Note: Descriptions are shown in the official language in which they were submitted.
~6~1~5a3
1 This in~ention relates to a novel method for the pre-
paration of highly improved catalyst compositions which effectively
catalyze reaction between an extensive combination of reactants in
either the liquid or gaseous phases. More particularly, this inven-
~ tion relates to a novel catalyst composition and a method for pre-
; paring the same, which comprises carbon fiber as a carrier and
transition metals uniformly deposited on the carrier by means of
a metal coating process wher~in non-aqueous solutions of appro-
priate organic derivatives of said metals are coated onto said
carrier, followed by the pyrolysis thereof.
This invention also relates to a modified procedure and
the products obtained thereby which comprise a multiple coating
~ of various catalytic compositions. This procedure involves the
- successive pyrolysis of the composition which has been initially ~ -;
coated on the carbon fiber carrier by the non-aqueous process, and
then submerged in an aqueous solution of inorganic salts of the
same or other kinds of metals.
The application and use of carbon fiber as a carrier has
` been known in the art because of i~s excellent resistance against
~ heat and its chemical stability. However, the use thereof has
involved difficulties in connection with the separation of the
products from the catalyst used as well as troublesome problems
; both in the recovery and re-activation of the inactivated catalyst.
These problems prompted the present inventors to find an improved
catalyst composition and method for preparing the same which would
solve most of the difficulties which have hitherto been e~perienced
with such carriers and which would fully meet the necessary re-
quirements of the catalyst art. An essentially disadvantageous
nature of carbon fiber in this connection lies in the fact that
carbon fiber initially has ver~ little affinity toward an aqueous
::
: :, ., -
~, . . . .
~06~ 3
1 system. This property, inherent to carbon fibers, immediately
conflicts with obtaining a uniform coating of metals as providad
by conventional aqueous procedures. This factor has definitely
limited the application of carbon fibers as a catalyst carrier in
spite of its excellent thermal and chemical stabilities.
Hence, the key feature of this invention directly relates
to the solution of the above-mentioned difficulty by a novel and
improved combination of techniques. Hence, the catalytic composi-
tion of the invention is prepared by submerging the carbon fiber
in a non-aqueous solution of suitable organic derivatives of the
metals whi¢h are to actually act as the catalyst, drying the fiber
and subsequently pyrolyzing it. By this procedure, a ca~alyst
;, composition composed of carbon fiber firmly and uniformly coated
with the given metal is unfailingly obtained. Furth~rmore, the
metal-coated fiber thus obtained is further treated analogously
with an aqueous solution of inorganic salts of the same or another
metal, dried and subsequently pyrolyzed to form a combined compo-
sition which i9 firmly coated with a thick metal layer.
.. . .
Accordingly, one of the object of the present invention
is to provide a catalyst composition comprising carbon fiber having
a coating of an appropriate metal which acts as a catalyst firmly
bonded thereon~
Another object of the invention is to provide a method
for preparing said catalyst composition.
A further object of the invention is to provide a catalyst
- composition comprising a multiple coating of various catalytic
metals on carbon fiber and a process for preparing the same.
A still further object of the invention is to provide a
novel catalyst composition and a method for preparing the same
3~ which overcomes the disadvantages and drawbacks of the prior art~
`:
393
These and other objects and advantages oE the present
invention will become apparent to those skilled in the art from
a consideration of the following specification and claims.
Carbon fibers to be employed in the present invention
may be obtained from polyacrylonitrile, cellulose, various pitches,
etc., and all such carbon fibers are equally applicable. An en-
tirely wide rang~ of dimensional forms of carbon fibers, including
filaments, yarn, woven or non-woven textiles, etc., can be employed
in the present invention.
-' 10
The catalytic metals to be deposited upon said carbon
fibers are selected from the metals of Group VIII of the Periodic
Table, such as platinum, palladium, ruthenium, rhodium, osmium,
iridium, iron, cobalt and nickel and other metals ~;uch as zincr
copper, silver, gold, chromium, magnesium and manganese. Mixtures
of such metals may be employed. Since the invention relates to
a catalyst composition, the primary requirement of such a metal
is that it be capable of acting as a catalyst in c~nnection with
any desired chemical reaction.
The organic derivativ s of the metals to be employed in
the present invention should fulfil the requirement that the
thermal decomposition thereof proceeds such that only the organic
component is cleaved therefrom to leave the elemental metal on ~ ;
the surface of the carbon fiber. Exemplary compounds which can
be used in the present invention include tetrakis (triphenyl-
. ~
phosphine) palladium, phenyl silver, benzyldibromogold, platinum
naphthenate, palladium naphthenate, ruthenium naphthenate, rhodium
naphthenate, iridium naphthenate, iron naphthenate, silver naphthe- -
nate, gold naphthenate, platinum rosinate, palladium rosinate,
ruthenium rosinate, rhodium rosinate, iridium rosinate, iron
3~ -
rosinate, silver rosinate, gold rosinate, palladium abietate,
:;:
.,
3 - -
~.
.~ .
