Note: Descriptions are shown in the official language in which they were submitted.
CA 02362261 2001-08-07
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TITLE
HYDROPEROXIDE DECOMPOSITION PROCESS
FIELD OF THE INVENTION
The invention generally relates to an improved catalytic process for
decomposing alkyl or aromatic hydroperoxides to form a mixture containing the
corresponding alcohol and ketone. In particular, the invention relates to
decomposing a hydroperoxide by contacting it with a catalytic amount of a
heterogenous catalyst comprised of gold, wherein one or more additional metals
selected from Periodic Group VIII is/are also present with gold.
BACKGROUND OF THE INVENTION
Industrial processes for the production of mixtures of cyclohexanol and
cyclohexanone from cyclohexane are currently of considerable commercial
significance and are well described in the patent literature. In accordance
with
typical industrial practice, cyclohexane is oxidized to form a reaction
mixture
containing cyclohexyl hydroperoxide (CHHP). The resulting CHHP is
decomposed, optionally in the presence of a catalyst, to form a reaction
mixture
containing cyclohexanol and cyclohexanone. In the industry, such a mixture is
known as a K/A (ketone/alcohol) mixture, and can be readily oxidized to
produce
adipic acid, which is an important reactant in processes for preparing certain
2o condensation polymers, notably polyamides. Due to the large volumes of
adipic
acid consumed in these and other processes, improvements in processes for
producing adipic acid and its precursors can be used to provide beneficial
cost
advantages.
Druliner et al., U.S. Patent No. 4,326,084, disclose an improved catalytic
process for oxidizing cyclohexane to form a reaction mixture containing CHHP,
and for subsequently decomposing the resulting CHHP to form a mixture
containing K and A. The improvement involves the use of certain transition
metal
complexes of 1,3-bis(2-pyridylimino)isoindolines as catalysts for cyclohexane
oxidation and CHHP decomposition. According to this patent, these catalysts
3o demonstrate longer catalyst life, higher CHHP conversion to K and A,
operability
at lower temperatures (80-160°C), and reduced formation of insoluble
metal-
containing solids, relative to results obtained with certain cobalt(II) fatty
acid
salts, e.g., cobalt 2-ethylhexanoate.
Druliner et al., U.S. Patent No. 4,503.257, disclose another improved
catalytic process for oxidizing cyclohexane to form a reaction mixture
containing
CHHP, and for subsequently decomposing the resulting CHHP to form a mixture
containing K and A. This improvement involves the use of Co304, Mn02; or
Fe304 applied to a suitable solid support as catalysts for cyclohexane
oxidation
~: -: ~ ~~. ~~, PCT/ ~ ~..
CA 02362261 2001-08-07 ,
r6a' < . -, ~- ~. ,, v.
and CHHP decomposition at a temperature from about 80°C to about
130°C, in
the presence of molecular oxygen.
Sanderson et al., U.S. Patent No. 5,414,163, disclose a process for
preparing t-butyl alcohol from t-butyl hydroperoxide in the liquid phase over
catalytically effective amounts of titanic, zirconia, or mixtures thereof.
Sanderson et al., U.S. Patent Nos. 5,414,141, 5,399,794 and 5,401,889,
disclose a process for preparing t-butyl alcohol from t-butyl hydroperoxide in
the
liquid phase over catalytically effective amounts of palladium with gold as a
dispersing agent supported on alumina.
Druliner et al., U.S. provisional application 60/025,368 filed September 3,
1996 (now PCT US97/15332 filed September 2, 1997), disclose decomposing a
hydroperoxide by contacting it with a catalytic amount of a heterogenous
catalyst
of Zr, Nb, Hf and Ti hydroxides or oxides. Preferably, the catalyst is
supported
on Si02, A1203, carbon or Ti02. Alumina is a preferred support.
1 S WO A-98/34894 discloses a process for decomposing hypoperoxides to
their corresponding alcohol and ketone.
Further improvements and options are needed for hydroperoxide
decomposition to KJA mixtures in order to overcome the deficiencies inherent
in
the prior art. Other objects and advantages of the present invention will
become
apparent to those skilled in the art upon reference to the detailed
description
which hereinafter follows.
