catalyst
; is a solld sulfate-bound zl~conlum oxide catalystJ a
solid sulfate-bound thorlum oxide catalyst or a solid
sulfate-bound hafnium oxide catalyst. Although not
preferred, the reactants can be used in inert liquid
diluents such as hydrocarbons. Normally, the catalyst
can be reused with good selectivity. If necessary, the
solld anlon-bound metal oxide catalyst can be removed
from the-reaction site and can be regenerated by
calcination in alr or oxygen at a temperature of 300 to
. . . . .
~2~3~9~
UD 1392
950C. for a period of 1 to 4 hours.
An advantage of the invention process is that it
pfoduces a narrow moiecular range of products with a
minimum of undesirable high molecular weight co products
or by-products.
The polyoxyethylation of an alcohol is a process of
reactlng an alcohol with ethylene oxlde to produce a
polyether, as in the reaction below, in whlch R of the
alcohol can be aliphatlc or aromatic:
o
/ \
ROH + nCH2 CH2 - ~RO (CH2CH2O)nH
The number of moles (n) of ethylene oxide reacted can
range from 1 to greater than 200. The reaction occurs
by a stepwise addition of the polymerization process
usually catalyzed by acids or bases. The average
molecular welght of the product alcohols is determined
by the moles of ethylene oxlde reacted compared to the
moles of hydroxyl groups in the starting alcohol. The
product can contain s~gniflcant amounts of unreacted
starting alcohol, depending on the relative reactivity
of the starting alcohol compared to the reactivity of
the product alcohols. All unhindered hydroxyl groups of
' . ' ~ ' . .
''
g%
8 UD 13928
monohydrlc and polyhydric alcohols react, but some may
be more reactive than others. The process temperatures
u~ually range from 80 to 180C. with the pressure at a
level (e.g,, 20 to 100 p.s.-l.g.) needed to maintain
S co~ditions ln the reactor. Often an excess of alcohol
and/or cyclic epoxlde iB used.
The invention also involves a composition
containing (a) a liquid or solid epoxide compound having
the formula:
1
R R C- ~ 3 4
wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3J and
wherein n is 0 to 3, with the proviso that Rl, R2, R3
and R4 can be the same or di~ferent, (b) an
active-hydrogen compound, such as, a secondary
monohydric alcohol, a dlhydric alcohol1 a trihydric
alcohol, a polyhydric alcohol, an alkoxylated ethylene
glycol or a glycol ether, the active-hydrogen compound
being in the gaseous or liquid state, and (c) a
catalytic amount of at least one solld anion-bound metal
oxlde catalyst. The anion-bound metal oxide catalyst is
an amorphous or primarily amorphous compound. The
~28309;:
UD 1392a
active-hydrogen compound ls one which does not poison
the catalyst.
The inventlon further involves reacting at least
one molecule of a liquid or solld epoxide compound
havlng the formula:
RlR2C - ~ ~ CR R4
wherein Rl, R2, R3 and R4 are each H or -(CH2)nCH3, and
wherein n is 0 to 3, with the proviso that Rl, R2, R3
and R4 can be the same or different, with at least one
other molecule of the above-identified liquid or solid
epoxide compound in the presence of a catalytic amount
of a~ least one solid anion-bound metal oxide catalyst.
The molecules of epoxide compound can be the same
epoxlde compound or different epoxide compouds. The
anion-bound metal oxlde catalyst is an amorphous or
primarily amorphou.s compound.
The invention still further involves a composition
including (a) at least one liquid or gaseous epoxide
, 20 compound having the formula:
.
.
. . " .
~L~83~9Z
UD 13928
r-- o~
1, 1 .
, RlR2C ---CR3R4
whereln Rl, R2, R3 and R4 are each H or -(CH2)r~CH3, and
wh~rein n is 0 to 3, with the proviso that R1, R2, R3
and R4 can be the same or different, and (b) a catalytic
amount of at least one solid anion-bound metal oxide
catalyst. The anion-bound metal oxlde catalyst is an
amorphous or primarily amo~phous compound.
The lnvention also lnvolves the alkoxylation
process o~ reacting an epoxide compound having the
formula:
, ---- O
RlR2C - - 3 4
wherein R1, R2, R3 and R4 are each H or -(CH2)nCH3, and
wherein n is 0 to 3, with the proviso that R1, R2, R3
and R4 can be the same or different, with a sodium salt
of an acid sulfate of a secondary monohydric alcohol
havlng 10 to 20 carbon atoms, the secondary monohydrlc
alcohol salt bein~ in the liquid state, in the presence
of a catalytic amount o~ at least one solid anion-bound
metal oxide catalyst. The anion-bound metal oxide
1~83~ UD 13928
11
catalyst is an amorphous or primarily amorphous
compound. The molar ratlo of the epoxlde compound and
t,he secondary monohydric alcohol salt is usually between
3:1 and 1:3.
The invention further involves the composltion
comprised of (a) a liquid or gaseous epoxide compound
having the fo~ula:
O_ 1
R R C ~ 3 4
wherein Rl, R2, R3 and R4 are each H or -(CH2)nC~3, and
whereln n is 0 to 3, with the proviso that R1, R2, R3
and R4 can be the same or different, (b) a sodium salt
of an acid sulfate of a secondary monohydric alcohol
having 10 to 20 carbon atoms, the secondary monohydric
alcohol salt being in the liquid state, and (c) a
catalytlc amount of at least one solid anion-bound metal
oxide catalyst, The anlon-bound metal oxide catalyst is
an amorphous or primarily amorphous compound. The molar
ratio of the epoxide compound and the secondary
monohydric alcohol salt is usually between 3-1 and 1:3.
Another important aspect of the invention is that
it encompasses solid anion-bound metal oxide catalysts
which are: (a) sulfate-bound tin oxide catalyst, (b)
l~æs;~g'~
~D 13928
12
sulfate-bound nickel oxlde catalyst, (c) sulfate-bound
aluminum oxide catalyst, (d) sulfate-bound magnesium
~xide catalyst, (e) sul~ate-bound rubidium oxide
catalyst, (f) sulfate-bound thorium oxlde catalyst, (g)
; sul~ate-bound hafnium oxide catalyst, or (h) an
anion-bound metal oxide catalyst wherein the anion ls
S04, BF4, C03, B03, HP04, SeO4, MoO4, B407 or P~6, and
the metal oxide is an oxide of zlrconium, nlckel,
aluminum, tin, magnesium, iron, titanium, thorium,
hafnium or rubidium. The anion-bound metal oxide
catalyst is an amorphous or primarily amorphous
catalyst. The catalysts are useful in the
above-described alkoxylation processes and in the
processes set out in the above prior art section.
DETAILRD DESCRIPTION OF' T~E INVENTION
As used herein, all parts, ratios, percentages and
proportions are on a weight basis unless otherwise
stated herein or otherwise obvious herefrom to one
skilled in the art.
The anion-bound metal oxide catalysts of the
invention are heterogeneous catalysts, that is, they are
useful in heterogeneous catalysis. Heterogeneous
catalysis lnvolves a catalytic reaction in which the
33~9Z
UD 13928
13
reactants and the catalyst comprises two separate
phases, e.g., gases over sollds, or liquids containing
f,inely-divided solids as a disperse phase. (By way of
contrast, homogeneous catalysls involves a catalytic
reaction in which the reactants and the catalyst
comprlse only one phase, e.g., an acid solution
catalyzlng other llquid components.) The subJect
alkoxylation reactions of the invention occur on the
surface of the solid catalyst particles. The individual
steps of heterogeneous catalytic processes probably
involve the following:
(l) Diffusion of reactants to surface.
(2) Adsorption of reactants on surface.
(3) ~eaction of absorbed reactant to form adsorbed
product.
(4) Desorption of product.
(5) Diffusion of product into main stream of a
liquid or vapor.
The reaction rates of alkoxylation reactions were
unexpectedly significantly increased by the solid
anion-bound metal oY~ide catalysts of the invention.
While a catalytic amount of catalyst is to be used,
preferably 0.5 to 50 weight percent of the cataly~st is
~;283(~
UD 13928
14
used based on the total weight of the reactants. Of
course, higher levels of the catalys~ can be used and
m~xtures of the catalysts can be used. One or more
promoters can also be used.
~ One of the preferred anion-bound metal oxide
catalysts is zirconlum oxysulfate catalyst. It provides
a substantial lncrease of reaction rate in ethoxylatlons
with excellent selectlvity. For example, the use of
zlrconlum oxysulfate catalyst in the ethoxylation of
ethylene glycol produces very little of the undesirable
1,4-dloxane.
Production of the catalyst involves, for example,
reactlng a compound havlng an anion with the metal
hydroxide, such as, Zr(OH)4, Zr(OH)4.xH20, Hf(OH)4,
Fe(OH)3, Al(OH)3, Th(OH)4, Nl(OH)2, and Mg(OH)2. (Any
other sultable method can be used to prepare the
catalyst.)
The metal hydroxlde can be produced by hydrolyzing
metal oxy-anlon group compounds~ such as, ZrOC12.8H20,
3)2-2H20, Zr50g(S04)-xH20~ ZrO(C2H302)2
ZrOBr2.xH20, ZrOI2.8H20, ZrO5, HfOC13.8H20,
ZrOOHCl.nH20, ZrO(OH)NO3 and ZrO(SO4). The hydrolysis
can be achieved uslng a hydrolyzing agent, such as,
ammonlum hydroxide, sodium hydroxlde, potassium
hydroxlde, barlum hydroxide, lithium hydroxlde,
: .
~283~ X
UD 13928
magneslum hydroxlde, Na2S04, (NEI4)2HP04 and so forth-
Following hydrolysis, the solids are removed from the
hydrolysis solutlon, usually by flltration, dried (at
say 100C. or any other appropriate temperatu~es) and
optionally particulated or powdered.
The metal hydroxide is t~eated with the reactlve
compound containing an anlonic group under suitable
conditions. The anion can be monovalent or divalent or
have a highe~ valence. Examples of the reactive
compounds having an anionic group are H2SO4, phosphoric
acld, nltric acid, etc. Such acids are examples of the
reactive compounds havlng an anionlc group, but Lewis
acids can also be used as such reactive compounds
; having an anionlc group. A Lewis acid ls a substance
15 that can act as an electron-pair acceptor. Lewis acids
include trivalent derivatives of boron and aluminum, as
well as salts of many other metals. Examples of
specific Lewis acids are BF3, BC13, AlC13, AlF3, FeC13,
4' 2' 1~ g 12~ AlH3~ PFs~ Sb~5 and S03.
If one starts with compounds such as ZrOS04 and
TiOS04, the sulfate-bound metal oxide compounds can be
p~epared dlrectly by adding the hydrolyzing agent (e.g.,
sodium hydroxide) to a solutlon of the ZrOSO4, TiOS04 or
the like.
The solld anion-bound metal oxide catalyst ls
30~
~D 13928
16
normally dried (at 100C. or any other sultahle
temperature) before belng calcined, The dryin~ step to
be used ls any technique whlch sufficiently evaporates
the volatile constituents of the impregnating solution.
Calcination of the anlon-bound metal oxlde catalyst
can be done ln air or oxygen at a temperature of 300 to
950C., preferably 500 to 800OC., fo~ a suitable period
of tlme. The calclnation is normally conducted for one
to four hours, or more. Zirconium oxysulfate catalyst
productlon preferably lnvolves calcination ~n air at a
temperature o~ about 575C.
The calcined catalyst has lts water molecules
removed by the calcination, so the calcined catalyst
should be kept in an air tight container, such as, a
desiccator, untll it is used.
The zirconium catalysts of the invention are not
zirconyl salts, such as, zirconium oxysulfate. Instead,
the zirconium catalysts of the invention are anion-bound
zirconium oxldes. The anlon, for example, S04, bridges
the zirconium oxide moieties. Examples of such anions
are S04, BF4s C03, B03, HP04, SeO4, MoO4, B407 o~ PF6,
and the metal oxide is zirconlum, nickel, aluminum, tin,
magnesium, iron, titanium, thorium, hafnium or rubidium.
Metal oxides of Group IVB metals are most preferred.
25 The anion bound to the metal oxide in the catalysts can
~9 ~ UD 13928
17
be inorganic anions and/or organic anlons. Inorganlc
anlonic groups are preferred, wlth the sulfate group
b~lng the most preferred.