1~4i 3~3
1 silver abietate, zinc stearate, silver stearate, zinc oleate,
cyclopentane ~arboxylic acid silver salt, cyclohexane carboxylic
acid silver salt, platinum dibutyldithiocarbamate, palladium
dibutyldithiocarbamate, copper clibutyldithiocarbamate, silver
dibutyldithiocarbamate, bis-cyclohexanone oxime-palladium
dichloride, bis-furfuraldoxime-palladium dichloride, bis-benz-
aldoxime-palladium dichloride, bis-methylethylketone, oxime-
palladium dichloride, bis-acetoxime-palladium dichloride, bis-
acetaldoxime~palladium dichloride, pentacarbonylruthenium, dode-
; 10 cacarbonyl-triruthenium, dihydro-ruthenium-tetracarbonyl, octa-
carbonyl-dirhodium, dodecacarbonyl-triosmium, dodecacarbonyl- -~
tetrairidium, nonacarbonyl-diiron, dodecacarbonyl~tetracobalt,
- tetracarbonyl-nickel, hexacarbonyl-chromium, actylpentacarbonyl-
manganese, methylpentacarbonyl manganese, ~-cyclopentadienyl-
trimethyl-platinum, ~-cyclopentadienyl-trimethyl-platinum, ~-allyl-
~-cyclopentadienyl-palladium, di-~-cyclopentadienyl-tetracarbonyl--
diruthenium, ~-cyclopentadienyl-dicarbonyl-ruthenium, ~-cyclo-
pentadienyl-dicarbonyl-rhodium, di-~-cyclopentadienyl-tetra-
carbonyl-diosmium, di-~-cyclopentadienyl-osmium, ferrocene,
20 ~-cyclopentadienyl-dicarbonyl-cobalt, di-~-cyclopentadienylcobalt
tribromide, di-~-cyclopentadienyl-nickel, ~-cyclopentadienyl-~-
allyl-nickel, dibenzene-chromium, di-~-cyclopentadienyl-manganese,
platinum tert-butyl mercaptide, palladium tert-butyl mercaptide,
copper tert-butyl mercaptide, silver tert-butyl mercaptide, gold
tert-butyl mercaptide, palladium benzimidazole-thiolate, silver ?
benzoimidazole-thiolate, gold benzimidazole-thiolate, palladium
benzothiazole-thiolate, silver benzothiazole-thiolate, and gold
benzothiazole-thiolate.
Liquid organic compounds which may be used as solvents
30 ~or these organic derivatives include organic solvents such as
benzene, toluene, xylene, halog~nated benzenes, tetralin, nitro-
benzene, etc.; alcoholic solvents such as isopropanol, tertiary-
. ;. . ~ ::: .
1o6;~l393
1 butanol, propylene glycol, benzyl alcohol, c~clohexanol, etc.;
ether-type solvents such as dialkyl ether, tetrahydrofuran,
dioxane, polyethylene glycol, etc:.; terpenoid compounds such as
terpineol, lavender oil, rosemary oil, etc.; ketone-type solvents
such as methyl ethyl ketone, methyl isobutyl ketone, etc.; esters
such as alkyl formates, alkyl acetates, etc.; aliphatic hydro-
carbons and their halogenated compounds such as chloroform, carbon
tetrachloride, ethylene dichloride, trichloroethylene, cyclohexane,
pentane, hexane, etc., and various miscellaneous solvents including
dimethylformamide, dimethylacetoamide, dimethyl sulfoxide, cyclo-
hexanone ! etc. Mixtures o~ these solvents may be employed as
appropriate.
The method by which the catalytic metals are applied on
the carbon fiber is described in the following. The carbon fiber
.; .
- as a carrier in the form of a filament, yarn or woven or non-woven
textile is submerged in a non-aqueous solution of the above-
mentioned organometallic derivatives, then dried and pyroly2ed.
This treatment is repeatedly carried out when required.
Further treatment of the above-obtained composition
with inorganic metal salts is carried out as follows. The compo-
sition is submerged in an aqueous solution of the inorganic salts,
then dried and subse~uently pyrolyzed. In some cases, the treat-
ment is accomplished under relatively mild conditions.
Inorganic salts employed in this invention include
palladium chloride, ammonium palladium chloride, chloroplatinic
acid, ruthenium chloride, iridium chlorider rhodium chloride,
silver nitrate, chloroauric acid, nickel sulfate, cobalt nitrate
and chromium nitrate. As to the concentration of the aqueous
solution of inorganic salt, no strict restriction thereon is ;
necessary. HoweverJ a concentration of about 3~ to 15% by weight
~ 5 ~
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33
generally gives satisfactory results. A too highly concentrated
solution thereoE tends to cause a poor uniformity of coating, and
too great of a dilu~ion may make it necessary to conduct the
treatment several times because of a deficient amount of metal
;- deposited upon the carbon fiber.
The chemical species of the catalytic layer formed in
connection with the invention depends upon the nature of the metal
used. For example, hardly oxidizable metals such as silver,
platinum, gold, palladium and the like form an elemental metallic
0 layer, whereas readily oxidizable metals such as manganese, nickel,
chromium and the like form an oxide layer upon pyrolysis of their
`;~ organic or inorganic derivatives. Hence, in the present applica-
A- tion, the term "metal" should be understood as including both
metals and metal oxides.
The use of a compound of a metal provides a layer of a
single kind of metal on the carbon fiber, whereas the use of a
. .
- mixture containing a plurality of different metal compounds forms
a multiplicity of metallic layers or alloys, depending upon the
conditions of pyrolysis and the nature of the metals employed.
Also, the thickness of the metallic layer is easily controlled by
a modification of the treatment conditions.
Xn accordance with the invention, the employment of
- soluble organometallic derivatives has been found to afford the
; ready and facile preparation of stock solutions, which provides
:
many advantages over previously known coating procedures.
The use of carbon fibers as carriers in the form of a
textile involves the significant advantage that, since a great
, . . variety of shapes of carrier is thus available, the catalyst
composition can be easily separated from the resulting products
and unconverted material, as compared with the procedures known
in the prior art where activated carbon particles are used as the
- 6 -
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: . .
:.', `. ' ' ' " ' :
~L0~i~893
1 carrier. This i5 especially txue when filaments, yarn or woven
or non-woven textiles are used as the carrier, the catalytic
; composition itself serving as the filtering agent. Moreover,
re-activation of the spent catalyst can be carried out very
readily. In fact, in some cases, re~activation can be performed
merely by washing the composition with appropriate solvents in
order to remove any products or by-products adsorbed on the surface
of the catalyst.