SUMMARY OF THE INVENTION
In accordance with the present invention, an improved process is provided
in which a hydroperoxide is decomposed to form a decomposition reaction
mixture containing a corresponding alcohol and ketone. The improvement
comprises decomposing hydroperoxide by contacting a hydroperoxide with a
catalytic amount of a catalytic amount of a heterogenous catalyst comprised of
gold, wherein one or more additional metals selected from Periodic Crroup VIII
islare also present with gold. Moreover, the catalysts are optionally
supported on
a suitable support member, such as Si02, A12O3, carbon, zirconia, Mg0 or Ti02.
Preferably the additional metal is Pt or Pd. The process may optionally be
run in the presence of hydrogen gas.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides-an improved process for conducting a
hydroperoxide decomposition step in an isadustrial process in which an alkyl
or
aromatic compound is oxidized to form a mixture of the corresponding alcohol
and ketone. In particular, cyclohexane can be oxidized to form a mixture
containing cyclohexanol (A) and cyclohexanone (K). The industrial process
2
AMENDED SHEET
' CA 02362261 2001-08-07 ~~~~~~ rt, ~, PCT/ ~ ~ -,
involves two steps: first, cyclohexane is oxidized, forming a reaction mixture
containing CHHP; second, CHHP is decomposed, forming a mixture containing K
2?
AMENDED SHEET
'~.'~ ~- ,~ . ~ y ";
CA 02362261 2001-08-07
WO 00/53550 PCT/US99/05228
and A. As previously mentioned, processes for the oxidation of cyclohexane are
well known in the literature and available to those skilled in the art.
Advantages of the present heterogenous catalytic process, relative to
processes employing homogenous metal catalysts, such as metal salts or
metal/ligand mixtures, include longer catalyst life, improved yields of useful
products, and the absence of soluble metal compounds.
The improved process can also be used for the decomposition of other
alkane or aromatic hydroperoxides, for example, t-butyl hydroperoxide,
cyclododecylhydroperoxide and cumene hydroperoxide.
The CHHP decomposition process can be performed under a wide variety
of conditions and in a wide variety of solvents, including cyclohexane itself.
Since CHHP is typically produced industrially as a solution in cyclohexane
from
catalytic oxidation of cyclohexane, a convenient and preferred solvent for the
decomposition process of the invention is cyclohexane. Such a mixture can be
used as received from the first step of the cyclohexane oxidation process or
after
some of the constituents have been removed by known processes such as
distillation or aqueous extraction to remove carboxylic acids and other
impurities.
The preferred concentration of CHHP in the CHHP decomposition feed
mixture can range from about 0.5% by weight to 100% (i.e., neat). In the
industrially practiced route, the preferred range is from about 0.5% to about
3%
by weight.
Suitable reaction temperatures for the process of the invention range from
about 80°C to about 170°C. Temperatures from about 110°C
to about 130°C are
typically preferred. Reaction pressures can preferably range from about 69 kPa
to
about 2760 kPa (10-400 psi) pressure, and pressures from about 276 kPa to
about
1380 kPa (40-200 psi) are more preferred. Reaction time varies in inverse
relation
to reaction temperature, and typically ranges from about 2 to about 30
minutes.
As noted previously, the heterogenous catalysts of the invention include
Au, Ag, Cu (including, but not limited to, Au, Ag and Cu sol-gel compounds)
and
certain non-Au/Ag/Cu sol-gel compounds, preferably applied to suitable solid
supports. The inventive process may also be performed using Au, Ag or Cu in
the
presence of other metals (e.g., Pd). The metal to support percentage can vary
from about 0.01 to about 50 percent by weight, and is preferably about 0.1 to
about 10 wt. percent. Suitable, presently preferred supports include Si02
(silica),
A1203 (alumina), C (carbon), Ti02 (titania), Mg0 (magnesia) or Zr02
(zirconia).
Zirconia and alumina are particularly preferred supports, and Au supported on
alumina is a particularly preferred catalyst of the invention.
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Some of the heterogenous catalysts of the invention can be obtained
already prepared from manufacturers, or they can be prepared from suitable
starting materials using methods known in the art. These methods can include
sol-gel techniques as described in more detail below for preparing both
Au/Ag/Cu
sol-gel compounds and other non-Au/Ag/Cu sol-gel compounds. Supported gold
catalysts can be prepared by any standard procedure known to give well-
dispersed
gold, such as evaporative techniques or coatings from colloidal dispersions.