Other anion-bound oxide catalysts can be used in
place of anion-bound zlrconlum oxide catalyst, although
the anlon-bound zlrconium oxide catalyst is most
preferred. Examples of other anlon-bound metal oxides
are anlon-bound lron oxlde (preferred), anion-bound
alumlnum oxide, anlon-bound nickel oxide, anion-bound
tln oxlde, anlon-bound magneslum oxlde, anion-bound
rubldlum oxlde, anlon-bound titanlurn oxide (preferred),
anlon-bound thorlum oxide (most preferred), and
anlon-bound hafnlum oxlde (most preferred). Thorium
oxide catalysts may be more advantageous than zirconium
oxide catalysts since they are very lnsoluble and
thorium is not amphoteric like zirconlum. Amphoteric
means actlng as either an acid or base. Experimentation
has found that anion-bound cerium oxlde, anion-bound
; lanthanum oxlde, anlon-bound tungsten oxide and certaln
other anion-bound metals do not work as catalysts Ln the
lnvention process of catalytlcally alkoxylat-lng certain
compounds. This lack of catalytic activity of certain
anion-bound metal oxldes shows the unexpected nature of
the invention.
The metal oxldes used in the anlon-bound metal
283~9V~
UD 13928
18
oxlde catalysts are amorphous or used in amorphous form.
~or example, one uses the amorphous forms of alurnina as
o~posed to the crystalline forms of alumina. The metal
oxldes can also be primarlly or mainly amorphous, that
isl more of the metal oxide is in the amorphous state
than ln the crystalllne state. The crystalline formlng
metal oxides, such as, calcium oxide, are not used.
Only solid, insoluble catalysts are used so that a
hetero~eneous catalytic reaction is involved. Catalysts
based on K, Ba and Na a~e soluble in the reactants
and/or product and/or diluent, so they are not used in
the lnvention.
1,4-dioxane or 1,4-diethylene dioxide is
undeslrable, but is produced to a small extent by all of
the lnvention catalysts. The anion in the catalyst
needs to be bound totally or else it leaches into the
reaction medium and increases the acidity with the
resultant productlon of dioxane. Pre~erably 2 to 3
weight percent of the anion (e.g., SO4) is bound to the
metal oxide. The use of Na2SO4 in place of H2SO4
elimlnates the minor dioxane p~oductlon caused by the
latter, but Na2SO4 causes a slower reaction rate. In
general, the more baslc the anion-bound metal oxide
catalyst is, the less the amount of dioxane that is
produced.
.. :
~2~33[)~3~
UD 13928
19
The anion-bound metal oxide catalyst is usually
used in a flnely-dlvided particulate stake. Mixtures of
a,nion-bound metal oxlde catalysts can be used.
Carriers or supports can be used to support the
ani-on-bound metal oxide catalyst. The support is used
in a partlculate form and can be porous or nonporous,
although the former is prefer~ed. Usually the support
particles have diameters between 1 and 5 mm.
Preferably, car~iers are used which are inert to the
reactants and products of the sub~ect alkoxylatlon
reactions.
The preferred carriers are sillca gel and 4 A
alumlna-silica sieves. Examples of other useful inert
carriers are dlatomaceous earth, sllica, alumina (e.g.,
~ - alumlna), slllca-alumina, calcined clays, charcoal
and zeolltes.
The catalysts can even be used ln a porous,
unsupported form.
The anlon-bound metal oxlde catalysts can be
regenerated or reactlvated by calcination, for example.
Zirconium oxysulfate catalyst is preferably regenerated
by calcination ln alr at a temperature of about 575C~
Generally regeneratlon calcination is run in air or
oxygen at a temperature between 300 and 950Co ~
25 preferably between 500 and 800C., for a period of time
'
~2~33~9~
UD 13928
which is usually one to four hours, or more.
Generally the recovered catalyst does not have to
b~ regenerated and can be used as is wlth no loss of
selectivlty.
~ The reactants withln the scope of the invention are
in the gaseous and/or liquld state, althou~h a reactant
could be used ln the solid state lf lt was in a
flnely-divided particulate form, for example, suspended
ln A llquld carrler (dlluent) or a different llquld
reactant. Solld reactants can also be used if they are
; dlssolved ln a liquid solvent. The anlon-bound metal
oxlde catalyst ls used in a solld form.
Examples of liquid nonpolar dlluents from whlch the
appropriate diluent can be selected are: acetlc acid
nitrile, anthraceneJ benzene, chlorobenzene, 1,2-di-
chlorobenzene, ethylbenzene, isopropylbenzene,
l-lsopropyl-4-methylbenzene, nltrobenzene, propyl-
benzene, 1~3J5 trlmethylbenzene, benzolc acid nitrlle,
perchloro biphenyl, 1,3-butadlene, 2-methyl-1,3-
butadlene, butane, butanoic acid nltrlle, carbondisulflde, carbon tetrachloride, chloroform,
cyclohexane, methyl cyclohexane, perfluoro cyclohexane,
~; cyclopentane, decalln, decane, ethane, bromoethane,
chloroethane, 1,2-dibromoethane, l,l-dichloroethane,
difluoro-tetrachloro ethane, nltroethane,
32
UD 13928
21
pentachloroethane, 1,1,2,2-tetrachloroethane,
1,1,2-trichloro ethane, trlchloro-trifluoro ethane,
e~hylene, perchloroethylene, trichloroethene, heptane,
perfluoroheptane, hexane, hexene-l, malonic acid
dinitrile, methane, bromomethane, dichloromethane,
dichloro-difluoro methane, cllchloromethane,
nltromethane, tetrachloro-difluoro methane,
trichloro-monofluoro methane, naphthalene, nonane,
octane, pentane, l-bromopentane, 1-chloropentane,
pentene-l, phenanthrene, propane, l-bromopropane,
2,2-dimethylpropane, 1-nltropropane, 2-nitropropane,
propene, 2-methylpropane, propionic acid nitrile,
styrene, hydrogenated terphenyl, tetralin toluene and
m-xylene.
Examples of liquid moderately polar diluents from
which the appropriate diluent can be selected are:
acetic acid butyl ester, acetic acid ethyl ester, acetic
acid methyl ester, acetic acid pentyl ester, acetic acid
propyl ester, N,N-diethyl acetic acid amide,
N,N-dimethyl acetic acid amide, acrylic acid butyl
ester, acrylic acid ethyl ester, acrylic acid methyl
ester, adlpic acld dioctyl ester, benzoic acid ethyl
ester, benzoic acid methyl ester, l-iodobutane, carbonic
acld ester, vinyl chlGride, N,N~diethyl formic acid
amide, N,N-dimethyl formic acid amide, formic acid ethyl
~L283~9;2
UD 13928
22
ester, formlc acid methyl ester, formlc acid
2-methylbutyl ester, formic acid propyl ester, furan,
furfural, lactic acid butyl ester, lactic acid ethyl
ester, methacrylic acld butyl ester, methacrylic acid
ethyl ester, methacrylic acld methyl ester, oxalic acid
diethyl ester, oxalic acid dimethyl ester,
l-iodopentane, phosphoric acid triphenyl ester,
phosphoric acid tri-2-toly ester, phthalic acid dibutyl
ester, phthalic acid diethyl ester, phthallc acid
dihexyl ester, phthalic acid dirnethyl ester, phthalic
acid dl-2-methylnonyl ester, phthalic acid dioctyl
ester, phthalic acid dipentyl ester, phthalic acid
dipropyl ester, propionic acid ethyl ester, propionic
acid ethyl ester, propionic acid methyl ester, l-methyl
2-pyrolldone, sebaclc acid dibutyl ester, sebacic acid
dioctyl ester and stearic acid butyl ester.
Examples of liquid hydrogen-bonded diluents from
which the appropriate diluent can be selected are:
N-ethyl formic acid amide, N-methyl formic acid amide
20 and N-methyl methacrylic acid amide.
Mixtures of inert diluents can be used.
The heterogeneous catalytic reactions of the
invention can be effected, for example, in one of three
ways: (1) ln batch processes; (2) in continuous
25 ~lxed-bed proce~ses; and (3) in continuous ~luldized
:.
.
33~9Z
UD 13928
23
reactor processes. In a batch reactor, the catalyst is
kept suspended ln the reactant by shaklng or stirring.
I~ a fluidized reactor, the catalyst ls at a particular
original level. As the velocity of the reactant stream
ls 1ncreased, the catalyst bed expands upward to a
second level, and at a crltical velocity it enters into
vlolent turbulence. The fluidlzed reactor is
part1cularly useful for removlng or supplying the heat
necessary to maintain a fixed catalyst temperature. The
fluidized reactor can usually be employed only on a
rather large scale slnce good fluidization requires a
reactor larger than about 1.5 inch in diameter.
The process of the invention broadly involves the
liquid or gaseous use of anion-bound metal oxide
heterogeneous catalysts for the alkoxylation of actlve-
hydrogen compounds, preferably hydroxyl-containing
compounds, such as, primary or secondary alcohols~ diols
or triols. Mixtures of active-hydrogen compounds can be
used.
Active-hydrogen organic and inorganic compounds
incIude, for example, hydrogen-containing compounds
(ROH, polyols), carboxylic acids (RC02E3), thiols (RSH),
amines (RNH2 or R2NH), ammonia, water, hydrohalic acids
(HX where X is a halogen), alkyl-OCH2CH20H, HCN, and
bisulfites of metals such as alkali and alkaline earth
~283~92 UD 13928
24
metals. R above is generally a saturated aliphatic
hydrocarbon moiety ~branched or unbranched alkanes), a
s~turated monocyclic moiety or an aromatic hydrocarbon
moiety (l.e., an arene moiety). Such organic moleties
ca~ be substltuted with nonreactive or non-lnte~ering
3ubstituents such as halogens, NO2, etc. The
actlve-hydrogen compounds broadly have the formula HQ
(where Q 18 a saturated or aromatic organlc molety or an
lnorganic molety).
The invention can be used to alkoxylate any of the
primary or secondary monohydric alcohols, dihydric
alcohols (dlols), trlhydric alcohols and polyhydric
alcohols (polyols), glycol ethers and alkoxylated
ethylene glycols, all o~ which are su~table
active-hydrogen compounds provlded any particula~
lndivldual compound does not poison the anion-bound
metal oxlde catalyst. Such hydroxyl-containing
compounds can be substituted with non-interferlng
groups, such as, nitro groups, halo groups and the llke.
The monohydric alcohols can be the primary alkyl
(monohydrlc) alcohols having 1 to 12 carbon atoms, such
as, methanol, ethanol, n-propanol, n-butanol, l-pent-
anol, l-hexanol, l-heptanol, l-octanol, l-decanol,
l-dodecanol, lsopropanol, lsobutanol, 2-methyl-1-
25 butanol, 3-methyl-1-butanol, 2-methyl-1-pentanol, 3-
~L283~2
UD 13928
methyl-l-pentanol, 4-methyl-1-pentanol, 2-ethyl-1-but-
anol, and 2,4-dimethyl-1-pentanol. The monohydric
; a~cohols can be the secondary alkyl (monohydric)
alcohols havlng 2 to 12 carbon atoms, such as, 2-buta-
nolJ 2-pentanol, 3-methyl-2-butanol, 2-hexanol, 3-hex-
anol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, 2,4-
methyl-3-pentanol, and 2-octanol. The monohydric
; alcohols can be paraffinlc alcohols (the above alkyl-
alcohols) or olefinlc alcohols (e~g~ allyl alcohol).
The monohydric alcohols can be alicyclic monohydric
alcohols having 3 to 10 carbon atoms, such as, cyclo-
hexanol, cycloheptanol, cyclopropanol, cyclobutanol,
cyclopentanol and cyclooctanol.
The invention process can be used to alkyoxylate
any of the allphatic, aromatic or heterocyclic compounds
containing two hydroxy ~roups, preferably separated by
at least two carbon atoms. The dlols can be substituted
if desired with varlous noninterfer~ng (non-functional)
substituents such as ether groups, sulphone groups,
tertiary amlne g~oups, thioether g~oups, chlorine atoms,
bromlne atoms, iodine atoms, fluorine atoms, etc.
Typical compounds which can be used a~e listed below
merely by way of illustration and not lirnitation:
Ethylene glycol, diethylene glycol, 2,2-dimethyl
propane-1,3 diol, butane-1,4-diol, hexane-1,6-diol,
~Z~3092 UD 13928
26
octane-1,8-dlol, decane-1,10-diol, dodecane-1,12-diol,
butane-1,2-dlol, hexane-1,2-diol, l-0-methyl glycerol J
2~0-methyl glycerol~ cyclohexane-1,4-methyl-diol,
hydroquinone, resorcinol, catechol, bis(parahydroxy-
ph~nyl) butane, 4,4'-dihydroxybenzophenone, naptha-
lene-1,5-diol, biphenyl-4-4'-dlol, 2,2-bls(3-methyl-
4-hydroxyphenyl) propane, 2,2-bis(4-hydroxy-dibromo-
phenyl) propane, etc.