Because of the excellent thermal and chemical stability
of carbon fiber, the removal of adsorbed contaminants can be easily
carried out either by heat treatment at elevated temperatures or
by a chemical treatment such as oxidation, reduction or the use
; of a strong mineral acid or organic solvent. This is an obvious
advantageous characteristic of the present invention.
Another advantage of the invention is that reactions at
elevated temperatures can be performed with the use of conventional
autoclaves.
The following examples are given merely as illustrative
. . . .
of the present invention and are not to be considered as limiting.
Unless otherwise noted, the percentages recited therein are by
weight.
The reactions exemplified, particularly those carried
out in the gaseous phase at ordinary pressure with the catalyst
compositions of the invention, were performed with the use of
- the following apparatus in the manner described herein. The
composition prepared in the form of a textile material was formed
into round plates having a diameter of 3 to 5 cm, and then the
plates were laminated and bound with a stainless steel ring to
form a packed solid. The resulting solid material was perpendi-
cularly supported in the middle part of a Pyrex glass tube having
an inner diameter of 4 cm. The reaction t~e thus obtained was
_ 7 _
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:.. - -. . ~ ~
. . . . .
10~i4~ 3
1 used for the desired reactions. The reaction temperature was
controlled with the use of an appropriate electric furnace.
The mixture of gases was circulated at a rate of flow
of 0.02 - 0.08 m/min.
Liquid phase reactions were carried out using a conven-
tional reaction flask equipped with a refluxing condenser, and
the catalyst composition was placed at the center of the bottom
thereof.
EXAMPLE 1
Carbon fiber woven textile made from polyacrylonitrile
(250 m2/g) was submerged in a 5% chloroform solution of palladium
naphthenate and dried. It was then thermally treated for one hour
at 220C.
A similar treatment was repeated three times and, as a
- result, there was obtained a catalytic composition coated with ~.7%
- of palladium.
EXAMPLE ?
. f~Jy~r~l7y
. 3~ Carbon fiber non-woven textile made from~alcohol (PVA)
; 20 (80 m2/g) was immersed in a 10~ toluene solution of palladium tert-
butylmercaptide, dried and then heat-treated for one hour at 250C.
Treatment in this manner two times gave a catalytic -
composition with 7~ of palladium. ;
EXAMPLE 3
.
Carbon fiber woven textile made- from PVA (120 m2/g) was -
submerged in a 5% dimethylformamide solution of bis-acetaldoxime
- palladium dichloride, dried and subsequently pyrolyzed over a
period of 2 hours at 200C.
Treatment in this manner three times yielded a composi-
tion bearing 6~ of palladium.
~064~3
EXAMPLE 4
Carbon fiber woven t~xtile made from polyacrylonitrile
(160 m2/g) was submerged in a 3% chloroform solution of platinum
naphthenate and drLed. It was then thermally treated for one
hour at 270C.
A similar treatment was repeated three times and, as
a result, there was obtained a catalyst having 6~ of platin~n.
EXAMPLE 5
. .
Carbon fiber non-woven textile made from PVA (110 m2/g)
was submerged in a 3~ ethereal solution of ~-cyclopentadienyl-
trimethylplatinum and dried. The resulting material was then
thermally treated for one hour at 150C.
A similar treatment was repeated three times, and there
was obtained a catalyst having 7~ of platinum.
EXAMPLE 6 ~ :
Carbon fiber woven textile made from polyacrylonitrile
(120 m2/g) was submerged in a 5~ ethereal solution of phenyl
silver maintained at -50C in dry ice-acetone, and was then kept
at 50C in a nitrogen atmosphere for one hour.
This treatment was repeated three times to give a
catalyst containing 10~ silver.
EXAMPLE 7 ;
Carbon fiber woven textile made from PVA (170 m2/g) was
submerged in a 5~ chloroform solution of silver naphthenate and
dried, and then was thermally treated for one hour at 250C.
A similar treatment was repeated three times, and there
was obtained a catalyst having 7% of silverO
EXAMPLE 8
Carbon fiber woven textile made from PVA (120 m2/g) was
' '
_ g _
.... . . :. ~.
-
.
10~ 3
1 submerged in a 10% chloroform solution of silver naphthenate a~d
dried, and then it was thermally treated for 2 hours at 250C.
A similar treatment was repeated three times and, as a
result, there was ~btained a catalyst having 8~ of silver.
EXAMPLE 9
Carbon fiber woven textile made from polyacrylonitrile
(80 m /g) was submerged in a 3~ ethereal solution of dodecacarbonyl~
triruthenium and dried, and then was thermally treated for one
1 hour at 160C.
O
A similar treatment was repeated three times, and the
material was further treated for 3 hours at 300C with the result
~hat a catalyst having 5% of ruthenium oxide was obtained. ;
- EXAMPLE lO
~ Carbon fiber non-woven textile made from polyacrylo-
; nitrile (80 m2/g) was submerged in a 3% tetrahydrofuran solution
. of cyclopentadienyl-methyl-dicarbonyl-ruthenium. Ethanol was~ `-
:, .,
added to the above solution which was kept at 50C for one hour,
and then the composition was washed, dried and further treated
with a 10% hydrogen peroxide solution to give a composition coated - ;~
with 7% of ruthenium oxide.
EXAMPLE 11
Carbon fiber woven from pitch (120 m2/g) was submerged
in a 5~ ethereal solution of di-~-cyclopentadienyl-osmium and
dried. It was then thermally treated ~or one hour at 200 C.