In particular, ultra-fine particle sized gold is preferred. Such small
particulate gold (often smaller than l Onm) can be prepared according to
Haruta,
1o M., "Size-and Support-Dependency in the Catalysis of Gold", Catalysis Today
36
(1997) 153-166 and Tsubota et al., Preparation of Catalysts V, pp. 695-704
( 1991 ). Such gold preparations produce samples that are purple-pink in color
instead of the typical bronze color associated with gold and result in highly
dispersed gold catalysts when placed on a suitable support member. These
highly
dispersed gold particles typically are from about 3 nm to about 15 nm in
diameter.
The catalyst solid support, including Si02, A1203, carbon, MgO, zirconia,
or Ti02, can be amorphous or crystalline, or a mixture of amorphous and
crystalline forms. Selection of an optimal average particle size for the
catalyst
supports will depend upon such process parameters as reactor residence time
and
2o desired reactor flow rates. Generally, the average particle size selected
will vary
from about 0.005 mm to about 5 mm. Catalysts having a surface area larger than
10 m2/g are preferred since increased surface area of the catalyst has a
direct
correlation with increased decomposition rates in batch experiments. Supports
having much larger surface areas can also be employed, but inherent
brittleness of
high-surface area catalysts, and attendant problems in maintaining an
acceptable
particle size distribution, will establish a practical upper limit upon
catalyst
support surface area. A preferred support is alumina; more preferred is a,-
alumina
and y alumina.
A "sol-gel technique" is a process wherein a free flowing fluid solution,
"sol", is first prepared by dissolving suitable precursor materials such as
colloids,
alkoxides or metal salts in a solvent. The "sol" is then dosed with a reagent
to
initiate reactive polymerization of the precursor. A typical example is
tetraethoxyorthosilicate (TEOS) dissolved in ethanol. Water, with trace acid
or
base as catalyst to initiate hydrolysis, is added. As polymerization and
crosslinking proceeds, the free flowing ''sol" increases in viscosity and can
eventually set to a rigid "gel". The "gel" consists of a crosslinked network
of the
desired material which encapsulates the original solvent within its open
porous
structure. The "gel" may then be dried, typically by either simple heating in
a
4
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WO 00/53550 PCT/US99/05228
flow of dry air to produce a xerogel or the entrapped solvent may be removed
by
displacement with a supercritical fluid such as liquid C02 to produce an
aerogel.
These aerogels and xerogels may be optionally calcined at elevated
temperatures
(>200°C) which results in products which typically have very porous
structures
and concomitantly high surface areas.
In practice of the invention, the catalysts can be contacted with CHHP by
formulation into a catalyst bed, which is arranged to provide intimate contact
between catalysts and reactants. Alternatively, catalysts can be slurried with
reaction mixtures using techniques known in the art. The process of the
invention
1o is suitable for batch or for continuous CHHP decomposition processes. These
processes can be performed under a wide variety of conditions.
Adding air or a mixture of air and inert gases to CHHP decomposition
mixtures provides higher conversions of process reactants to K and A, since
some
cyclohexane is oxidized directly to K and A, in addition to K and A being
formed
by CHHP decomposition. This ancillary process is known as "cyclohexane
participation", and is described in detail in Druliner et al., U.S. Patent
No. 4,326,084, the entire contents of which are incorporated by reference
herein.
Other gases may also be added or co-fed to the reaction mixture as needed.
Inert
gases such as nitrogen may also be added to the reaction alone or in
combination
2o with other gases.
The results of the CHHP decomposition reaction, such as the K/A ratio or
conversion rate, can be adjusted by choice of catalyst support, gases added to
the
reaction mixture, or metals added to the heterogeneous catalysts of the
invention.
Preferably, metals added to the heterogeneous catalysts of the invention
are for use as promoters, synergist additives, or co-catalysts are selected
from
Periodic Group VIII, hereby defined as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
Most preferred is Pd and Pt.
One preferred gas that can be added to the reaction mixture is hydrogen.
An advantage of the addition of hydrogen is that the K/A ratio can be varied
according to need. The addition of hydrogen can also convert impurities or
by-products of the reactions, such as benzene, to more desirable products.
The process of the present~invention is further illustrated by the following
non-limiting examples. In the examples, all temperatures are in degrees
Celsius
and all percentages are by weight unless otherwise indicated.