Mixtures of different diols can be used. It is
also withln the ~urview of the invention, though less
- preferred, to use the compounds containing more than two
hydroxy groups, for example, glycerol, diglycerol,
hexanetriol, pentaerythrltol, etc. Moreover, it is
within the scope of the inventlon to utillze the sulfur
analogues o~ the dlols. Thus, for example, instead of
using the compounds containing two hydroxy groups, one
can use the analogues containing either (a) two -SH
groups or (b) one -SH group and one -OH group.
Among the pre~erred compounds are the aliphatic
dlols, ~or example, those of the type:
HO (CH2)n
wherein n has a value from 2 to 12. Another category of
aliphatic hydroxyl-containlng compounds are the
~ :
..., ,,.. : ~.
~, .
UD 13928
27
polyethylene glycols, i.e.:
Ho_cH2_cH2- [0-CH2-CH2 ]~1-O-CH2-CH2-OH
wherein n has a value from zero to 10. A category of
aromatic diols are the bisphenols, that is, compounds of
the type:
Dl
R~ ~ ~R'
R OH
HO
wherein R-C-R represents an aliphatic hydrocarbon group
contalnlng 1 to 12 carbon atoms and R' represents
hydrogen or a lower alkyl radical, In this category
are: 2,2-bis(parahydroxyphenyl) propane;
: 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and
bromlnated derivatlves of bisphenol A, such as,
~ 15 2,2-bis(4-hydroxy-dibromophenyl) propane~
; The alkoxylation of diols can p~ovide dimers or
polymers.
The use~ul trihydric alcohols include glycerol,
1,2,3-butantriol and l,l,l-trihydroxymethylethane. The
use~ul polyhydrlc alcohols include those having the
formula CH2OH(CHOH)nCH2OH, wherein n is 2 to 5~ such as,
~2~331[)9Z
UD 13928
28
arabitol, adonltol, xylltol, mannitol and sorbitol.
Preferably the invention alkoxylation process is
u~ed w$th glycol ethers, ethylene glycols (i.e., to
produce CARBOWAX~-type products) or Tergltol-type
products.
CARBOWAX~ ls the reglstered tradema~k o~ Unlon
Carblde Corporatlon for a serles of polyethylene
glycols. Ethylene glycol can be used to make the
CARBOWAX~ polyethylene glycols or the CARBOWAX~
polyethylene glycols can be used to make higher
molecular weight CARBOWAX~ polyethylene glcyols. For
example, CARBOWAX~ polyethylene glycol 200 can be used
to make CARBOWAX~ polyethylene glycol 400. Speclfically,
the CARBOWAX~ polyethylene glycols are liquid and solld
polymers of the general formula H(OCH2CH~)nOH, where n
is greater than or equal to 4. In general, each
CARBOWAX~ polyethylene glycol is followed by a number
which corresponds to its average molecular weight.
Generally, the invention process is not prefe~red for
using CARBOWAX~ polyethylene glycols having an average
molecular weight above about 600 to 800 as startlng
materlals because such CARBOWAX~ polyethylene glycols
are solids at room temperature (although they are liquid
at the reaction temperatures, e.g.z 110C.). Examples
of useful CARBOWAX~ polyethylene glycols are: CARBOWAX0
~83~
UD 13928
29
polyethylene glycol 200, whlch has an average n value of
4 and a molecular weight range of 190 to 210; CARBOWAX~
pplyethylene glycol 400, wh:Lch has an average n value
between 8.2 and 9.1 and a molecular welght range of 380
to ,420; and CARBOWAX~ polyethylene glycol 600, which has
an average n value between 12.5 and 13.9 and a molecular
welght range of 570 to 630.
The anlon-bound zirconlum oxide catalyst has a high
selectivlty to ethylene glycol. The reaction
temperature ls not important and can be run at 50 to
110C at a 5:1 weight ratlo of H2O to ethylene oxide and
at varlous catalyst concentratlons greater than 90
percent o~ ethylene glycol is produced. At a 10:1
weight ratio, greater than 95 percent of ethylene glycol
is produced.
TERGITOL~ is the registered trademark of Union
Carblde Corporation for a serles of the sodium salts of
the acid sulfate of secondary alcohols of 10 to 20
carbon atoms which are nonionic or anionic su~factants.
Examples of the TERGITOL~ are: TERGITOL~ Pentrant 08,
whlch is C4H9CH(C2H5)CH2SO4-Na; TERGITOL~ Pentrant 4,
which is C4HgCH(C2H5)C2H4CH~(SO4Na)CH2CH( 3)2;
TERGITOL~ Pentrant 7, which is C4HgCH(C2H5)C2H4CH~
(so4Na)c2H4cH(c2H5)2
Examples o~ useful glycol ethers are ethylene
3~3Z
UD 13928
~lycol monoethyl ethe~, ethylene glycol monobenzyl
ether, ethylene glycol monobutyl ether, ethylene glycol
mpnomethyl ether, ethylene glycol monohexyl ether,
ethylene glycol monophenyl ether, ethylene glycol
monooctyl ether, propylene glycol monomethyl ether and
propylene glycol phenyl ether.
The actlve-hydrogen compound can be a saturated
carboxylic acld, HOCOR. The carboxylic acid can be a
stralght-chaln alkanoic acld (CnH2nO, wherein n is 1 to
35), such as, methanolc acld, ethanoic acid, propanoic
acld, butanoic acid, pentanoic acld, hexanoic acid,
heptanolc acld, octanoic acld, nonanoic acid, decanoic
acld, undecanoic acid, dodecanoic acid, trldecanoic
acid, tetradecanolc acld, pentadecanoic acid,
hexadecanoic acid, heptadecanolc acld, octadecanolc
acld, nonadecanoic acid, eicosanoic acid, docosanoic
acid, tetracosanoic acid, hexacosanoic acid,
octacosanoic acid, triacontanoic acid, trltriacontanoic
acid, and pentatriacontarlolc acid. The active-hyd~o~en
compound can be a b~anched alkanoic acid, such as,
isopropanolc acid, lsobutanoic acid, 2-butanolc acid,
3-methyl-l-butanoic acid, 2-methyl-l-butanoic acid,
2-pentaonoic acid, 3-pentanoic acid~ 2-methyl-l-
pentanoic acid, 3-methyl-1-pentanoic acid,
2-ethyl-l-butanoic acid, 2-hexanoic acid, 3-hexanoic
~za3~9~
UD 13928
31
acld, 2-methyl-2-pentanoic acld, 2,4-dlmethyl-3-
pentanoic acid and 2-octanolc acid.
, The carboxyllc acld can be a dienoic acld
(CnH2n 42)' such as, 2,4-pentadlenolc acid,
2,4-hexadlenoic acld, 2,4-decadienolc acld,
2,4-dodecadlenoic acld cls-9-, cis-12-octadecadlenolc
acld, trans-9,trans-12-octadecadienoic acid, and
9,13-docosadlenoic acid~ The carboxylic acld can also
be a trienolc acid (CnH2n_6O2), such as, 6,10,14-
hexadecatrienolc acid, cis-9-, cis-12,cis 15-octadeca-
trlenoic acid9 cls-9-, trans-ll,trans-13-octadecatri-
enoic acld trans-9,trans-ll,trans-13-octadecatrienoic
acld cis-9-, cis-ll,trans-13-octadecatrlenoic acid, and
trans-9,trans-12,trans-15-octadecatrienolc acid. The
carboxylic acld can further be a tetraneoic acid
(CnH2n 82)~ such as, 4,8,12,15-octadecatetraenolc acid,
9,11,13,15-octadecatetraenoic acid, 9,11,13,15-octadeca-
tetraenolc acld, and 5,8,11,14~eicosatetraenoic acid.
The carboxyllc acid can also be a pentaenolc acid
(CnH2n 102)~ such as, 4,8,12,15,19-docosapentaenoic
acid.
The carboxyllc acid can be a substltuted, saSurated
carboxylic acid, such as, lodoacetic acid,
o-nitrophenylacetic acid, p-nitrophenylacetic acid,
trichloroacetlc acid, trifluoroacetic acid, bromoacetic
.i :
3~
UD 13928
32
acld, 2-bromobutyric acid, 2-bromohexadecanoic acid,
2-bromohexanoic acid, 6-bromohexanoic acid, 2-bromo-3-
~ethylbutyric acid, (p-bromophenoxy)acetic acid,
2-bromopropionlc acid, 3-bromopropionic acid,
ll-bromoundecanoic acld, chloroacetlc acld, 3-chloro-
buty^lc acld, 3-chloro-2,2-climethylpropionlc acid,
(4-chloro-2-methylphenoxy)acetlc acid, o-chlorophenoxy-
acetlc acld, p-chlorophenoxyacetic acld, 2-(o-chloro-
phenoxy)p~oplonic acid, p-chlorophenylacetic acid,
2-chlorop~opionlc acld, 3-chloropropionic acld,
2,3-dlbromopropionic acid, dichloroacetic acid,
2,4-dichlorophenoxyacetic acid, (2~5-dihydroxyphenyl)-
acetic acid, (3,4-dimethoxyphenyl)acetlc acid,
2,4-dinit~ophenylacetlc acld, (2,4-dl-tert.-pentyl-
phenoxy)acetic acid, 2-(2,4-di-tert.-pentylphenoxy)-
buty~ic acid, ethoxyacetic acld, 3~11-dihydroxytetra-
decanoic acid, 2,15,16-trihydroxyhexadecanoic acld,
aleoprollc acld and aleprestic acid. Normally, the
substituents on any of the active-hydrogen compounds
should be non-interfering, but if deslred, substituents
having active hydrogens, such as, -OH or -SH, can be
used (of course, not all -OH and -SH substituents will
be reactive).
The actlve-hydrogen compounds can be a sulfonic
acid, RSO3H, wherein R is a univalent organic radical
' ' ` ' ` ' ' ... r.. ,.. . :.. ,.~, . . . .
1~8309~
UD 13928
33
tsaturated, alicycllc o~ aromatic) J such as, the
alkanesul~onic acids~ for example, methanesulfonic acid,
e,thanesulfonic acid, propanesulfonic acid,
butanesul~onlc acid, pentanesulfonic acid and
he~anesulfonic acld, alkarenesulfonic acids (RnARS03H,
where R is alkyl and n is l to 3), such as,
p-toluenesulfonic acid, arenesulfonic acids, such as,
2-naphthalenesul~onic acid, l,3-benzenedlsulfonlc acid,
2,6-naphthalenedis~llfonic acld and 1,3,6,8~naphthalene-
tet~asul~onic acid, fluorlnated and chlorofluorinatedsulfonic acids, such as, CF3S03H, ClCF2S03H, Cl2C~S03H~
CHF2S03H and ClCHFS03H, other substituted sul~onic
aclds, such as, p-hydroxybenzene sulfonlc acid, and
other sulfonlc acids, such as, methanedisul~onlc acld
and methanetrlsul~onlc acld.
The active-hydrogen compounds can be other sul~ur
aclds where sulfur is substltuted for one or more
oxygens in the carboxylic group, such as, methanethlollc
acid (HCOSH), methanethionlc acid (HCSOH), ethanethionic
acid (CH3COSH), ethanethlonic acid (CH3CSOH),
methanethionothiolic acid (HCSSH) and ethanethiono-
` thiollc acid (CH3CSSH).
The active-hydrogen compounds can be alkanethiols
(e.g., having 1 to 20 carbon atoms), such as,
methanethiol, ethanethiol, 2-propanethiol,
~2~33~9~2
UD 13928
34
l-propanethiol, 2-methyl-2-propanethiol, 2-butanethiol,
2-methyl-1-propanethiol, l-butanethiol, 1-pentanethiol,
l,-hexanethiol, l-heptanethlol, l-octanethiol,
l-decanethiolJ 1 dodecanethiol, l-hexadecanethiol,
l-octadecanethiol, and cyclohexanethiol, and aromatic
thiols, ~uch as, benzene thiol (or phene thiol).
Besides monothiols, other thiols can be used such as
dithiols, trithiols and tetrathiols (e.g.,
1,2-ethanedithiol), and substituted thiols (e.g.,
l-amino-2-propane thiol).
Thioglycolic acid and other sulfur analogue acids
can be used as the active-hydrogen compound.
The active-hydrogen compounds can be
alkyl-OCH2CH20H, such as, Cellosolve~ (C2H50CH2CH20H),
methyl Cellosolve~ and butyl Cellosolve~.
The active-hydrogen compounds can be bisulfites of
metals, such as, NaHS03, KHS03, LiHS03, Mg(HS03)~,
Zn(HS03)2 and Be(HS03)2.
The alkoxylating compounds used in the invention
alkoxylation process are epoxide compounds having the
!, formula:
.
~0~ 1
RlR2C ~--- 3 4
. ~ .