A similar treatment was repeated three times, and there
was obtained a catalyst having 6~ of osmium.
EXAMPLE 12
- --
Carbon fiber woven textile made from polybenzimidazole
~80 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclo
;`` ~ .'
-- 10 --
...:: ::
1~6~1~93
pentadienyl-manganese, dried and then thermally treated for one
hour at 200C.
A similar treatment was repeated three times and there
was obtained a cat~lyst having 7~ of man~anese dioxide.
EXAMPLE 13
Carbon fiber woven textile made from cellulose (80 m2/g)
was submerged in a 10% ethereal solution of methyl-pentacarbonyl-
manganese, dried and then thermally treated for 2 hours at 200C.
A similar treatment was repeated three tlmes and, as
a result, there was obtained a catalyst having 11~ of manganese
dioxide.
EXAMPLE 14
-:
; Carbon fiber woven textile made from pitch (80 m2/g)
was submerged in a 5% tetrahydrofuran solution of ~-cyclopenta-
dienyl-~-allyl-nickel, dried and then thermally treated in a
hydrogen atmosphere at 100C for one hour.
This treatment was repeated two times, and there was
obtained a catalyst having 5% of nickel. -
EXAMPLE 15 .
Carbon fiber woven textile from pitch (80 m2/g) was
submerged in a 6% ethereal solution of tetracarbonyl-nickel and
dried. It was then thermally treated in a nitrogen atmosphere
at 130C for one hour. ~ -
: This treatment was repeated three times, and there was
obtained a catalyst having 5~ of nic]cel.
EXAMPLE 1 6
Carbon fiber woven textile made from PVA (120 m2/g) was
submerged in a 6% tetrahydrofuran solution of di~-cyclopentadienyl- `-
cobalt-tribromide, dried and then thermally treated in a nitrogen
atmosphere at 100C for one hour.
:,
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106~1!393
1 A similar treatment was repeated three times, and there
was obtained a catalyst having 5% of cobalt.
EXAMPLE 17
Carbon fiber woven textile made from polyacrylonitrile
(200 m~/g) was suhmerged in a 10% ethereal solution of dodeca-
carbonyl-tetracobalt and dried. It was then thermally treated in
a nitrogen atmosphere at 150C for one hour.
A similar treatment was repeated three times and, as
a xesult, there was obtained a catalyst containing 7~ of cobalt.
.
EXAMPLE 18
Carbon fiber woven textile from pitch (200 m2/g~ was
submerged in a 5% benzene solution of di(benzene)-chromium, dried
:~
and then tbermally treated in a nitrogen atmosphere at 300C for
one hour. There was obtained a catalyst having 1.5% of chromium.
EXAMPLE 19
Carbon fiber non-woven textile made from PVA (80 m2/g)
was submerged in a 10% trichlene solution of iridium naphthenate ~ -
20 and dried. It was then thermally treated for one hour at 300C. ;~
This treatment was repeated two times, and there wasobtained a catalyst containing 7% of iridium.
EXAMPLE 20
Carbon fiber non-woven textile made from PVA ~110 m2~g)
; was submerged in an 8% diisopropyl-ethereal solution of octa- -
carbonyl-dirhodium and dried. The resultant was then thermally
treated for one hour at 80C.
;~ A similar treatment was repeated three times, and there
was obtained a catalyst having 7% o~ rhodium.
. ~.
~ - 12 -
: ' :
~1 06~ 3
1 EX~MPLE 21
_ .
Carbon fiber non-woven textile made from cellulose
(80 m2/g) was submerged in a 5~ tetrahydrofuran solution of
acetyl-pentacarbonyl-manganese, ciried, and then thermally treated
for one hour at 100C.
~ similar treatment was repeated three times, and there
was obtained a catalyst having 6% of manganese dioxide.
The obtained composition was further submerged in a 5~
chloroform solution of palladium naphthenate, dried and then heated
at 250C for 30 minutes to give a composition coated with 1.5% of
palladium.
~- EXAMPLE 22
Carbon fiber woven textile made from polybenzimidazole
~80 m2~g) was submerged in a 5~ ethereal solution of nonacarbonyl-
diiron, dried and then thermally treated for one hour at 200~.
The above-treated textile was further submerged in a 5%
i
tetrahydrofuran solution of dodecacarbonyl-triruthenium, dried
and then thermally treated for one hour at 200C.
As a resultj there was obtained a catalyst having 7
- of metal.
~EXAMPLE 23
; Carbon fiber woven textile made from polyacrylonitrile
(80 m /g) was submerged in an ethereal solution containing 1.5%
of dodecacarbonyl-triruthenium and 1.5~ of octacarbonyl-dirhodium,
dried and then thermally treated for one hour at 160C.
After a similar treatment was repeated three times, the
above textile was thermally treated in air at 400C. As a result,
there was obtained a catalyst having 4% of metal.
'
- 13 - ~
11~6~ 3
I EXAMPLE 24
Carbon fiber woven textile made from polyacrylonitrile
(250 m2/g) was submerged in a chloroform solution containing 5~
of palladium naphthenate and 1% of ruthenium naphthenate, dried
and then thermally treated for 2 hours at 400C.
A similar treatment was repeated three times, and there
was obtained a catalyst having 4.0~ of metal.
. .
~ EXAMPLE 25
..
A carbon fiber woven textile made from polybenzimidazole
(80 m2/g) was submerged in an ethereal solution containing 5% of
di-~-cyclopentadienyl-manganese and 5% of nonacarbonyl-diiron,
and then dried and pyrolyzed at 350C for one hour.