EXPERIMENTS
Experiment 1 ~1.4% Au on Carbon
~ g of 20-3~ mesh (0.~-0.85 mm) charcoal carbon (EM Science. Cherry
Hill, N~ was calcined in flowing helium (100 mL/min) at 400°C for 1
hour. This
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WO 00/53550 PCT/US99/05228
material was then slurried into a solution of 0.1 g gold trichloride in 10 mL
water
containing 1 mL concentrated HCI. The slurry was stirred for 1 ~ minutes at
room
temperature and then evaporated to dryness on a rotary evaporator. The
recovered
solid was calcined in flowing nitrogen (100 mL/min) at 400°C for 1
hour, cooled
and then stored in tightly capped vial for testing as a CHHP decomposition
catalyst.
Experiment 2 ~1.4% Au on Silica
5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume
1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium (100 mL/min)
at 400°C for 1 hour. This material was then slurried into a solution of
0.1 g gold
trichloride in 10 mL water containing 1 mL concentrated HCI. The slurry was
stirred for 1 S minutes at room temperature and then evaporated to dryness on
a
rotary evaporator. The recovered solid was calcined in flowing nitrogen
(100 mL/min) at 400°C for 1 hour, cooled and then stored in tightly
capped vial
for testing as a CHHP decomposition catalyst.
Experiment 3 ~14% Au on Silica
5 g of <2 micron silica gel with surface area 450 m2/g and pore volume
1.6 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium
(100 mL/min) at 400°C for 1 hour. This material was then slurried into
a solution
of 1.0 g gold trichloride in 10 mL water containing 1 mL concentrated HCI. The
slurry was stirred for 15 minutes at room temperature and then evaporated to
dryness on a rotary evaporator. The recovered solid was calcined in flowing
nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then stored in
tightly
capped vial for testing as a CHHP decomposition catalyst.
Experiment 4 - Plain Silica Control
5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume
1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100
mL/min)
at 400°C for 1 hour. This material was then slurried into a solution of
10 mL
water containing 1 mL concentrated HC1. The slurry was stirred for 15 minutes
at
room temperature and then evaporated to dryness on a rotary evaporator. The
recovered solid was calcined in flowing nitrogen (100 mL/min) at 400°C
for
1 hour, cooled and then stored in tightly capped vial for testing as a CHHP
decomposition catalyst.
Experiment 5 ~1.4% Au on a-Alumina
5 g of 6-12 mesh a-alumina spheres (Calsicat, Erie, PA) was slurried into
a solution of 0.1 g gold trichloride in 10 mL water containing 1 mL
concentrated
HCI. The slurry was stirred for 15 minutes at room temperature and then
evaporated to dryness on a rotary evaporator. The recovered solid was calcined
in
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flowing nitrogen (100 mL/min) at 400°C for 1 hour, cooled and then
stored in
tightly capped vial for testing as a CHHP decomposition catalyst.
Experiment 6 ~13% A~ on Silica
g of + 8 mesh silica gel with surface area 300 m2/g and pore volume
5 1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100
mL/min)
at 400°C for 1 hour. This material was then slurried into a solution of
1.0 g silver
nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry was
stirred for 15 minutes at room temperature and then evaporated to dryness on a
rotary evaporator. The recovered solid was calcined in flowing nitrogen
(100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined
another 1 hour in
flowing hydrogen (100 mL/min) and then stored in tightly capped vial for
testing
as a CHHP decomposition catalyst.
Experiment 7 ~ 4.5% Cu on Silica
5 g of + 8 mesh silica gel with surface area 300 m2/g and pore volume
1 cc/g (Alfa Aesar, Ward Hill, MA) was calcined in flowing helium ( 100
mL/min)
at 400°C for 1 hour. This material was then slurried into a solution of
1.0 g
copper nitrate in 10 mL water containing 1 mL concentrated HN03. The slurry
was stirred for 15 minutes at room temperature and then evaporated to dryness
on
a rotary evaporator. The recovered solid was calcined in flowing nitrogen
(100 mL/min) at 400°C for 1 hour, cooled to 200°C and calcined
another 1 hour in
flowing hydrogen (100 mL/min) and then stored in tightly capped vial for
testing
as a CHHP decomposition catalyst.
Unlike Experiments 1-7, Experiments 8-13 were carned out according to
the general gold deposition technique of Tsubota et al., Preparation of
Catalysts V,
pp. 695-704 (1991) to produce ultra-fine gold particles. These supported
catalysts
were purple/pink in color compared to the bronze/gold (higher loadings) or
brown/grey (lower loadings) supported catalysts of Experiments 1-7.