. , .
~ Z !33~Z
UD 13928
~herein Rl, R2~ R3 and RL~ are each H or -(CH2)nCH3, and
whereln n is 0 to 3, with the proviso that Rl, R2, R3
and-R4 can be the same or different. The useful
epoxldes are basically derivatives of ethylene oxide.
Examples of the alkoxylating compound are ethylene
oxide, propylene oxide, trimethylene oxide
(2-methyloxlrane), isobutylene oxide,
2,2,3-trimethyloxirane, cis-2-butene oxide,
trans-2-butene oxide, ~ -butylene oxide,
2,2,3,3,-tetramethyloxirane, 2,3-diethyleneoxirane,
2,3-dipropyleneoxirane, 2,3-dibutyleneoxlrane,
2-butyleneoxirane, 2-isobutyleneoxirane and
2-ethylene-3-propylene oxirane. The preferred
alkoxylatlng agent is ethylene oxide because lt is much
more reactive than propylene oxide and the higher
members of the subJect epoxide compounds.
A narrow molecular weight range of products is
produced with a minimum of undesirable high molecular
weight by-products or co-products.
The following examples are illustrative of the
invention.
.
.
q.z~3~09Z
UD 13928
36
EXAMPLE 1
P,reparation 0~ Sulfate~Bound Zirconium Oxide Catalyst
500 ml. of NH40H (14.8M), 500 ml. of distilled
water and 64.5 g of zlrconyl chloride (yellow solld)
were combined and the mixture was placed in a 2 liter
beaker having a watchglass cover. The solution was
stirred for 3 hours. A ~ine white solid rormed quickly
as the stir~lng began. The llquid was filte~ed off in a
Buchner ~unnel. The solid filtrate was placed in a
vacuum oven and dried at 100C. and 30 inches of ~acuum.
After drying in the vacuum oven, about 35 g o~ white
solid was obtained. The solid was washed in a Buchner
funnel using a total of 25 ml. o~ water. The solid was
then treated with lN H2S04 in the form of an acidlc
aqueous solution (pH 1). The solid was divided and
placed in two Pyrex tubes. The solid was calcined ~or 3
hours at 600C. (with air flow). The calcined solid was
light yellow and was sulfate-bound zirconium oxide
(catalyst). 29.6 g of the catalyst was obtained. The
pH of the catalyst in water was acidic.
~283~92 ~D 13928
37
EXAMPLE 2
Preparation Of CARBOWAX~ Polyethylene Glycol 200 Using
Sulfate-Bound Zirconlum Oxide Catalyst
50.7 g of ethylene glycol and 5.0 g of sulfate-
bound zirconium oxide catalyst (prepared by the method
of Example 1) were charged to a Parr bomb. The bomb,
three tlmes, was purged with N2 and evacuated. The bomb
was left under 15 pounds per square inch gauge of
pressure of N2. The bomb was heated and stirred
vigorouslyO Ethylene oxide was added to the bomb based
on the following schedule:
;~ TABLE I
; Reactor Reactor Total Ethylene
Time, Temp. 3 Pressure, Oxide Feed,
15 Mins. C. p~Soi~g~ 1grams
0 8L~ 18/41 6.o
~ 96 24/36 8.1
- 7 86 24/40 13.2
81 24/36 16.1
;~ 20 14 79 24/36 19.8
~Z83~
UD 13928
38
17 81 24/40 25.7
23 78 24/42 32.1
,31 820 24/39 37.1
79 24/37 40.6
48~ 81 26/43 ~6.2
59 840 27/45 52.2
73 820 29/44 57.6
81 30/41 61.1
163 840 29/45 67.2
10212 84 30/45 71,9
234 104 33/54 75.3
241 93 34/56 80.2
261 99O 36/51 9 -
307 97 38/60 94.2
15322 98 41/63 99~ 6
349 97 42/65 105.1
355 96 57/65 106.9
37 97 52/68 110.8
375 97 62/6~ 112.8
20400 98 54
600 16 35
Note:
1. The first number is~ the p~essure be~ore the
.
8 3~ UD 13928
39
ethylene oxide addition, and the second number is the
pressure after the ethylene oxide addition.
An exotherm of 8 to 9 CO occurred immediately
aftSr the ethylene oxide was added to the bomb. The
pressure began to quickly drop. Further exotherms of 8
to 9C. occurred after each addition of ethylene oxide
through the addition totalling 40.6 grams. Then no
exotherm was observed in con~unct~on with ethylene oxlde
additions until the addition totalling 67.2 grams. At
that an exotherm of 4 to 5C occurred. Even larger
exotherms occurred thereafter at some of the subsequent
ethylene oxide additions. The temperature was raised to
100C. before the addition totalling 75.3 grams. The
pressure dropped back quickly and completely after
ethylene oxide additions during the first part of the
run, but slowed somewhat later in the run. (The
pressure dropped faster after reaching 28 p.s.i.g.)
Presure also began building later in the run, but this
was partly a function of the increased temperatureO
(The pressure rose from 31 p.s.i.g. to 33 p.s.i.g. when
the temperature was raised to 100C.) After 600 minutes
the heat was shut off from the bomb. The product was
slightly hazy (possibly due to fine catalyst particles
in suspension therein), had a pH of 7 and was slightly
-
gL2y33o~z
UD 13928
viscous. The product was analyzed uslng vapor phase
chroma~ography. The product was CARBOWAX~ polyethylene
g,lycol 200 produced by the ethoxylation o~ ethylene
glycol~
The sulfate-bound zirconium oxlde catalyst was
recovered usine a flne sintered glass funnel. The
recovered catalyst was washed with ethylene glycol - the
pH at thls point of the catalyst in water was neutral.
The catalyst was then washed wlth methyl alcohol - the
pH was neutral. The catalyst was dried ln an oven at
130C.; after 1.5 hours the pH of the catalyst was 3;
and after 3 hours the pH of the catalyst was 3. The
recovered catalyst was then calclned for 1.5 hours at
575C. with an airflow.
EXAMPLE 3
_.
Preparation of Methyl Cellosolve~ Using Sulfate-Bound
Zirconlum Oxlde Catalyst
50.0 g (1.56 moles) o~ methanol, contalnlng 0.225
percent of water, and 1.0 g o~ sulfate-bound zirconlum
oxlde catalyst (prepared by the method of Example 1)
were charged to a Parr bomb. The bomb was purged with
N2 and evacuated three tlmes. The bomb was left under
16 p.s.i.g. of N2. The bomb was heated and stlrred
",. , ~ . ~
~33C)~Z
UD 13928
41
vigorously. Ethylene oxlde was added to the bomb based
on the following schedule:
,
TABLE II
Reactor Reactor Total Ethylene
5Tlme, Temp., Pressure, Oxide Feed,
Mins. C. p.s.l.g. grams
0 81 34/:38 3.5
19 79 35/35 7.1
7o 790 36/46 12.0
10123 79 40/47 17.2
179 79 44
overnite 16 20
It took 7 mlnutes for the pressure to reach 36 p.s.i.g.
in the bomb, at which tlme the ~irst addition was made.
The pressure reached 36 p.s.l.g. at the 45 mlnute point.
The reactants reacted at the moderate rate, i.eO,
"cooked down'l well. After 179 minutes the heat was shut
o~f from the bomb. The product was methyl Cellosolve~
produced by the ethoxylation of
20 methanol.
.. ; ~ . : , . . .
:;
~D 13928
42 1~ a3092
EXAMPLE 4
Example 3 was repeated, except that the sta~ting
methanol contalned 0.768 percent o~ water (water was
a~ded). The reaction occurred at about the same rate as
in Example 3, but the reaction "cooked down" to slightly
lower pressure. The product was methyl Cellosolve~
p~oduced by the ethoxylation of methanol.
31D9Z
UD 13928
43
EXAMPLE 5
~ xample 3 was repeated, except that the starting
methanol contained 0.0315 percent water. The methanol
was dried over actlvated ~ A sieves. The reaction
occurred at about the same rate as and "cooked down"
slmilarly to Example 3. The product was methyl
Cellosolve~ produced by the ethoxylation of methanol.
All of the above water determinations ln Examples 3
~ to 5 were made on a Photovolt Aquatest IV electronic
`' 10 titratOr.
The purpose of Examples 3 to 5 was to determine the
effect of water content on the preparation of methyl
Cellosolve~ using sulfate-bound zirconium oxide
catalyst. The reactions in Examples 3 to 5 we~e run
with all of the conditions the same except for the water
content of the starting alcohol. Water did not seem to
adversely effect the reaction rate, in fact, a slight
increase ln activity was observed. The conversion to
product could not be correlated with the water content.
A peak was observed in all of the vapor phase
chromatography scans with retentlon time similar to
ethylene glycol, but the area percent of this peak did
not vary significantly between runs.
UD 13928
44
EXAMPLE 6
Preparation Of CARBOWAX~ Polyethylene Glycol Using
Sulfate-Bound Zirconium Oxide Catalyst
52.9 g of ethylene glycol and 5.0 g of sulfate-
bound zl~conium oxide catalyst was charged to a Parr
bomb. The bomb was purged with N2 and evacuated three
tlmes. The bomb was left under 16 p.s.i.g. of N2. The
bomb was heated to 80C. and stirred vigorously.
Ethylene oxide was added to the bomb based on the
following schedule:
TABLE III
Reactor Reactor Total Ethylene
Time, Temp., Pressure, Oxide Feed,
Mins. C. p.s.i.g~ grams
:
15 0 7O 19/40 6.3
6 77 20/40 12.4
12 77 22/44 19.4
21 82 23/44 26.4
77 24/43 33.4
2045 81 26/46 41.1
.:. ~
~L~B'30~92J
UD 13928
48 80 2~
An exotherm of about 30C. occurred upon the first
addltion of ethylene oxlde. The ethylene oxide was
rapidly consumed. The exothe~ms became smaller on
subsequent additlons. At the slx minute addition, the
; exotherm went to 99C. At the 30 minute addition, the
exotherm went to 84C. At the 45 mlnute add~tion, the
exotherm went to 85C. The rate of ethylene oxide
consumptlon also decreased, and the pressure built up
somewhat in the bomb (posslbly due to volume effect).
After 48 minutes the heat was turned off and the
catalyst was flltered off from the liquid p~oduct. The
product was analyzed using vapor phase chromatography.
The sample tested contained 0.21 percent of dioxane.
The product was clear and colorless and had a neutral
pH. The product was CARBOWAX~ polyethylene glycol
(viscous liquld polyethylene glycol) prepared by the
ethoxylatlon of ethylene glycol.
3~Z
UD 13928
46
'
EXAMPLE 7
J
Preparatlon of CARBOWAX~ Polyethylene Glycol Using
; Sulfate-Bound Zlrconlum Oxide Catalyst
The flltered sulfate-bc)und zi~conium oxide catalyst
(5.0 g) from Example 6 was placed ln a Pa~r bomb. The
catalyst was not washed, so a small amount of the liquid
product of Example 6 remained in the bomb. 50.7 g of
ethylene glycol was charged to the bomb. The bomb was
pu~ged with N2 and evacuated three timesa The bomb was
left unde~ 16 poS~i~g~ of N2. The bomb was heated and
stl~red vigorously. Ethylene oxide was added to the
bomb based on the following schedule.
TABLE IV
Time, Reactor Reactor Total Ethylene
15 mins. Temp~, P~essu~e, Oxlde Feed,
C. p.s.i.g. grams
0 81 19/37 6.2
9 79 22/42 11.9
17 77 24/39 16.5
2027 24
1 Z83~92
47 UD 13928
An exotherm to 90C. occurred upon the first addition of
ethylene oxide. The exotherm was not as great as and
the rate of reaction was slower than the lnitial
reaction in Example 6. At the 9 minute addition, the
exotherm went to 880C. At the 17 minute addition, the
exotherm went to 86C. The catalyst apparently lost
some actlvity during the reaction. After 27 minutes the
heat was turned off and the bomb was allowed to set at
room temperature for about 64 hours. The product was
analyzed using vapor phase chromatography. The sample
tested contained 0.29 percent of dioxane. The product
was clear and colorless, and had a neutral pH. The
product was CARBOWAX~ polyethylene glycol prepared by
the ethoxylation of ethylene glycol.