This treatment was repeated three times, followed by
~aking in air at 400C for 3 hours, to produce a textile coated
with 8% by weight of metal. The resulting composition was sub-
sequently submerged in a chloroform solution containing 0.2~ of
palladium naphthenate and 0.2~ of platinum naphthenate, dried and
then pyrolyzed at 300C for 2 hours to give a catalyst having ~ ;
0.1% of platinum and palladium. ~
EXAMPLE 26 ~ -
... :. - :
A carbon fiber woven textile made from pitch ~80 m2/g) ;-~
was submerged in a 5% pentane solution of methyl-pentacarbonyl-
manganese and dried. It was then heated in a hydrogen àtmosphere '~
at 100C for one hour.
The treated textile was then submerged in a 5% aqueous
- solution of ruthenium chloride and pyrolyzed at 400C for 3 hours
to give a catalyst having 5% of metal.
EX~MPLE 27
--
- Carhon fiber woven textile made from cellulose (170 m2/g)
was submerged in a 5% chloroform solution of palladium naphthenate,
' ' ,:
. .
- 14 -
,
~(~6~393
1 dried and then thermally treated at 220C ~or one hour. There
was obtained a composition having 2% of palladium.
The composition obtained in the above procedure was
submerged in a formaldehyde-aqueous solution containing 30% of
PdC12 maintained at -10C. To the mixture was added 30~ potassium
hydroxide aqueous solution, and it was kept at 60C for 30 minutes.
The composition was washed, dried and subsequently treated at
100C for one hour to give a catalyst having 5% of palladium.
EXAMPLE 28
1 0
A carbon fiber woven textile made from polyacrylonitrile
~- (200 m2/g) was submerged in a 5% chloroform solution of palladi~
naphthenate, dried and thermally treated at 200C for 30 minutes
to give a composition containing 3.5~ of palladium.
The treated textile subsequently was submerged in an
aqueous solution consisting of 2% of ammonium palladium chloride
and small amounts of formic acid. The solution was heated up to
60C and a 30% aqueous solution of potassium hydroxide was added
thereto. After 30 minutes, the textile was dried, and, as a
result, there was obtained a catalyst having 5.5% of palladium.
EXAMPLE 29
A carbon fiber non-woven textile made from polyacrylo-
nitrile (120 m2/g) was submerged in a 5% chloroform solution of
palladium naphthenate, dried and then thermally treated at 230C
for 2 hours.
The obtained composition was submerged in an aqueous
solution containing 20% sodium sorbate, a small amount of sodium
hydroxide and palladium chloride dissolved in dilute hydrochloric
acid. The whole mixture was heated up to 60C, dried and finally
treated with hydrogen at 80C for 2 hours to give a catalyst having
6% palladium.
- 15 -
:- .: : : : , - :
33
1 EXAMPLE 30
Carbon fiber non-woven textile made from PVA (170 m2/g)
was submer~ed in a 5% toluene solution of platinum dibutyldithio-
carbamate, dried and then thermally treated for 2 hours at 250C.
The above-treated textile was further submerged in an
; .
aqueous solution of chloroplatinic acid and was alkalized by
- adding NaCO3 thereto. After the addition of hydrazine, the
mixture was heated to 60C and allowed to stand for one hour and
dried. A catalyst having 5% platinum was obtained.
EXAMPLE 31
A carbon fiber woven textile made from PVA (80 m2/g) was
submerged in a 5% tetrahydrofuran solution of ~~allyl-~~cyclo-
pentadienyl platinum, dried and then thermally treated at 130C
for one hour. The treated textile was then submerged in a S0
aqueous solution of hexachloroplatinic acid, and 40% formalin was
added to the solution. To the resulting mixture maintained at
0C, a 30% aqueous solution of sodium hydroxide was added, and
the mixture was allowed to stand for 12 hours. Washing the
produced composition with water and then drying at 50C gave a ~ ~
catalyst having 4~ of platinum. ~;
EXAMPLE 32
Carbon fiber non~woven textile made from PVA (80 m2/g)
was subme~ged in a 3% toluene solution of platinum tert-butyl
mercaptide, dried and then thermally treated for one hour at
200C~ The composition thus obtained was further treated similarly
as described in the latter part of Example 31, and there was
obtained a catalyst containing 5~ of platinum.
.
EXAMPLE 33
--------__
Carbon fiber woven textile made from pitch (120 m2/g)
was submerged in an 8~ ethereal solution of platinum tert-butyl-
mercaptide, dried and then thermally treated for one hour at 200C
,:
.; ............. ~ . . ............................ ..
.-:: -: . . . .
-: .
iO~4893
to give a composition having l~ of platin~n. Furthexmore, the
above textile was submerged in a 50~ aqueous solution of chloro-
platinic acid, and 40~ of formalin was added to the solution.
To the resulting mixture maintained at 0C, a 30%
aqueous solution of sodium hydroxide was added, and the mixture
was allowed to stand for 12 hours. Washing the treated composition
with water and drying at 50C gave a catalyst having 4% of platinum.
EXAMPLE 34
Carbon fiber woven textile from PV~ (120 m2/g) was sub-
merged in a 2~ chloroform solution of gold naphthenate, dried and
then thermally treated for one hour at 240C to give a catalyst
composition having l~ of gold.
The above-treated textile was submerged in an aqueous
solution containing ammonium palladium chloride and formic acid,
and then a 20% aqueous solution of potassium hydroxide was added
to the solution. The resulting mixture was maintained at 60C
for one hour, dried at 50C and, as a result, there was obtained
a catalyst having 4% of palladium. -
EXAMPLE 35
Caxbon fiber non-woven textile from PVA (80 m2/g) was
submerged in a 2% chloroform solution of gold naphthenate and
dried. It was then thermally treated for one hour at 230C. By
this treatment, the textile obtained contained 1% of gold.
