CA1064893A

CA1064893A - Catalyst composition and method for preparing the same

Info

Publication number: CA1064893A
Application number: CA232,563A
Authority: CA
Inventors: Elichi Asada; Toshio Takiguchi
Original assignee: Shoei Chemical Inc
Current assignee: Shoei Chemical Inc
Priority date: 1974-08-03
Filing date: 1975-07-30
Publication date: 1979-10-23
Also published as: DE2532254A1; AU8297875A; AU496822B2; DE2532254B2; DE2532254C3; FR2280430B1; JPS5018878B1; BR7504940A; FR2280430A1

Abstract

ABSTRACT OF THE DISCLOSURE

A catalyst comprising carbon fiber coated with at least one catalytic metal, such as the metals of group VIII of the Periodic Table or Zn, Cu, Ag, Au, Cr, Mg or Mn. The catalyst is prepared by submerging the carbon fiber, in the form of a filament, yarn or woven or non-woven textile, in a non-aqueous solution containing an organic compound of the metal or metals to be deposited on the fiber, drying and then pyrolyzing the compounds contained thereon. Optionally, the fiber may then be submerged in an aqueous solution containing an inorganic compound of the metal or metals, dried and pyrolyzed. The resultant cata-lyst composition is useful for a variety of chemical reactions, particularly those carried out in the gaseous state.

Description

~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 ::

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~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.
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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~

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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, :;:
., ~.
.~ .

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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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 ... ..

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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.

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. ;

.
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 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.

. .
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

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.

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.

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.

- --Carbon fiber woven textile made from polybenzimidazole ~80 m2/g) was submerged in a 5~ ethereal solution of di-~-cyclo ;`` ~ .' ...:: ::

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.

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.

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; 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.

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.

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.

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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.

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.

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.
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~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 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, ' ' ,:
. .

, ~(~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.

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.

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.

:- .: : : : , - :

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.

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. ~;

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.
.

--------__ 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

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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.

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. -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.

~)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.

' 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.

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

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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.

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 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.

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.

.
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.

.~.. , - ~ .

-, .

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.
~,' .

. 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.

-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.

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.

.

;~. : , . . : .
. . .

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.

:, 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.

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 - ~ , . . . . .

.:~: , . . .
., ~ , 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%). ~;

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. ;

A dioxane solution of adipic acid was treated at 60 atm.
.' .

.. . .. . .

: 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.

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.

.

; 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%

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:

: . :
.~ :
~ . . - . , 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.

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%.

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%.

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 -~`

. 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.

. =_ . . :
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.
' ~ . . . ~
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.

, ~ ~, .. . . ... . ... ....

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.

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 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 30Using the catalyst in Example 32, gaseous hydrogen was introduced at 25C at 1 atm., the solvent being acetic acid. The :, -, - - : .. : . . .

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.

. . ~

.
~, ~

.. .~ . - .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A catalyst comprising carbon fibre in a form chosen from the group consisting of a filament, yarn and woven or non-woven textile coated with at least one catalytic metal selected from the group consisting of Pt, Ru, Rh, Os, Ir, Fe, Co, Ni, Zn, Cu, Ag, Au, Cr, Mg, and Mn and alloys thereof.

2. A process for preparing a catalyst comprising carbon fibre in a form chosen from the group consisting of a filament, yarn and woven or non-woven textile as a carrier and at least one catalytically active metal layer, the metal being selected from the group consisting of Pt, Ru, Rh, Os, Ir, Fe, Co, Ni, Zn, Cu, Ag, Au, Cr, Mg, and Mn and alloys thereof, uniformly deposited on the carbon fibre which comprises submerging the fibre in one or more non-aqueous solutions containing one or a plurality of organic compounds of the metal or metals to be deposited on said fibre, drying the thus-treated fibre, heating the dried carbon fibre at a temperature sufficient to pyrolyze the com-pounds contained thereon, further submerging the obtained metal coated carbon fibre in at least one aqueous solution containing one or more inorganic compounds of said metal or metals, drying the thus-treated fibre, and heating the dried carbon fibre at a temperature sufficient to pyrolyze the compounds contained thereon.