EXAMPLE 8
.~
Preparation of CARBOWAX~ Polyethylene Glycol ~sing
; Sulfate-Bound Zirconium Oxlde Catalyst
42.3 g. of ethylene glycol and 4.2 g o~ sulfate-
bound zirconium oxide catalyst were charged to a Parr
bomb. The bomb was purged with N2 and evacuated three
times. The bomb was left under 16 p.s.i.g. o~ N2. The
30~Z~
UD 13928
48
bomb was heated and stirred vigorously. Ethylene oxide
was charged to the bomb based on the following schedule:
TABLE V
Time, Reactor Reactor Total Ethylene
mlns. Temp., Pressure, Oxlde Feed~
C. p.s.i.g. grams
0 820 18/41 6.4
9 77 20/41 12.3
21 80 22/46 18.8
10 61 81 22
An exotherm went to 99C. upon the first addition o~ the
ethylene oxide. The ethylene oxide was consumed fairly
~ rapidly. The second additlon of ethylene oxide produced
; only a small exotherm (to 84C~) and the reaction slowed
; considerably. At the 21 minute additlon, the exotherm
went to 82C. The product was analyzed using vapor
phase chromatography, indlcattng that a substantial
amount of product was produced. The sample contained
0.12 percent of dioxane. The product was colorless and
sllghtly hazy (probably due to catalyst in suspension).
The product was CARBOWAX~ polyethylene glycol prepared
~2 830g ~ UD 13928
49
by the ethoxylation of ethylene glycol.
EXAMPLE 9
Hydrolysis Of Zirconyl Chloride
500 ml. of dlstilled wat;er and 64.5 e of
ZrOC12.8H20 were placed ln a beaker and mixed. 40 ml.
of concentrated NH40H solution was added with mixlng to
the beaker. The pH of the mixture was about 10. 8.4
ml. of concentrated HCl solution was added to the
admixture to bring the pH back to 7. The admixture was
filtered on a M sintered glass funnel. The pH of the
solid filtrate in water was neutralO The solid filtrate
was placed in a large Soxhlet extractor mounted on a 2
liter flask. The solid filtrate was washed with
distilled water in the Soxhlet extractor. The liquid
mixture was refluxed in the Soxhlet extractor for 13.5
hours. A check of the solid for Cl was essentially
negative. The solld was dried overnight in a vacuum
oven at 100 to 110C. and 30 inches of vacuum over
MgS04. The solid was slightly off white and had the
consistency of talcum powder tvery fine). The solid was
not a hard cake as had been previously observed in thls
example. 28.09 g of the solid were recovered - the
~3~ UD 13928
solid had a neutral pH in water. The solid was placed
in 400 ml. of distilled water. Stirring was started and
the pH was 7. After stlrring for 2 hours the pH was
still neutral. The llquid admixture was filtered on a C
sintered glass funnel. Some of the solid passed through
thé filter. The solid ~iltrate was placed in a vacuum
oven at 80~C. and at 30 inches of vacuum over MgSO4.
The flltrate was dried over a weekend in the vacuum oven
(the temperature reached 90C.). The solid was slightly
A 10 off-white in color and was a fine free-flowing powder.
The pH of the solid in water was neutral; this was the
first tlme the pH indicated neutral for Zr(OH)4. The
product was zirconium hydroxide.
EXAMPLE I0
15 Preparation of Various Anion-Bound Zirconium Oxide
Catalysts
Four samples of Zr(OH)4 (prepared by the method of
Example 10) were each treated with a dlfferent solution,
respectively, of NH4BF4, (NH4)2HPO4, (Me4N)PF6 and
20 H2SO4. (Me4N)PF6 is tetramethylammoniumhexa~luorophos-
phate. NH4BF4 is ammonium tetrafluroborate. Reference
is made to Table VI below ~or the treating agents and
~.q~3~2
UD 13928
51
other presslng data. Each Zr(OH)4 sample in the
respective solution was stirred for 5 to 10 minutes and
~hen filtered on a Buchner funnel. Each of the four
solids was calcined in a Pyrex tube at 575C. (w1th an
air flow) for 3 hours.
33C)~
o el qo ~l ~o3~
'3
o,
Page 5 2
~'~83~92
UD 13928
53
5 g of the calcined filtrate from the sulfuric acld
treated material was washed overnight with distilled
w~ter in a Soxhlet extractor. The distilled water a~ter
the wash had a pH of 2 to 3 and had a very fine, white,
gel~tinous solld floating in it. The wash water tested
positive for SO4(BaC12 test). The solid was removed
from the Soxhlet extractor. The solid in water had a pH
of 4. The solld was then calcined in a Pyrex tube at
575C. (with an air flow) for 3.5 hours. After
calcinlng the solid was yellow; upon cooling, the solid
turned light yellow. The solid product in water had a
pH of 2. The product was sulfate-bound zirconium oxide
catalyst.
EXAMPLE 11
-
Preparation Of CARBOWAX~ Polyethylene Glycol Using
Phosphate-Bound Zlrconium Oxlde Catalyst
42.9 g of ethylene glycol and 4.17 g of zirconium
oxy acid phosphate catalyst (as prepared in Example 10)
were charged to a Parr bomb. The bomb was purged with
; 20 N2 and evacuated three times. The bomb was left under
16 p.s.l.g. of N2. The bomb was heated and stirred
vigorously. Ethylene oxide was charged to the bomb
based on the followlng :chedule:
. . .
,
` ~ ~
~LZ~330~2
,~S ~ ~ S~
o C o = o ~ cn ct~
r ~ ~ r~ r S
O o o o ~ O o. ~ C
r~ r ,~ `r ~
Page 5 4
-
UD 13928
Upon flrst addlng ethylene oxide, a 30C. exotherm
occurred. Thereafter, the exotherms decreased. Also,
t,he rate of reaction, which was very rapld at flrst,
slowed as the reaction proceeded. Durlng the run, the
re~ction was stopped after 23 minutes and later started
up again by contlnued heatlng and further ethylene oxlde
additions. The liquid product was analyzed using vapor
phase chromatography. The product contained 0.25
percent of dioxane. The product was clear and pinkish
and was a little hazy (probably due to catalyst ln
suspension). The pinkish color was due to a bad batch
of ethylene oxide, which had a slight color and fine
particulates ln lt. The pH of the product was neutral.
The catalyst was filtered off from the liquid product.
At that point the pH of the catalyst was 1 to 2. After
washing the catalyst with methanol, the sllghtly wet
catalyst (from methanol) had a pH of 3. The product was
CARBOWAX~ polyethylene glycol prepared by the
ethoxylation of ethylene glycol.
" '
,'
~a30'9Z
~D 13928
56
EXAMPLE 12
Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconium
Oxi~e Catalyst
,
57,9 g of l-butanol and 4.96 g of sulfate~bound
zlrconlum oxlde catalyst (as prepared ln Example 10)
were charged to a Parr bomb. The pH of the mlxtu~e was
neutral. The bomb was purged with N2 and evacuated
three times. The bomb was left under 17 p.s.l.g. of N2.
The bomb was heated and stlrred vlgorously. Ethylene
oxlde was charged to the bomb based on the following
~chedule:
"'.' 3q~3~X
I Yl
1~ . ~ e~~ ~7~a
I:E' ~
~1
~ ~ .
~1 ~
o~ ~ r~
=
~,
~1 o~ o~ Z
Page 5 7
~,'28309~
UD 13928
58
Upon flrst adding ethylene oxide, a 22C. exotherm
occurred with rapid reaction of the lngredients. The
s~econd ethylene oxide produced a rnuch smaller exotherm
and the reaction rate was slower. The temperature was
ral~sed to about 100C~, whereupon the rate of reaction
was faster and the exotherms lncreased for awhlle.
After 73 minutes, the heat was shut off and the sealed
bomb was allowed to set overnight. Two more additlons
of ethylene oxlde were made. The bomb was evacuated
before the sample was taken in order to remove excess
ethylene oxlde. The product was analyzed uslng vapor
phase chromatography and shown to be ethoxylates of
l-butanol. It was difficult to determine that dloxane
was produced due to the close proximlty of dioxane
retentlon time to that of l-butanol. The ll~uld product
was fairly clear, and had a sllgh~ color due to catalyst
in suspenslon and from the bad batch of ethylene oxlde.
The pH of the product was neutral.
:`
~83~ UD 13928
59
EXAMPLE 13
J
Hydrolysis of Zirconyl Chloride and Treatment With
Su~furic Acid
16 g of ZrOC12 8H20 was dissolved in 200 ml. of
; 5 dlstllled water 1n a 500 ml. Erlenmeyer flask. 21 g of
silica gel and 50 ml. of water (to aid stlrring) were
added. Enough NH40H was added while stirrlng to obtain
a pH of 7. The mixture became very thlck as a white
gelatinous precipitate formed. The solution was stirred
for about one hour. A solid was filtered out and dried
overnight in a vacuum oven at 80 to 90C. and under 30
lnches of vacuum over MgS04. 29.33 g of sillca gel and
a flne whlte solid was recovered. The material had a pH
ln water of 3. The material was sieved on a U.S. No. 8
screen to ellminate the fines - 22.10 g of greater than
8 mesh material remained. The sillca gel appeared to be
coated with white material. The silica gel fizzed and
broke up when placed in water. 22.10 g of the silica
gel was treated with 166 ml. of lN H2SO4 and then
2n calcined in Pyrex tubes at 575C. (with alr flow) for 3
hours. The material appeared physically unchanged and
still had a "coated" appearance. The pH of the material
~.Z83~9~ ,
UD 13928
in water was 2 to 3. 20.2 g of the product was
obtained. The solid product was sulfate-bound zlrconium
o~ide catalyst bound to silica gel carrier.
.
, EXAMPLE 14
Hydrolysls Of Zirconyl Chloride And Treatment With
Sulfuric Acid
16 g of ZrOC12 8H2O was dissolved in 200 ml. of
distilled water in a 500 ml. Erlenmeyer flask. 41 g of
4 A sieves and 100 ml. of water (to aid stirring) were
added. Enough NH40H was added while stirring to obtaln
a pH of 7. The mixture became very thick as a white
gelatinous precipltate formed. The solution was stirred
for about one hour. A solid was filtered out and dried
overnight in a vacuum oven at 80 to 90 C. and under 30
inches of vacuum over MgS04. The material had a neutral
pH in water. The materlal was sieved on a U.S. No. 20
screen to eliminate the fines - 49.49 g of the greater
than 20 mesh material remained. The sieves appeared to
have abso~bed Zr(OH)4, a white powder - very little
fines were present~ The sieves appeared to have white
powder on their surface, but the color was uneven. 10
g. of the sieve mater~al was treated with 75 ml of lN
. :
3~ ~
UD 13928
61
H2S04. Some white color went into the H2S04. The
H2S04-treated sieve material was calcined in Pyrex tubes
~t 575C. (with air flow) for 3 hours. Some f~ne
particles were present after calcining. The pH of the
sleve material in water was 5 to 6. The solid product
was sulfate-bound zirconium oxlde catalyst bound to 4 A
sieves.
EXAMPLE 15
Preparation Of CARBOWAX~ Polyethylene Glycol Using
Sillca Gel-Supported Sulfate-Bound Zlrconlum Oxide
Catalyst
155.2 g of ethylene glycol (a syrupy liquld) and
20.2 g of silica gel-supported sulfate-bound zirconium
oxide catalyst (as prepared ln Example 13) were
thoroughly mixed and placed ln the reactor tube (one
inch diameter) of a recirculatlng loop reactor. The
reactor tube was purged with N2 and evacuated three
times. The reactor tube was left under 15 p.s.i.g. of
N2. The reactor tube was heated to about 80C.
Ethylene oxide was charged to the reactor tube based on
the following schedule:
~ ~83~9h
UD 13928
62
Reactor Reactor Total Ethylene
Time, Temp.,l Pressure, Oxide Feed,
Mins. C. p.s.i.g. grams
0 800/820 19/32 5.1
780/970 22/40 8.1
9 75/98 22/40 10.7
13 70/820 22/42 12.1
18 800/780 22/42 13.4
22 75'/73 22/43 14.7
26 780/740 22/45 16.2
31 79/73 22/45 17.4
36 72/70 22/45 18.7
41 77/68 22/45 20.1
46 80o/68 22/42 2105
52 850/670 22/52 24.2
57 76/72 24/52 29.7
63 80/79 24/56 35.6
79 780/760 24/55 43.3
84 80/69 23/55 50.9
92 790/69 24t54 58.6
102 83/760 26/55 65.5
116 83/71 26/55 72.1
127 80/700 25/55 80.3
142 (2) 81/69 28
~2~
UD 13928
63
142 15 22
174 850/600 28/58 85.1
195 830/670 30/58 90.0
199 85/64 30 91.9
Note: 1. The first number ic; the temperature
of the bomb, and the second number is
the temperature inslde of the reactor tube.
2. Reactor shut down overnight and then
restarted.
To samples taken durlng the run and the final product
were analyzed by means of vapor phase chromatography.
The product had a pH in water of neutral. The catalyst
was washed with methanol to remove color caused by
ethylene oxide. The product was CARBOWAX~ polyethylene
glycol produced by ethoxylation of ethylene glycol.