Experiment 8 ~1 % Au on MAO
10 g of powdered - 200 mesh Mg0 (Alfa Aesar, Ward Hill, MA) was
slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1
mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium
carbonate solution and then 0.69 g sodium citrate was added. After stirring
for
2 hours at room temperature the solid was recovered by filtration and washed
well
with distilled water. The recovered solid was calcined in flowing air
(100 mL/min) at 250°C for 5 hour, cooled and then stored in tightly
capped vial
for testing as a CHHP decomposition catalyst.
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Experiment 9 ~1 % Au on ~~-Alumina
g of powdered - 60 mesh ~y-alumina (Alfa Aesar, Ward Hill, MA) was
slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1
mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium
5 carbonate solution and then 0.69 g sodium citrate was added. After stirring
for
2 hours at room temperature the solid was recovered by filtration and washed
well
with distilled water. The recovered solid was calcined in flowing air
(100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly
capped vial
for testing as a CHHP decomposition catalyst. The resulting catalyst was
to purple/pink in color and had a gold particle size of 8nm as determined by x-
ray
diffraction (XRD).
Experiment 10 ~1% Au on Silica
10 g of silica + 8 mesh granules (Alfa Aesar, Ward Hill, MA) was slurried
into a solution of 0.2 g gold trichloride in 50 mL water containing 1 mL
concentrated HCI. The pH of the slurry was adjusted to 9.6 with sodium
carbonate solution and then 0.69 g sodium citrate was added. After stirring
for
2 hours at room temperature the solid was recovered by filtration and washed
well
with distilled water. The recovered solid was calcined in flowing air
(100 mL/min) at 250°C for 5 hours, cooled and then stored in tightly
capped vial
for testing as a CHHP decomposition catalyst.
Experiment 11 ~1% Au on Titanic
10 g of powdered - 325 mesh titanic (Alfa Aesar, Ward Hill, MA) was
slurried into a solution of 0.2 g gold trichloride in 50 mL water containing 1
mL
concentrated HCI. The pH of the slurry was adjusted to 7.0 with sodium
carbonate solution and then 1.5 g sodium citrate was added. After stirnng for
2 hours at room temperature the solid was recovered by filtration and washed
well
with distilled water. The recovered solid was calcined in flowing air
(100 mL/min) at 400°C for S hours, cooled and then stored in tightly
capped vial
for testing as a CHHP decomposition catalyst.
Experiment 12 ~1% Au on Zirconia
10 g - 325 mesh zirconia (Calsicat #96F-88A, Erie, PA) was slurried into a
solution of 0.2 g gold chloride in 50 mL water and 1 drop conc. HCI. The
slurry
was stirred gently as the pH was adjusted to 9.6 with O.1M sodium carbonate
solution. The slurry was stirred gently while 0.69 g sodium citrate solid was
slowly added and then stirred for 2 further hours. After filtering and washing
well
with distilled water; the solid was calcined in flowing air for 5 hours at
250°C.
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Experiment 13 ~1 % Au and 0.1 % Pd on Alumina
g - 60 mesh y-alumina was slurried into a solution of 0.2 g gold and
0.02 g palladium tetraamine chloride in 50 mL water and one drop of conc. HCI.
The slurry was stirred gently as the pH was adjusted to 9.6 with O.1M sodium
5 carbonate solution. The slurry was again stirred gently while 0.69 g sodium
citrate solid was slowly added and then stirred for 2 further hours. After
filtering
and washing well with distilled water, the solid was calcined in flowing air
for 5
hours at 250°C .
EXAMPLES
to Examples 1-22 were run in batch reactor mode, in stirred 3.5 mL glass
vials, sealed with septa and plastic caps. Vials were inserted into a block
aluminum heater/stirrer apparatus that holds up to 8 vials. Stirring was done
using
Teflon~-coated stir bars. Each vial was first charged with 1.5 mL of n-octane
or
undecane solvent, approximately 0.005 or 0.01 g of a given crushed catalyst, a
stir
bar and the vial was sealed. Vials were stirred and heated approximately
10 minutes to assure that the desired reaction temperature of 125°C had
been
attained. Next, at the start of each example, 30 ~L of a stock solution of
CHHP
and TCB(1,2,4-trichlorobenzene) or CB (chlorobenzene), GC (gas
chromatography internal standard, were injected. Stock solutions consisted of
2o mixtures of about 20 wt % TCB or CB in CHHP. The CHHP source contained up
to 2.0 wt % of combined cyclohexanol and cyclohexanone. Vials were removed
from the aluminum heater/stirrer after a 0.5 to 10 minute period and were
allowed
to cool to ambient temperature.