The ~bove-treated textile was submerged in an aqueous
solution containing 30% of chloroplatinic acid and 30% of formalin.
To the resulting mixture maintained at 0C a 50% sodium hydroxide
solution was added and the mixture was allowed to stand for 12
hours. Washing the treated textile with water accompanied by
drying at 50C gave a catalyst having 7% of platinum.
- 17 -
~)648~3
~ EXAMPLE 36_
-~ Carbon fiber woven textile from PVA ~120 m2/g) was sub-
merged in a 10~ chloroform solution of gold naphthenate, dried
and then thermally treated for 2 hours at 240C. By this treat-
ment, the textile was coated with 1% of gold.
The textile was further submerged in an aqueous solution
consisting of 2~ of ammonium palladium chloride and formic acid.
To the mixture maintained at 60Cj a 30~ aqueous solution of
;~ potassium hydroxide was added and, after 30 minutes, it was washed
with water and dried at 50C. The catalyst obtained contained 66
of palladium.
EXAMPLE 37
' A carbon fiber woven textile made from PVA (130 m2/g)
was submerged in a 5% chloroform solution of silver naphthenate
and dried. It was then thermally treated for one hour at 200C. ~ ~-
The above-treated textile was submerged in an aqueous -
solution containing 30% of silver nitrate and 10% of sodi~
hydroxide, and a 30% aqueous solution of hydrogen peroxide was
further added slowly thereto. The mixture was kept at 30C for
one hour, dried at 50C and a catalyst having 10% of silver was
obtained.
- EXAMPLE 38
Carbon fiber woven textile from pitch ~80 m2/g) was
- submerged in a 5% ethereal solution of di-~-cyclopentadienyl~-
tetracarbonyl-diosmium and dried. It was then thermally treated
in a nitrogen atmosphere at 100C for 2 hours. By means of this
treatment, the above textile was coated with 2% of osmium. ~-
.
The textile was then submerged in an aqueous solution
; 30 containing 2% of ammonium palladium chloride and formic acld. A
' .
- 18 -
.,. - . ~:
8~3
1 30% aqueous solution of potassium hydroxide was added thereto and
the solution was heated up to 60C. After 30 minutes, washing with
water and drying at 50C gave a catalyst containing 5~ palladium.
EXAMPLE 39
Carbon fiber woven textile made from PVA (120 m2/g) was
submerged in a 10% e-thereal solution of di-~-cyclopentadienyl-
nickel, dried and then thermally treated in a nitrogen atmosphere
at 150C for 2 hours. By this treatment, the textile was coated
with 2% of nickel.
The textile was furthermore submerged in an aqueous
solution containing 30% of nickel sulfate, 10% of sodi~n hypo-
phosphite and lO~i of sodium acetate, allowed to stand for 30
minutes at 98-99C, and then dried. The treated textile was
; finally subjected to a hydrogen atmosphere at 250C for 2 hours
and, as a result, a catalyst having 5% of nickel was obtained.
EX~4PLE 4D
A carbon fiber woven textile made from pitch (80 m2/g)
was submerged in a 6~i tetrahydrofuran solution of ~-cyclopenta-
- 20 dienyl-~-allyl nickel and dried. It was then thermally treated `
under nitrogen at 130C for 2 hours. By this treatment, the
textile was coated with 2~i of nickel.
Ater a lO~i aqueous solution of sodium hypophosphite
was added to the 30~ aqueous solution of nickel sulfate, the
treated textile was submerged therein, and it was maintained at
`-98-99C for 30 minutes. After washing with water and drying,
the treated textile was finally treated in a hydro~en atmosphere
at 250C for 2 hours, and a catalyst having 6% of nickel was
obtained.
~ 30
: ':
~ - 19 - .,
; . - . . ~ ,. ,,:
1~6413~3
EXAMPLE 41
A carbon fiber woven textile made from PVA (120 m2/y)
was submerged in a 7~ tetrahydrofuran solution of ~-cyclopenta-
dienyl-dicarbonyl-cobalt and dried. It was then thermally treated
under nitrogen at 130C for 2 hours. By this treatment, the
textile was coated with 1% of cobalt.
The above-treated was further submerged in a 30% aqueous
solution of cobalt nitrate, and a 4~ aqueous solution of sodium
hydrogen carbonate was added thereto. The solution was maintained
at 80C for 2 hours.
After washing with water and drying, the textile was
finally treated in a hydrogen atmosphere at ~70C for 2-3 hours,
and a catalyst having 4% of cobalt was obtained.
EXAMPLE 42
A carbon fiber woven textile made from polyacrylonitrile
- (80 m2/g) was submerged in a 10% ethereal solution of dodeca-
carbonyl-tetracobalt and dried. It was then thermally treated in
l a nitrogen atmosphere at 160C for one hour. Subsequently, the
'! 20 above-treated textile was submerged in a 30% a~ueous solution of
cobalt nitrate. A 4% aqueous solution of sodium hydrogen carbonate
was added thereto, and the solution was heated at 80C for 2 hours.
; Aftex washing and drying, the treated textile was final]y
treated in a hydrogen atmosphere at 270C for 2-3 hours, and a
catalyst having 6% of cobalt was obtained.
EXAMPLE 43
.
Carbon fiber woven textile made from pitch (160 m2/g)
was submerged in an 8% tetrahydrofuran solution of di-~-cyclo- ;
pentadienyl-chromium and dried. It was then thermally treated
in a nitrogen atmosphere at 180C for 2 hours. By this treatment,
the above textile was coated with 2% of chromium.
- 20 -
.~.. , - ~ .
-, .