EXAMPLE 16
Preparation Of Sulfate Bound Zirconium Oxide Catalyst
lO g of Zr(OH)~ and 150 ml. of 0.5N H2S04 were
placed in a beaker and stirred for a few minutes. The
UD 13928
64
solld was flltered off from the solution. The solid was
calcined in a Pyrex tube at 575C. (with air flow) for
3 3/4 hoursO The calcined solid was white and had a pH
ln water of 1. The solid was stored in a desiccator
unt-il needed. The product was sulfate-bound zirconium
oxlde catalyst.
EXAMPLE 17
Ethoxylation Of 2-Octanol Using Sulfate-Bound Zirconlum
Oxlde Catalyst
49.9 g of 2-octanol and 3.0 g of sulfate~bound
zlrconium oxyide catalyst (as prepared by the method of
Example 16) were charged to a Parr bomb. The bomb was
purged with N2 and evacuated three times. The bomb was
left under 15 p.s.i.g. of N2. The bomb was heated and
stlrred vigorously. Ethylene oxide was added to the
bomb based on the following schedule:
~283~9~
UD 13928
TABLE X
Reactor Reactor Total Ethylene
Time, temp., Pressure, Oxlde Feed,
Mins. C. p.s.l.g. grams
.
0 82 18/366.6
7 (1) 30
11 115 31/5411.4
19 112 31/5817.0
44 108 33/5220.2
52 107 48/4920.5
113 107 26 20.5
Note: 1. The reactor temperature was lncreased to
110C.
Immedlately after the ethylene oxide was added to the
bomb an exotherm to 85C. occurred. At the 7 minute
polnt ln the run, the temperature of the reactor was
increased to 110C. and the reactor pressure ~ose to 31
p.s.i.g. When ethylene oxide was added at the 11 mlnute
point in the run, an exotherm to 125C. occurred. No
noticeable exotherms occurred thereafter during the run.
The product was analyzed using vapor phase
chromatography. The product had a neutral pH in water.
~28309~ UD 13928
66
The product ~as ethoxylates of 2-octanol.
;
, EXAMPLE 18
Pre~aration Of Sulfate-Bound Zirconium Oxide
50 g of commercial Zr(OH)4 (sllghtly damp, file
white powder, with NH3 odor) was washed free of NH3 with
distilled H2O. After the 750 ml. washing, the pH was
neutral. The powder was washed with an additional 250
ml. of dlstllled H2O. The pH was still neutral. A
check of the wash water for Cl was negative (AgNO3
test). The powder was dried overnight in oven at 100C.
in an open beaker. 29.61 g of fine white powder was
- removed after drylng. No NH3 odor was evident. The pH
of the solid in H2O was neutral.
10 grams of the treated Zr(OH)4 was treated with
150 ml. of lNH2S04 in a beaker with stirring for 5 to 10
minutes. The solution was filtered on No. 42 filter
paper. The solld filtrate was dried for 2.5 hours in an
open beaker in a 100C. oven. The pH of the filtrate in
wate~ waq 3. The solld was calclned in a Pyrex tube at
575C. (with air flow) for 2-3/4 hours. The pH of the
~; calcined solid ln water was 0 to 1. One liter of
distilled water and the solid were stirred overnight in
~'
.
.
~33C~
UD 13928
67
a beaker at room temperature. The slid was ~iltered
off. The solid filtrate was calcined in a Pyrex tube at
5~75C. (with air flow) for 3.5 ours. The calcined solid
was white and had a pH in water of l to 2. The product
was sulfate-bound zlrconium oxlde catalyst.
EXAMPLE 19
Preparatlon Of Phosphate-Bound Zlrconium Oxide Catalyst
10 grams of the treated Zr(OH)4 (prepared by the
method of Example 18) was treated wlth 150 ml. of lN
(NH4)2HPO4 solutlon ln a beaker with stlrring for 5 to
10 minutes. The solutlon was filtered on No. 42 filter
paper. The solid filtrate was dried for 2.5 hours in an
open beaker in a 100C. oven. The pH of the flltrate in
water was 8. The solid was calcined in a Pyrex tube at
57-5C. (with air flow) for 2-3/4 hours. The pH of the
calcined solid in water was 2. One liter of distilled
water and the solid were stirred overnight in a beaker
at room temperature. The solid was filtered off. The
solid flltrate was calcined in a No. 5 Pyrex tube at
575C. (with air flow) for 3.5 hours. The calcined
solld was llght yellow and had a pH in water of 3 to 4.
The ~irconlum oxy-anlon product was phosphate-bound
. . .
~~3092
UD 13928
68
zirconlum oxide catalyst.
~ EXAMPLE 20
Pr~paration Of Fluoride-Bouncl Zi^conlum Oxide Catalyst
9.61 grams of the treated Zr(OH)4 was treated with
150 ml. of lN HF solution in a beaker with stlrring for
5 to 10 minutes. The solution was filtered on No. 42
fllter paper. The solid filtrate was dried for 2.5
hours ln an open beaker in a 100C. oven. The pH of the
~iltrate in water was 4. The solid was calcined in a
; 10 Pyrex tube at 575C. (with air flow) for 2-3/4 hours.
One liter of distilled water and the solid were stirred
overnlght in a beaker at room temperature. The solld
was filtered off. The solid filtrate was calcined in a
Pyrex tube at 575C. (with air flow) for 3.5 hours. The
calcined solid was pinkish and had a pH in water of 4,
and was stored in a desiccator until needed. The
produc~ was fluoride-bound zirconium oxide catalyst.
~.
33C~
UD 13928
69
EXAMPLE 21
J
Preparation Of CARBOWAX 200~ Polyethylene Glycol Using
Phosphate-Bound Zlrconium Oxide Catalyst
51.3 g of ethylene glycol and 5.0 g of
phosphate-bound zlrconlum oxlde catalyst (p~epared by
the method of Example 19) were charged to a Parr bomb.
The pH of the mixture was 5. (The pH of ethylene glycol
by itself was 6.) The following formula was used to
determine the amount of ethylene oxide needed:
Wt. Of Starting Compound x M.W. of Product
Wt. Of Starting Compound
Wt. of Product - Wt. Of Starting Compound
Wt. Of Ethylene Oxide
51.30 g x 200 165.30 g (Product) - 51.30 g
62.07 g Y
Y = 114.0 g of Ethylene Oxide
The bomb was purged wlth N2 and evacuated three times.
The bomb was left under 16 p.s.i.g. of N2. The bomb was
heated to 80C. and stirred vigorously. Ethylene oxide
was charged to the bomb based on the following schedule:
` ` ~æ~3~9-~:
UD 13928
TABLE XI
Reactor Reactor Total Ethylene
Time, Temp.,Pressure, Feed,
Mins. C.p.s.i.g. Grams
- 0 77 19/28 3~
79 23/38 8.2
8 88 32/45 12.2
9 91 40/47 14.3
91 40/47 16.1
12 89O 40/47 18.1
14 860 40/46 19.6
16 820 40/46 21.7
17 78 40/46 23.5
83 40/46 24.9
23 82 40/46 26.8
78 40/46 28.1
28 830 40 40.1(3)
59 83 43 (3)
59 81 26/44 46.1
61 83 40/50 50.0(3)
76 (2) 44
81 126 40/57 51.9
84 130 40 (3)
246 122 54 97.0
314 122 51/56 97.8
30~
UD 13928
71
324 121 51/58 9~.7
338 121 51/64 99.7
356 122 52 100.8
364 122 52/72 102.4
, 378 122 54/72 103.7
394 121 54/72 104.6
414 122 54/72 107.0
438 122 54/64 105.0
439 121 55/76 109.4
454 121 56/74 112.3
484 121 56/80 114.7
50~ 121 60
(4) 17 38
; Note: 1. Turned off reactor heat and restarted
the next day.
.
2. The reactor temperature was increased to
125C.
3~ Constant feed o~ ethylene oxide to the
the reactor and then the periodic
addition was resumed as indicated.
4. The reaction heat was Cllt and the
-
- ~z~9~ ~
UD 13928
72
ingredlents were allowed to set ove~nlght
in the sealed bomb.
The reaction proceeded rapidly and an exotherm of 4 to
10C. was observed on the first few additlons. The rate
Or reaction slowed somewhat as ethylene oxide was added,
but still was fairly rapld; and pressure built up
somewhat (some due to volume effect). The bomb was
allowed to set overnight at room temperature after
40.1 g of ethylene oxide had been added. The reaction
was started at about 120C. the followlng morning, and
exotherm again was observed, as well as good activity.
(A slow constant feed was tried at a couple points
during the reaction with good results - fairly stable
pressure.) The pressure built up eventually, so the
constant feed was stopped (ethylene oxide was not
consumed rapidly enough). Addition of ethylene oxide
was difficult at the end of reaction due to high reactor
pressure (higher than the feed). The liquld product was
clear and colorless, and had a pH of 6. The catalyst
was filtered out using No~ 1 filter paper and then an F
sintered glass funnel. The product was analyzed using
vapor phase chromatography. The catalyst was rinsed out
of the bottom of the bomb with about 100 ml. of
distilled water. The pH of the wash water was 6 and the
~L~Z~313~X
UD 13928
73
pH of the catalyst was 5. The catalyst was light brown.
The catalyst was calcined in a Pyrex tube at 575C.
(~with alr ~low) for 1 hour and then stored in a
desiccator. The pH of the calcined catalyst in water
was 2 to 3. The product was CARBOWAX~ polyethylene
glycol 200 prepared by the ethoxylation of ethylene
glycol.
EXAMPLE 22
Preparatlon Of CARBOWAX~ Polyethylene Glycol 200 Using
Phosphate-Bound Zirconium Oxlde Catalyst
50.8 g of ethylene glycol and 4.56 g of
phosphate-bound zirconium oxide catalyst (which had been
recovered and recalcined ln Example 20) were charged to
a Parr bomb. The pH of the mixture was 5. (The pH of
ethylene glycol by itself was 6.) The following
calculation determined the amount of ethylene oxide
needed:
62.07 g 163.69 ~ (product) - 50.80 g
Y = 112.89 g of Ethylene Oxlde
The bomb was purged with N2 and evacuated three times.
12~33092
UD 13928
74
The bomb was left under 16 p.s.i.g. of N2. The bomb was
heated to 120C., stirred vigorously. Ethylene oxide
w~as charged to the bomb based on the following schedule:
_ TABLE XII
Reactor Total Top Of
Time, Reactor Pressure, Oxide Feed, Exotherm,
Mins. Temp.,_C. p.s.l g. grams C.
o 126 24/54 5.4 135C
120 26/58 9.8 131
9 121 28/58 13.6 130
13 121 28/60 18.0 131
18 120 28/60 21.5 130
24 119 29/60 24.8 132
0 121 30/62 27.6 129
34 120 31/60 30.1 125
38 120 32/64 32.7 126
43 119 32 (1)
136 121 56 (2)77.4
225 120 46 (3)
267 121 56 84.0
282 120 49/56 85.o
305 120 49/60 86.1
312 120 51/62 87.4
~830912
UD 13928
318 120 ~4/66 88.3
332 120 50/68 89.5
3,55 121 50/62 90.8
367 120 51/66 92.2
37~ 120 55/66 93.1
403 120 52/65 94.1
415 121 52/66 95.3
420 120 55/66 95.8
445 120 52 (4)
10 445 1~ 36 (5)
447 128 51/60 ~9.5
488 (6) 121 54/60 99.7
Notes:
1. Started constant feed of ethylene oxide.
2. Stopped constant feed of ethylene oxide.
3. Resumed making ethylene oxide additions.
4, Shut off reactor heat and allowed to set
overnight.
5. Resumed heating reactor.
20 6. Run was shut down shortly thereafter.
The reaction was started at about 120C. An
exothe~m was observed when ethylene oxide was added and
the reaction rate was readily comparable to Example 21.
~'Z~;30~3~
UD 13928
76
Exotherms contlnued for several additions of ethylene
oxide. After 38 minutes of the run, a constant ~eedlng
o~ ethylene oxide at a rate of 1 g per 1.5 minutes was
conducted. The reactor pressure at the start of the
co~stant feed was 43 p.s.i. The reaction slowed as the
total ethylene oxide feed approached 80 g. The feed
rate had to be slowed as the pressure built up. The
same happenlng had been observed ln Example 21. It was
not clear whether the slow down of the activity was due
to catalyst lnactivity, dilution effect (increased
volume of liquid vs. fixed amount of catalyst), o~ hlgh
bomb pressure. The liquld product was clear and
colorless and had a pH of 6. The liquid product was
poured from the bomb. The product was analyzed using
vapor phase chromatography. CARBOWAX~ polyethylene
glycol 200 was not quite produced because not quite
enough ethylene oxlde was added. The purpose of this
example is to see if the recovered and recalcined
catalyst could be used to produce CARBOWAX~ ethylene
glycol 200.