In Examples 1-10 (Table I) vials were analyzed directly for the amount of
CHHP remaining, using a 15 m DB-17 capillary column with a 0.32 mm internal
diameter. The liquid phase of the column was comprised of (50 wt% phenyl)
methyl polysiloxane. The column was obtained from J. and W. Scientific,
Folsum, California.
GC analyses for the amounts of CHHP in each solution were calculated
using the equation:
wt. % CHHP = (area % CHHP/area % TCB) x wt. % TCB x R.F.~HHP
R.F.~HHP (GC response factor for CHHP) was determined from
calibration solutions containing known amounts of CHHP and TCB, and was
calculated from the equation:
wt. % CHHP/area % CHHP
R.F.~HHP = ~, % TCB/area % TCB
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WO 00/53550 PCT/US99/05228
CHHP Decomp. = 100 x [1-(area % CHHP/area % 1'CB) final/
(area % CHHP/area % TCB initial]
In Examples 1-10 (Table I) the initial concentrations of CHHP in each vial
were approximately 2.2 wt %. The GC wt % CHHP;";tial ~d CHHP f~ai numbers
are only approximate because the amount of TCB per g solution ratios used in
GC
calculations were arbitrarily all made equal to 0.25 mg TCB/ g solution. Since
an
unheated sample of 1.5 mL n-octane and 30 ~L CHHP/TCB solution was
analyzed with each set of CHHP decomposition product vials made from the same
CHHP/TCB solution, accurate changes in CHHP/TCB ratios could be calculated.
Examples 11-13 (Table II), and Examples 14-16 (Table III), give batch
t-butylhydroperoxide (t-Bu00H) and % cumenehydroperoxide (Cumene00H)
decomposition results, respectively for 1% Au/Carbon and 10% Au/Si02
catalysts. Analyses for t-Bu00H and Cumene00H were done using a well
known iodometric titration procedure, described in Comprehensive Analytical
Chemistry, Elsevier Publishing Company, New York, Eds. C. L. Wilson, p. 756,
1960. Starting and product solutions of t-Bu00H and Cumene00H in n-octane,
followed by adding excess KI/ acetic acid solution, were stirred in sealed
vials at
ambient temperature for 10 minutes and were titrated with 0.1 M Na2S203
solution for amounts of I2 liberated by the t-Bu00H and Cumene00H present.
Examples 17-22 (Tables IV&V) were run as described for Examples 1-10
except that the reaction was run at 150°C and chlorobenzene was used as
a GC
internal standard in place of TCB and undecane was used in place of n-octane
solvent. In Tables IV and V, the amount of initial CHHP and final CHHP in the
reaction was determined by calculating the area of the CHHP GC peak divided
by the area of the chlorobenzene GC peak (area % CHHP/area % CB).
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TABLE
Method I ReactionTime,Wt% Wt% % CHHP
EX.Catalyst of Approx. CHHP CHHP
Wt% Temp.,min. initialfinalDecomp.
Prep CHHP C
1 1.4% Au/Carbon, Exp. 2.2 125 10 0.4070.22145.7
0.0100 1
2 1.4% Au/Carbon, Exp. 2.2 125 10 0.5370.28147.7
0.0103 I
3 1.4% Au/Si02, Exp. 2.2 125 10 0.4070.3913.9
0.0101 2
4 1.4% Au/Si02, Exp. 2.2 125 10 0.5370.43019.9
0.0101 2
14% Au/Si02, Exp. 2.2 125 10 0.4070.15462.2
0.0102 3
6 14% Au/Si02, Exp. 2.2 125 10 0.4070.13167.8
0.0104 3
7 0% Au/Si02, 0.0103Exp. 2.2 125 10 0.4070.3796.9
4
8 1.4% Au/A1203, Exp. 2.2 125 10 0.5370.44916.4
0.0102 5
9 13% Ag/Si02> Exp. 2.2 125 10 0.4070.24539.8
0.0102 6
4.5% Cu/Si02, Exp. 2.2 125 10 0.4070.11970.8
0.0103 7
TABLE II
Wt% Wt%
MethodReactionTime,t-Bu00Ht-Bu00H% t-Bu00H
EX.Catalyst, g of Temp., min. initialfinal Decomp.
prep. C
11 1.4% Au/Carbon, Exp. 125 10 0.35 0.20 44
0.0102 1
12 14% Au/Si02, Exp. 125 10 0.35 0.18 48
0.0102 3
13 none 125 10 0.35 0.33 5
TABLE III
Wt% Wt%
t-Cumene-t-Cumene-% t-Cumene-
Method ReactionTime,(OOH) (OOH) (OOH)
EX. Catalyst, g of prep. Temp., min. initial final Decomp.