L8~3
The treated textile was furthermore submerged in an
aqueous solution containing a 1 normal concentration of chromium
nitrate and a 1 normal concentratlon of ammonium nitrate, R 1
normal concentration of aqueous ammonium was added thereto, and
the solution was stirred at 80-90C. After washing and drying,
the treated textile was subjected to a hydrogen atmosphere at
250C for 3 hours, and a catalyst having 5% of chromium was
obtained.
~,' .
EXAMPLE 44
. 1 0
Carbon fiber woven textile made from polyacrylonitrile
(200 m /g) was submerged in a 10% chloroform solution of ruthenium
rosinate, dried and then thermally treated for one hour at 150C.
Subsequently, the above-treated textile was submerged in a 10%
aqueous solution of ruthenium chloride and was thermally treated
at 400C. As a result, a catalyst having 3% of ruthenium oxide
was obtained.
EXAMPLE 45
-
Carbon fiber non-woven textile from cellulose (80 m2/g)
was submerged in a 5~ tatrahydrofuran solution of palladium rosinate
and dried. It was then thermally treated for one hour at 300C.
The above-treated textile was further submerged in a 5%
aqueous soiution of ruthenium chloride, dried and thermally treated
at 400 C for 30 minutes. A catalyst having 1.5% of metal was
obtained.
EXAMPLE 46
A carbon fiber woven textile from pitch (120 m2/y) was
submerged in a 5~ cyclohexanone solution of dodecacarbonyl-tri-
ruthenium and dried. It was then thermally treated for one hourat 150C.
.
- 21 -
;~. : , . . : .
. . .
1~6~893
a The abova-treated tex-tile was further submerged in a
5% aqueous solution of rhodium chloride and thermally treated at
300C for one hour. A catalyst containing 2% of metal was
obtained.
:,
EXAMPLE 47
Carbon fiber non-woven textile made from cellulose
(80 m /g~ was submerged in a 0.5~ chloroform solution of palladium
naphthenate and dried. It was then thermally treated for 30
minutes at 250C. By this treatment, the above non~woven textile
; was coated with 0.1% of palladium.
The textile was further submerged in an aqueous solution
containing 10% of ruthenium chloride and 20~ of silver nitrate,
dried and thermally treated at 500C for one hour. The latter
treatment was repeated three times, and a catalyst haviny 5% of
, ruthenium and silver was obtained.
.`' ' ~ . .
` EXAMPLE 48
.
A mixture of circulating gases composed of CO (15%),
2 (17~) and N2 (68~) was treated with the catalyst obtained in
Example 21 at 100C with a flow rate of 0.08 m3/min. and under
1 atmosphere. Analysis of the resulting mixture disclosed a
.,
98.8% conversion of CO into CO2.
EXAMPLE 49
The catalyst obtained in Example 21 was used with a
` circulating gaseous mixture composed of CO (8~), SO2 (10%~, 2
I (20~) and N2 (62~) at 40C and 1 atmosphere with a flow rate of
- 0.06 m3/min.
`¦ The convarsion rate of CO and SO2 were as follows.
, 30
~i
- 22 -
- ~ , . . . . .
.:~: , . . .
., ~ ,
1~ ~ 4~ ~
1 at 40C CO : 93.3%
SO2: 96.7~
at 100C CO : 98.9%
SO2: 99.4%
EXAMPLE SO
The catalyst obtained in Example 2 was treated in a
hydrogen stream at 80C for 2 hours, and then it was used in a
circulating methanolic solution of quinone at room tempera~ure,
the flow rate thereof being 30 l/min. After 3 hours, hydroquinone
was obtained a~ a conversion rate of Z2%~ Then, the temperature
~ was raised to 60C to prevent the deposition of hydroquinone.
After further reaction was conducted for an additional
6 hours, hydroquinone was obtained with a final conversion rate
of 97.4~.
.~' . .
; EXAMPLE 51
., . . -- . .
The catalyst obtained in Example 14 was put in a 500;cc.
flask equipped with a H2 inlet tube and a refluxing condenser.
Gaseous hydrogen was introduced to an ethanolic solution of benzo-
nitrile in the flask at 35C for 6 hours to give both benzylamine
(64~) and diben2ylamine (12%). ~;
FXAMPLE 52
A dioxane solution of glycolic acid was reduced at 47 ~` ; -
atm. at 145C for 30 minutes in an autoclave with the use of the
catalyst obtained in Example 10~ From this reaction, ethylene
glycol was obtained with a conversion rate of 44~. Under similar
conditions, a conversion rate of 66% was obtained undex a pressure
` of 78 atm. ;
EXAMPLE 53
A dioxane solution of adipic acid was treated at 60 atm.
.' .
- 23 -
.. . .. . .
: l.t;3 ~48~3
1 at 176C for one hour by a procedure analogous to that described
in Example 52. From this reaction, hexamethylene glycol wa~
obtained with a 60% conversion rate.
EXAMPLE 54
An ethanolic solution of benzaldehyda was reduced at
25C at 1 atm. with the use of the catalyst obtained in Example 1.
After reduction with hydrogen for half an hour~ benzyl alcohol was
obtained in an 87% conversion rate~ A further reduction for 6
hours gave toluene in an 88% yielcl.
.
EXAMPLE 55
; In a mixture composed of 10% ethylene and 90% nitrogen,
the ratalyst obtained in Example 37 was maintained at 250C for
one hour. Then, the catalyst was used for the preparation of
ethylene oxide under the following conditions:
reaction pressure13.5 kg/cm2
reaction temperature 265C
: flow rate 0.05 m3/min.
- ~0 reaction time 200 hours
.