33092
UD 13928
77
EXAMPLE 23
P~reparation Of CARBOWAX~ Polyethylene Glycol 400 Using
Sulfate-Bound Zirconium Oxide Catalyst
,
42.0 g of CARBOWAX~ polyethylene glycol 200 and
3.81 g of sulfate-bound zlrconium oxide catalyst were
; charged to a Parr bomb~ The bomb was purged with N2 and
evacuated three times. The bomb was left under 16
p.s.l.g. of N2. The bomb was heated to 65C. and
stirred vlgorously. The catalyst used in thls reactlon
was less acidlc than others used ln some of these
examples. Also the starting reactlon was a lower
temperature to try to ellminate high exotherms and
possible color problems. Ethylene oxide was charged to
the bomb based on the following schedule:
15TABLE XIII
Reactor Total Ethylene
Time, Reactor Pressure, Oxide Feed,
Mins. Temp., C. p.s.i.g. grams
0 65 l9/37 6.3
20 8 65 32/43 9.9
18 62 40 (l)
37 129 34/50 12.5
33~
UD 13928
78
43 118 36/52 15.2
54 120 36/52 18.0
6~1 119 36/53 20.4
69 120 38/55 22.9
80~ 120 39/55 23.0
; 89 120 39/56 27.
100 120 40 (2)
100 18 19 (3)
116 65 22/35 32.8
121 55 34
138 129 52 (4)
145 122 40/58 34.2
151 124 40/58 35.9
155 131 40/58 37.7
172 125 40/70 39.4
183 121 38/68 40.8
193 124 40/58 42.0
230 123 36 (5)
260 31 22
Notes:
~` 1. Reactor temperature was ralsed to about 120C.
2. Reactor was shut down overnight.
3. Reactor was restarted.
4. Temperature was raised to about 120C.
1!33~
UD 13928
79
5. The heat was turned offO
~here was very llttle exotherm on the lnitial ethylene
oxide addition. Also~ the reactlon was slow at 65C.,
so the temperature was raised to about 120C. The
reactlon rate was much faster, but stlll no exotherm was
observed when ethylene oxide was added. The reaction
was stopped overnlght. At that point, the liquid
product was clear and colorless, and had a pH of 6. The
reaction restarted a-t 65C. to try to avold high
temperature operatlon and possible decomposltion. After
adding a small amount of ethylene oxide, the temperature
was raised to about 120C. (At one point in the run,
the temperature reached 135 to 136C. fo~ about 5
minutes.) After the lnitial slight exotherm, no further
exotherms we~e detected. The reaction was slow toward
the end. The reaction was stopped and the gaseous
ethylene oxide was removed. The liquld product was
light yellow and had a pH of 6. The (pinkish brown)
catalyst was ~iltered off. The catalyst was washed with
150 ml of distilled water, which resulted in a white
catalyst. The pH of the water was 3 to 4 and of the
catalyst ln the water was 3. The catalyst was light
- yellow in water and was white when dry. The molecular
weight of the product was too high and possibly the gas
.. ~
~2~3~92
UD 13928
chromatography column might be plugged, so no vapor
phase chromatography analysis was made. The catalyst
~as calcined ln a Pyrex tube at 575C, (with air flow)
for 3.5 hours.
.,
EXAMPLE 24
Hydrolysis Of ~thylene Oxlde Using Sulfate-Bound
Zlrconlum Oxide Catalyst
40.0 g of water and 3.30 g of sulfate bound
zirconlum oxlde catalyst (the recovered, recalcined
catalyst from Example 23) were charged to a Parr bomb.
The bomb was purged with N2 and evacuated three times.
The bomb was left under 16 p.s.i.g. of N2. The bomb was
hated to about 800C. and stlrred vigorously. Ethylene
oxlde was charged to the bomb based on the following
scheduie
TABLE XIV
Reactor Total Ethylene
Time, Reactor Pressure Oxide Feed~
Mins. Temp., C. p.s.i.~ grams
20 o 78 22/38 3.3
~2~33092
UD 13928
81
79 31/42 6.o
24 78 26/43 9.3
3'5 79 29/44 13.4
79 26 (l)
, 18 17 (2)
102 30/54 17.6
58 100 34/50 19.9
62 105 38/58 21.6
64 106 38/56 23.1
; 10 66 105 38/58 24.1
68 104 38/54 26.6
72 103 38/58 28.2
74 104 38/56 30.1
78 103 38/58 32.0
82 105 38/58 34.0
102 38/58 35.5
88 101 38/58 37.o
91 99 38/59 38.9
94 100 38/59 41.2
~0 99 100 38/59 43.2
103 99 38/59 45.3
105 99O 38/58 46 ~ 9
109 99 38/59 49.0
Notes:
33~2
UD 13928
82
l. Heat was turned off overnight.
2. Heat was applied again next day.
No exotherms were observed until the temperature was
ralsed to about 100C. Small exotherms (2 to 5C.)
were observed therea~ter when ethylene oxide was added.
The rate of reaction was fast;er at 100C., and remained
fairly fast throughout the reactlon. The reaction was
stopped, the bomb was evacuated and the catalyst was
filtered out. The liquld product was clear and
colorless, although some of the catalyst remained in the
product. The product had a pH of 4 to 5. 25.56 g of
water was removed from the product on a Rotavapor at
90C. and 30 inches of vacuum. 20.54 g of product
remalned as a kettle product. 75 ml of ethyl acetate
was added to the kettle product in a separation funnel
but layers were evldent. The material was removed and
drled over anhydrous MgS04 (no clumping was observed).
The solution was filtered and the ethyl acetate was
removed in vacuo from the solid filtrate. The solid
product was analyæed using vapor phase chromatography.
The product was hydrolyzed ethylene oxide (ethylene
glycol, dlethylene glycol, and triethylene glycol).
,~
,; ': '
~2~3~g~
UD 13928
83
EXAMPLE 25
Ethoxylation Of l-Butanol Using Sulfate-Bound Zirconium
Oxi~de Catalyst
74.1 g (1 mole) of l-butanol nd 3.30 g of
sulfate-bound zirconium oxlde catalyst were charged to a
Parr bomb. (The catalyst had been prepared by the
procedure of Example 1.) The bomb was purged with N2
and evacuated three times. The bomb was left under 16
p.s.i.g. of N2. The bomb was heated to about 100C. and
stirred vigorously. The pH of the materlal ln the bomb
was 6. Ethylene oxide was charged to the bomb based on
the rollowing schedule: -
TABLE XV
Reactor Total Ethylene
Time, Reactor Pressure Oxide Feed,
Mins. Temp.~ C. p.s.i.g. ~rams
O 112 24/33 5.5
17 110 33/42 ~.7
33 109 34/42 11.0
136 109 27
~LZ !33~9.~2
UD 13928
84
Once ethylene oxide was added, the reaction proceeded
s~owly. The reaction was kept at 109C. for two hours
after the last ethylene oxide addltlon, and then the
reactor system was shut down. A total of 11 grams of
ethylene oxide were used, so the molar ratio o~
l-butanol to ethylene oxlde was 4 to 1. The product was
clear and colorless and had a pH of 6. The catalyst was
filtered off. The catalyst was placed in a Pyrex tube
and calclned at 575C. (with air flow) for 3.5 hours.
The pH of the catalyst in water was neutral. The
product was ethoxylates of l-butanol.
EXAMPLE 26
Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconium
Oxlde Catalyst
74.1 g (1 mole) of l-butanol and 5.20 g of
sulfate-bound ~lrconium oxide catalyst (which had been
recovered and recalcined in Example 25) were charged to
a Parr bomb. The bomb was purged with N2 and evacuated
three times. The bomb was left under 16 p.s.i.g. of N2.
The bomb was heated to 80oC. and stirred vigorously.
The pH of the material in the bomb was 6. Ethylene
.
.
, ' ,, :
~2~33~
UD 13928
oxide was charged to the bomb based on the following
schedule:
TABLE XVI
Reactor Total Ethylene
Time, Reactor Pressure Oxide Feed,
Mins. Temp., C. p.s.i.g. grams
81 19/33 6.6
7 (1) 32
110 40/45 9.8
10 15 108 I~o/46 11.1
29
.
Note:
1. Raised temperature of the reactor.
"
Once ethylene oxide was added, the reaction proceeded
slowly and no exotherm was noticed. So the temperature
was raised to 110C. and the reactlon rate inc.eased.
No exotherms were noticed at the higher temperature
level. The reactor system was shut down. A total of
11.1 g of ethylene oxlde were used, so the molar ratio
Of l-butanol to ethylene oxide was 4 to 1. The liquid
product was clear and colorless and had a pH of 6. The
~283C~9;~:
UD 13928
86
catalyst was filtered off. The product was analyzed by
vapor phase chromatography. The excess catalyst was
r~nsed (but not washed) from the bomb using acetone.
The catalyst was calcined ln a Pyrex tube at 575C.
(wi-th air flow) for 3 hours. The pH of the calclned
catalyst was neutral. The product was ethoxylates Or
l-butanol.
EXAMPLE 27
Ethoxylation Of Glycerol Uslng Sulfate-Bound Zirconlum
Oxide Catalyst
60.2 g of anhydrous glycerol and 3.0 g of
sulfate-bound zirconium oxlde catalyst were charged to a
Parr bomb. (The catalyst had been prepared by the
; procedure of Example 1.) The bomb was purged with N2
and evacuated three tlmes. The bomb was left under 16
p.s.i.g. of N2. The bomb was heated to 80C. and
; stirred vigorously. The pH of the material ln the bomb
was 5 to 6. Ethylene oxlde was charged to the bomb
based on the follow~ng schedule:
- : ..,..,... ~ , ~.... ~ .
- :
~.283~2
UD 13928
~7
TABLE XVII
Reactor Total Ethylene Top Of
Time, Reactor Pressure, Oxide Feed, Exotherm,
Mi~s. Temp., C. p.s.i.g. grams C.
81 18/57 3.4 ~6
6 80 36/58 6.7 860
13 79 42/56 9.3 86
78 44/56 11.7 87
26 78 42/56 14.2 89
10 35 80 40/54 17.3 83
~2 44/54 19.6
59 80 29/47 22.0
107 81 24
A small exotherm (about 6C.) was observed for the first
few additions of ethylene oxide. The reaction rate was
slower than with ethylene glycol, but lt still was
fairly fast. The liquid product was clear and
colorless, and had a pH of 5. The catalyst was flltered
off, but the filtration was very difficult because the
~o liquid product was very thick (viscous). The product
was analy~ed by vapor phase chromatography. The
catalyst was washed with about 200 ml of distilled water
., :
~L283 [11~'2
UD 13928
88
and placed ln a test tube. The product was ethoxylated
glycerol.
EXAMPLE 28
Ethoxylation Of l-Butanol Uslng Sulfate-Bound Zirconlum
Oxide Catalyst
74.1 g (1 mole) of l-butanol and 3.0 g of
sulfate-bound ælrconium oxlde catalyst were charged to a
Parr bomb. (The catalyst had been prepared by procedure
of Example 1.) The bomb was purged wlth N2 and
; 10 evacuated three times. The bomb was left under 16
p.s.i.g. of N2. The bomb was heated to 110C. and
stirred vigorously. The pH of the material in the bomb
was 5 to 6. Ethylene oxide was charged to the bomb
based on the followlng schedule:
TABLE XVIII
Reactor Total Ethylene
Time, Reactor Pressure, Oxide Pressure,
Mlns. Temp., C. p.s.i.~ grams
0 110 22/32 5.3
110 32/40 8.4
, . ' , - .
~' ` `'', :
12~3~9~,
UD 13928
89
31 109 33/42 11.2
109 27
J
The ~eaetion rate was fairly slow but was eomparable
wit-h other l-butanol runs. The reactor was shut down,
and the catalyst was filte~ed out o~ the liquid product.
79.52 g of the llquid product was obtained. A total of
11.2 g of ethylene oxide was usedl so the molar ratio of
1-butanol to ethylene oxlde was 4 to 1. The liquid
produet was elear and eolorless and had a pH of 5 to 6.
The liquld product was analyzed by vapor phase
chromatography.
40 g of the llquid produet was dlstilled in the
fractionating column having a small eondensor. The
fraetions of the distillation were:
TABLE XIX
Pereent
Fractlon Temp., C~ Wt. g. Of Total Product
l-Bu~anol 11727.39 69.4
Butyl
Cellosolve~ 171 7.46 18.9
Product 4.61 11.7
(higher
ethoxylates) Total - 39.46 100
~33~2
UD 13928
28.71 g of the llquid product was separated lnto
1-butanol and butyl cellosolve on a Rotavapor.