C
14 1.4% Au/Carbon, 0.0103125 10 0.55 0.32 42
Exp. 1
14% Au/Si02, 0.0103 125 10 0.55 0.30 45
Exp. 3
16 none 125 10 0.55 0.54 2
11
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TABLE
IV
Approx. CHHP/CHHP/
MethodWt% ReactionTime,CB CB % CHHP
EX.Catalyst of CHHP Temp., min.initialfinalDecomp.
Prep C
17 1 %Au/MgO, 0.0102 Exp. 2.2 150 5 3.41 3.29 3.5
8
18 1%Au/y-A1203, 0.0120Exp. 2.2 150 5 3.41 0 100
9
19 I%Au/Si02, 0.0101 Exp. 2.2 150 5 3.41 0.91 73.3
10
20 1%Au/Ti02, 0.0106 Exp. 2.2 150 5 3.41 2.26 33.6
11
21 1 % Au/Zr02, 0.0054 Exp. 2 150 0.5 5.26 4.68 11.1
12
22 1% Au, 0.1% Pd/A1203,Exp. 2 150 0.5 4.82 3.01 37.5
0.0051 13
Examples 23-39 were run in a liquid full plug flow reactor, 30 inches
(76 cm) with a '/a inch (0.64 cm) diameter. Inlet and exit pressure was 150
psig
(1.03 MPa gauge) controlled with a back pressure regulator. The catalysts were
all prepared as in Experiment 13 on 2 mm spheres with the appropriate metal
salts and type of alumina, with the exception that reduction was performed by
flowing H2 at 150°C instead of sodium citrate. The feed consisted of
1.6%
CHHP in cyclohexane, about 1 % K and 2 % A, and varying amounts of water
and acid impurities consisting of monobasic and dibasic acids which would be
to typical of those produced in cyclohexane oxidation such as adipic acid,
succinic
acid, formic acid, and hydroxycaproic acid, in approximately equal amounts.
Analyses were performed on CHHP, K, and A by gas chromatography.
Cyclohexane, CHHP, K, and A were obtained from E. I. du Pont de Nemours and
Company, Wilmington, DE. The K/A ratio obtained after conversion of
cyclohexylhydroperoxide over the catalyst was calculated using the equation:
(mols K in product) - (mols K in feed)
(mols A in product) - (mols A in feed)
TABLE V
Ex. Catalyst %CHHP Conv. K/A
23 1 %Au-0.1 %Pd/y-A120364 1.1
24 1 %Au-0.1 %Pt/y-A120364 1. I
1 %Au-0.1 %Ru/y-A120321 I .01
26 1 %Au-0.1 %Ni/Y-A120334 1.00
27 I %Au-0.1 %Co/y-A120345 1.02
28 1 %Au-0. I %Pd/a-A120367 I .91
29 1 %Au-0.1 %Pt/a-A120368 1.84
12
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CA 02362261 2001-08-07
TABLE VI
Gas, %CHHP Feed Exit Benzene,
Ex.Catalyst sccm Conv. IUA Benzene, ppm
ppm
30 !%Au-O.I%Pd/OC-A12030 60 I.63- _
3 1 %Au-0. L %Pd/ac-AI203N2, 62 1.74- -
! 75
32 1 %Au-0. ! %Pd/oc-AH2, 78 0.47- -
1203 75
33 1%Au-0.1%Pd/OC-AI203H2, 66 0.61- -
25
34 I %Au-0.1 %Pd/CC-AI203H2, 61 0.73- -
10
35 1%Au-0.1%Pd/y-A1203H2, 51 0.31- -
75
36 1%Au-0.1%Pd/aC-AI203H2, - - 5140 4828 .
75
37 1%Au-0.I%Pd/0G-AI2030 - - 5140 5140
38 1%Au-0.18%Pt/a-A12030 51 1.84- _
39 1%Au-0.18%Pt/oc.-A1203H2, 73 0.41- -
75
i3
AMENDED SbEET
N .r