Composition of circulated gases:
ethylene 6.3%
O
C2 8%
N2 78
The conversion rate to ethylene oxide was 88.4%;
C2H4O/hr/Ag(g) = 31.6, which is higher by 4.3% than the 27.3%
mean value previously accepted for the alumina-silver catalyst. ; `~
j EX~MPLE 56
A mixture composèd of:
- 24 -
: . :
.~ :
~ . . - . ,
1 propylene 10%
2 13.5%
~2 8.5
N2 68%
was similarly treated as in Example 55 at 375C. Propylene oxide
was obtained therefrom with a maximum yield of 91.3% C3H6O/hr/Ag(g)=
33.4.
EXAMPLE 57
A circulating gas mixture containing methanol (20%~,
oxygen (10%) and nitrogen (70%) was treated using the catalyst
--- obtained in Example 37 at 340C and 7~5 kg/cm2 for 160 hours,
the flow rate of the mixed gas being 0.08 m3/min. From this run,
formaldehyde HCHO(g)/hr/Ag(g~=26.3, was obtained with a selectivity
of 99.5~ and a conversion rate of 58.4%.
These values are slightly higher in comparison with the
case where Ag-A12O3 catalyst was used with a selectivity of 99.5%
and a conversion rate of 51.6%.
EXAMPLE 58
A gaseous mixture composed of N2 (70%)' 2 (10%) and
ethyl alcohol (20%) was treated in a similar manner under similar
reaction conditions as in Example 57 to give acetaldehyde in a
21.6% conversion rate with a selectivity of 84.7%.
EXAMPLE 59
The air oxidation of benzene was conducted with the use
of the catalyst obtained in Example 43 in a circular reaction
system.
gas composition: C~H6: 10%
air: 90%
reaction temperature 370C -~`
- 25 -
. 10~;4B93
reaction pressure 1 kg/cm2
flow rat~ 0.06 m3/min.
,
From this system, maleic anhydride was obtained with a
47% conversion rate after 12 hours, and in an 84% conversion rate
after 60 hours.
EXAMPLE 60
. =_ . . :
The catalyst obtained in Example 38 was used for the
reaction of a gaseous mixture composed of NO (24~), 2 (20%) and
N2 (56~) having a flow rate of 0.06 m3/min~ at a reaction pressure
of 3.5 kg/cm2. The conversion rate ~rom NO to NO2 was as follows:
after 6 hours: 64% at 40C
7~ at 60C
96.6% at 66C
91% at 80C
88% at 100C
86% at 120C ~ ~
63% at 160C ~ -
., . :~ ,
In the case where a catalyst containing silica and
alumina as the carrier was used in a similar reaction, a maximum
conversion rate of 96% is attained at 270-300C. Hence, the use
of the composition of the invention attains a higher conversion
rate at lower temperatures as compared with the prior art
techniques.
'
EXAMPLE 61
~ . . . ~
The catalyst obtained in Example 31 is put in a 500 cc.
1ask equipped with a hydrogen inlet tube and a refluxing condenser.
To an acetic acid solution of phenol in the flask, gaseous hydrogen
was introduced at 40C. After 4 hours of reaction, cyclohexanol
(72~) and cyclohexane (16%) were obtained.
, ~ ~, .. . . ... . ... ....
1 EXAMPLE 62
An acetic acid solution of benzoic acid was reduced at
20C for 3 hours by a procedure analogous to that described in
Example 61 to produce cyclohexane carboxylic acid in an 88~ yield.
EXAMPLE 63
The catalyst obtained in Example 30 was used for the
reduction of certain aromatic organic compounds with the use of
tetrahydrofuran as a solvent at 5 atm. in an autoclave. The
results were as follows:
1. biphenyl phenylcyclohexanein 82~ yield (60C, 1 hr)
2. hydroquinone 1,4-cyclohexane-diolin 66% yield (50C, 1 hr)
3. ~-naphthol 1,2,3,4-tetrahydro-2-in 62% yield (50C~ 1 hr)
- naphthol
EXAMPLE 6 4
The catalyst obtained in Example 38 was made up into a
solid having a thickness of 1 cm. The obtained solid was used in
connection with the treatment of a gaseous mixture comprising C0,
H2S, N0 and S02 at 40C for over 20 hours. The rate of flow was
maintained at 0.05 m3/~in. The decrease in pressure owing to
transit through the catalytic textile was 0.2%.
The decrease of volume percentage of the components was
as follows~
; C0 : from11.6 to 0.3 ;
H2S: from7.3 to 0.9
N0 : from6.8 to 0.2
. . .
S02: from3.8 to 1.6
EXAMPLE 65
30Using the catalyst in Example 32, gaseous hydrogen was
introduced at 25C at 1 atm., the solvent being acetic acid. The
- 27 -
:, -, - - : .. : . . .
393
1 conversion rates using the following compounds in this procedure
were as follows:
,
After 2 hours:
1. from toluene hexahydrotoluene (67~)
; 2. from benzoic acid hexahydrobenzoic acid (76~)
3. from naphthalene decalin (88%)
4. from pyridine piperidine ~97~)
: .
5. from benzene cyclohexane ~65%~
tO 6. from quinoline decahydroquinoline (59%)
7. from cinnamic acid hydrocinnamic acid (44~
,
Hence, it can readily be seen from the above description
that the present invention provides a catalyst composition utiliz-
ing carbon fiber as a carrier wherein an organometallic compound,
including ~-bonded organometallic compounds, of a catalytic metal
is coated on the fiber, the thus-treated fiber is dried, and then
it is heated at a temperature sufficient to pyrolyze the compound
contained thereon. Plural coatings of the same or different metals
may be employed, if desired.
The invention being thus described, it will be obvious
that the same may be varied in many ways. Such variations are
not to be regarded as a departure from the spirit and scope of
the invention, and all such modifications are intended to be
included within the scope of the following claims.
. . ~
.
~, ~
- 28
.. .~ . - .