(c'ondltions: 60C. on water bath, vacuum pump on
condensor). The fractions were:
TABLE XX
.
; 1 Percent
Receiver Wt., g Of Total Product
Butanol 16.90 65.5
Kettle Product
Butyl Cellosolve
Higher Ethoxylates 8.92 34.5
Total -25.82 100
Note:
1. Probably lost some product to the vacuum.
EXAMPLE 29
Calcining Commerical Zirconlum Sulfate Oxide
Commercial zirconlum sulfate oxide was placed in a
Pyrex tube and calcined at 800C. (with air flow) for 2
3/4 hours. The pH of the catalyst after calcining was
2. The calcined catalyst was insoluble in water.
~ ' ~
1~830~ UD 13928
91
EXAMPLE 30
:
Preparation Of CARBOWAX~ Polyethylene Glycol Using
Calclned Commercial Zlrconium Sulfate Oxide
40~0 g of ethylene glyco:L and 2.5 g of` the calclned
commercial zlrconlum sulfate oxlde from Example 29 were
charged to a Parr bomb. The ~ormula for commerclal
zirconlum sulfate oxide ls ZrO(S04).H2S04.3H20. The
bomb was purged with N2 and evacuated three tlmes. The
bomb was left under 16 p.s.l.g. of N2. The bomb was
heated to 80C. and stlrred vigorously. The pH of the
material in the bomb was 5. Ethylene oxide was charged
to the bomb based on the following schedule:
TABLE XXI
Reactor To~al Ethylene Top Of
15 Tlme, Reactor Pressure, Oxide Feed, Exotherm,
Mins. Temp., C. p.s.l.~ grams C.
0 79 18/32 5.0 91
7 ~3 24/44 11.4 106
~ 11 79 25/40 16.3 87
;~ 20 18 820 30/46 22.1 (1)
27 81 28/46 29.5
.
~28301~Z
UD 13928
92
66 80 24/44 35.2 ~5
76 83 38/54 40.0
1~9 83 38
,
Note:
1. No exotherm was noticed.
Exotherms were observed upon the first few additions of
ethylene oxide. The reaction rate was slower than the
sulfate-bound zlrconium oxide catalysts prepared in the
above examples, but it was still fairly fast. The
reactor was shut down and the catalyst was filtered from
the liquid product. The liquid product was clear and
colorless, and had a pH of 5 to 6. The product was
analyzed by vapor phase chromatography. Catalyst was
rinsed from the bomb. The catalyst was calcined in a
Pyrex tube at 575C. (wlth a~r flow) for l hour. 2.05 g
of catalyst was recovered. The pH of the catalyst in
water was about 6. The product was CARBOWAX~
polyethylene glycol prepared by the ethoxylation of
ethylene glycol.
.
l3309~
- 93 -
EXAMPLE 31
Preparation of Sulfuric Acid - Treated Zirsil* 401
Catalyst
Zirsil* 401 (from Magnesium Elektron, Inc.)
was dried at 100C. in an open beaker over a
weekend. 25 g. of the dried white powder was treated
with 375 ml. of 1 N H2SO4 in a beaker with
stirring for about 5 minutes. The admixture was
filtered. The solid filtrate was dried at 100C. for
1.5 hours. The solid was calcined in Pyrex* tubes at
575C. (with air flow ) for 2 hours. Zirsil* 401 is
a composition which includes 52 percent of silicon
oxide, 16 percent of hydrous zirconium oxide, 12
percent of zircon, 2 to 3 percent of sodium iron at
120 ppm and titanium at 150 ppm, which has an
ignition loss at 1000C. for one hour of 20 percent
(mostly water), and which has a free moisture at
150C. for 15 minutes of 12 percent.
*Trademark.
D-13928
~2~ Z
UD 13928
94
EXAMPLE 32
'
Preparation Of Baslc Sulfate-Bound Zirconium Oxide
Cat21yst
35.0 g of baslc sulfate-bound zlrconium oxlde
(which had a pH of 2 in water) was placed ln a crucible
wlth the lid aJar and was calclned at 800C. (with alr
flow) for 3 hours. The pH of the catalyst ln water was
EXAMPLE 33
?
Treatment Of Sulfate-Bound Zirconium Oxide Catalyst With
Sodium Hydroxide
3.85 g of sulfate-bound zirconlum oxide catalyst
(which had a pH of 2 in water) was treated with 50 ml of
0.5 N NaOH solution in a beaker with stlrring for about
1 minute. (The catalyst had been prepared by the
procedure of Example 1.) The admixture was flltered.
..
The solid flltrate was calcined in a Pyrex tube at
575C. (wlth alr flow) for 1 hour. The pH of the
. .:
,', ~, ,'
~2~33(~92
UD 13928
calclned catalyst in water was 9.
' EXAMPLE 34
Preparation Of CARBOWAX~ Polyethylene Glycol Using Basic
Sulfate-Bound Zirconium Oxide Catalyst
540.1 g of ethylene glycol and 5.0 g of the
basic sulfate-bound zlrconium oxide catalyst Or Example
33 were charged to a Parr bomb. The bomb was purged
with N2 and evacuated three tlmes. The bomb was left
under 16 p.s.i.g. of N2. The bomb was heated about
850C. and stlrred vigorously. The pH of the materlal in
the bomb was 5 to 6. Ethylene oxide was charged to the
bomb based on the following schedule:
TABLE XXII
-- .
Reactor Total Ethylene
~ 15 Time~Reactor Pressure Oxide Feed,
: Mins. Temp., C. p.s.i.~ ams
o 85 18/46 5.9
: 25 105 23/54 9.5
' 43 110 24/56 13.8
:~ 20 63 112 25/50 16.7
:~`
~2~33(~
UD 13928
73 110 30/58 19.1
112 32/54 20.6
98 111 28/58 22.7
106 111 33 (1)
106~ 115 25/54 27.4
151 110 27/64 31.5
206 110 28/62 35.5
247 110 33/68 40.5
406 108 30
Note:
1. The reactor heat was cut off and the reactor
sat overnight.
,
No exotherm was notlced after the flrst ethylene oxide
addition. After the second ethylene oxide addition,
there was an exotherm to 123C. but there was no
reaction after 5 minutes because there was no pressure
drop. The pressure was increased to 110C. and there
was an exotherm to 114C. The reactor was shut down
after the run. The catalyst was filtered out of the
liquid product and placed ln a test tube.
. . .
-- ~2831D92
- 97 -
EXAMPLE 35
Hydrolysis of Zirconyl Acetate To Produce Sulfate-
Bound Zirconum Oxide Catalyst
30 g of (NH4)2SO~ were dissolved in
100 ml of distilled water. 11.26 g of zirconyl
acetate, i.e., ZrO(OAc)2 where OAc is C2H3O2,
was added to the solution. An additional 50 ml of
distilled water was added. At this point, the pH of
the solution was ~ to 5. A total of 9.5 ml o~ 4M
NaOH was added to the solution to raise the pH to 9.
The solid material was filtered out of the solution
and washed with acetone. The solid was calcined in
Pyrex* tubes at 575C. (with air flow) for 3.5
hours. The pH of the calcined solid in water was 1.
2 grams of the calcined material was set aside for
later use. The remainder of the calcined material
was washed with about 200 ml of distilled water and
th~n rinsed with acetone to dry it. The material was
then calcined in a Pyrex* tube at 520C. (with air
flow) for 23 hours. The pH of the solid in water was
1 to 2. The solid was sulfate-bound zirconium oxide
catalyst.
*Trademark.
D-13928
~.'
~2~33~2
UD 13928
98
EXAMPLE 36
P~eparation Of CARBOWAX~ Polyethylene Glycol Uslng
Sulfate-Bound Zirconium Oxide Catalyst
40.0 g of ethylene glycol and 2.0 g of
sulfate-bound zirconlum oxide catalyst (that whlch was
set aside ln Example 35 for a later use) were charged to
a Pa~r bomb. The bomb was purged with N2 and evacuated
three tlmes. The bomb was left under 16 p.s.l.g. of N2.
The bomb was heated to about 80C. and stirred
vigorously. The pH of the material in the bomb`
initlally was 5, but the pH stick slowly changed to 2.
Ethylene oxlde was charged to the bomb based on the
following schedule:
.
` TABLE XXIII
Reactor Total Ethylene Top Of
Time, Reactor Pressure, Oxide Feed~ Exotherm,
Mins. Temp., C. p.s.iog. grams C.
0 82 20/42 5.7 108
4 91 29/50 10.6 (1~
11 91 30/45 16.0 (1)
108 2~/55 20.0 128
31 110 32/55 23.6 119
~L2133~
UD 13928
99
37 103 32/60 27.5 130 (1)
47 112 34/60 30.2 124 (1)
54 112 36/60 34.7 117 (1)
67 109 34/60 40,0
99 - 114 34
An exotherm was observed upon the flrst ethylene oxide
addition, and the reactlon rate was fairly fast. At the
25 mlnute addition, the reaction temperature was raised
to about 110C. Thereafter, mild exotherms occurred and
the reaction rate remained fairly fast. After the
~eactor was closed down, the catalyst was filtered out
of the liquid product and discarded. The pH of the
liquid product was 5. The liquid product was analyzed
; uslng vapor phase chromatography~ The CARBOWAX~
polyethylene glycol product conta1ned a large amount of
undeslrable 1,4-dioxane.
EXAMPLE 37
Hydrolysis Of Hafnyl Chlorlde To Product Sulfate-Bound
Hafnyl Oxide Catalyst
16.4 g of HfOC12.8H20 were dissol~ed in 100 ml of
distilled water. The pH of the solution was 0 to 1.
lZ~3~9;~
UD 13928
100
Concentrated NH40H was added, with stirring, until the
solution pH reached 9 and a whlte, gelatinous
precipitate formed. 6 ml of MH40H were added to the
solution, which was stirred for 10 minutes. The product
precipitated out of the solution. The solid filtrate
was washed overnight in a Soxhlet extractor wlth
distllled water. The wash water in the Soxhlet
extractor with the catalyst had a pH of 7 and was
negative for Cl (AgN03 test). The wash water in the
flask had a pH of 7 and tested positive for Cl . The
solid was dried in an open beaker set in an oven (100
to 120C.) for about 24 hours. 7.05 g of solid was
obtained. The solid was treated with 106 ml of lNH2S04
in a beaker with stirring for about 5 minutes. The
solid was dried overnight at 110 to 120C. The pH of
the solid in water was 2. The solid was calcined in a
Pyrex tube at 575C. (with air flow) for 4.5 hours. The
resultant fine white powder had a pH of 1 in water. The
solid was sulfate-bound hafnyl oxide catalyst.
lZ~331D9~
~D 13928
101
EXAMPLE 38
Preparation Of CARBOWAX0 Polyethylene Glycol Uslng
Sulfate-Bound Hafnyl Oxide Catalyst
40.0 g of ethylene glycol and 2.0 g of sulfate-
bound hafnyl oxide catalyst (as prepared in Example 38)
were charged to a Parr bomb. The bomb was purged with
N2 and evacuated three times. The bomb was left under
16 p.s.i.g. of N2. The pH of the material ln the bomb
was 3 (and was slow to change). The bomb was heated to
100C. and stirred vigorously. Ethylene oxide was added
to the bomb based on the following schedule:
TABLE XXIV
.
Reactor Total Ethylene Top Of
Time, Reactor Pressure, Oxide Feed, Exotherm~
15 Mins. Temp., _C. p.s.i.g. grams C.
0 100 21/46 5.4 134
3 110 28/50 10.2 136
111 2~/50 15.1 135
8 111 30/50 20.2 135
20 10 111 30/50 25.3 130
13 109 32/50 30.1 124
.~ .
.. ~ ....
~,. . .
. .
~LZ~331[)~7~
UD 13928
102
16 109 33/50 33.0 116
111 33/50 35-l~ 115
23 110 34/52 37.7 113
109 35/50 40.0 (1)
49 ~ 110 35
Note:
1. No exotherm.
The reactlon was run at 100 to 110C. Fairly large
exotherms occurred run when ethylene oxide was added.
The reaction rate was very fast (when compared to the
fastest zlrconium compound catalyst tested in the above
examples). The catalyst was filtered from the product,
and washed with about 25 ml of methanol. The catalyst
was placed in a Pyrex test tube and placed in a 530C.
oven (with air flow) for about 12 days. The llquid
product was analyzed using vapor phase chromatography.
The product contained a fairly large amount of dioxane.
The product was CARBOWAX~ polyethylene glycol produced
by ethoxylation of ethylene glycol.
~ : '
~ .
