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US2895819A - Method for preparing a catalytic metal foam and use thereof - Google Patents

Method for preparing a catalytic metal foam and use thereof Download PDF

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Publication number
US2895819A
US2895819A US681435A US68143557A US2895819A US 2895819 A US2895819 A US 2895819A US 681435 A US681435 A US 681435A US 68143557 A US68143557 A US 68143557A US 2895819 A US2895819 A US 2895819A
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Prior art keywords
metal
foam
alloy
catalytic
preparing
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US681435A
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Fiedler William Stuart
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Bjorksten Research Laboratories Inc
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Bjorksten Research Laboratories Inc
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/08—Alloys with open or closed pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J25/00—Catalysts of the Raney type
    • B01J25/02—Raney nickel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/63—Processes of molding porous blocks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12479—Porous [e.g., foamed, spongy, cracked, etc.]

Definitions

  • This invention relates to a method for preparing a catalytic metal foam and to a method for utilizing said material.
  • a catalytic material in the form of a metal sponge has been prepared by leaching a 50% aluminum- 50% nickel alloy with a 25% warm caustic soda solution.
  • the sponge thus obtained is a black pyrophoric material dispersed in a solution which when used as a catalyst provides a large surface area compared to that of catalysts previously used.
  • the present invention provides a method for preparing a catalytic metal foam which due its structure provides a much greater surface area than the aforementioned catalytic metal sponge.
  • the method of the present invention consists of melting a metal alloy consisting of nickel and a metal or metals which can be easily removed from said alloy by leaching, vaporizing or other suitable means, causing a stream of molten metal alloy to flow into a pool of metal alloy, introducing into the interior of the pool a material adapted to effect foaming of the alloy, heating the body of molten metal alloy and material adapted to effect foaming to form a body of molten metal containing discrete cellular bubbles distributed therethrough, cooling the body and then treating said body in a manner as to remove the removable metal or metals from the alloy to provide a catalytic metal foam.
  • the catalytic metal foam thus treated may then be utilized :to catalyze an organic reaction by the addition of said foam thereinto.
  • the catalytic metal foam of the invention is utilized as a catalyst for hydrogenation and other reactions in which a nickel catalyst is suitable.
  • metal alloy foam I mean a body consisting of gas containing discrete cells distributed in a metal matrix in a generally uniform manner, each cell being entirely enclosed and generally being not connected to any neighboring cell.
  • Metal foam should not be confused with metal sponge which consists of interconnected cells which communicate in a metal matrix.
  • catalytic metal foam I mean a body of porous catalytic nickel which before treatment was a nickelmetal alloy foam.
  • An object of the present invention is a method for catalyzing an organic reaction utilizing a metal foam catalyst.
  • Another object is a method for preparing a metal foam catalyst.
  • Another object is a method for hydrogenating an organic solution by immersing in an organic solution a metal foam catalyst.
  • Another object is a new and novel catalytic material.
  • the invention is adapted to use a metal alloy foam consisting of nickel and a metal or metals which may be 2,895,819 Patented July 21, 1959 2 easily removed from the alloy.
  • Metals which may be used in the alloy with nickel include aluminum, magnesium, zinc and cadmium.
  • the alloys preferred for use in the method of the invention include those having a substantial temperature difference, preferably of 200 to 400 C., between the solid phase temperature and the liquid phase temperarture as shown in phase diagrams.
  • a wide temperature difference is not always necessary.
  • metal wherein its solid phase may be caused to predominate to cause decreased fluidity; the metal being foamed at the .temperature at which this occurs, such temperature being between the solid and liquidphase temperatures.
  • the metal alloy to be usedin preparing catalytic metal foam may be melted in a suitable furnace and then may be poured into a'heated vessel where the material adapted to effect foaming may-be added.
  • Metal alloy foam suitable for use in preparing catalytic metal foam maybe produced continuously or in a batch process.
  • the metal is first heated in a furnace or vessel until the metal is melted and is at a temperature desirable for foaming.
  • the metal is poured into a heated vessel in which foaming is to take place.
  • a material adapted to effect foaming is then fed into the molten metal until sufficient material has been added to produce a low density foam. The material is immediately exposed to additional heat to cause additional expansion of the cells within the metal alloy foam.
  • the foam thus formed may be cooled by quenching with water and the metal alloy foam may then be treated by using a warm caustic soda solution to cause removal of the easily removable metal to provide a catalytic metal foam or the metal alloy foam maybe heated to a temperature at which the metal adapted to be easily removed from the metal alloy foam is vaporized and may then be removed by subjecting to a predetermined amount of vacuum or may be treated by any suitable means which produces the desired catalytic metal foam.
  • the foam may be .continuouslytreated.
  • the invention also relates to a method for adding to an organic reaction, a catalytic metal foam formed by the aforedescribed method to catalyze said reaction.
  • a catalytic metal foam formed by the aforedescribed method to catalyze said reaction.
  • a 28% nickel-72% aluminum alloy foam may be used to prepare a metal alloy foam by melting and adding a material adapted to effect foaming.
  • the metal alloy foam thus produced may then be leached with a 25% warm caustic soda solution.
  • a portion of the resultant material may then be added in the form of a block to an organic solution such as benzene to cause hydrogenation of said solution.
  • Another organic reaction which may be catalyzed by the product of my method is benzoylmethionine which is converted to benzoylaminobutyric acid.
  • a catalytic metal foam maybe formed from a nickelzinc alloy foam.
  • the alloy foam is prepared by melting the alloy, adding a foaming agent, heating and then cooling.
  • the resultant foam is then heated to a temperature below the melting temperature of the alloy and above the vaporization point of zinc so that upon subjection to a small amount of vacuum, the zinc vapors can be easily removed thusproviding a nickel catalytic foam.
  • the resultant catalytic foam may then be used for the hydrogenation of vegetable 'oils.
  • Example 1 v 784 g. aluminumxis heatedto 900 C. in a steel crucible, and at that temperature 305 g. nickel are added and allowed to dissolve.
  • the alloy is stirred and allowed to cool to 854 C. at which time a foaming agent (20% zirconium hydride) is stirred into the mixture with an iron rod.
  • the resultant body is cooled by quenching with water.
  • the cooled metal alloy foam is then leached with a 25% caustic soda solution causing removal of aluminum.
  • a /2 g. sample of the aforementioned foam is'then added to a container containing 4 liters of hexene and is subjected to 1500 lbs./sq. in. pressure provided by hydrogen.
  • the system is allowed to run in this manner for 8 hours at which time 3.9 liters of hexane are obtained.
  • Example 2 800 g. zinc are placed in a pressed steel crucible and heated to 950 C. 200 g. of'm'ckel are then added and allowed to dissolve. The alloy is stirred well and then 3.38 g. of zirconium hydride suspended in zinc powder are added and stirred therein using an ironrod. The foam is formed immediately and is cooled. The foam is then put in a pressure chamber and the foam subjected to a temperature of 900 C. and the pressure reduced from 760 mm. pressure to .1 mm. pressure of mercury to remove the zinc from the alloy. After two hours, the foam is' removed and provides a catalytic nickel foam. A /2 g.
  • a method for preparing a catalytic metal foam comprising providing a molten pool of metal alloy consisting of a catalytic metal and at least one metal adapted to be easily removed from said metal alloy after foaming; introducing into the interior of the pool, a material adapted to effect foaming of thealloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, treating said body to remove said metal adapted to be easily removed body to remove said metal adapted to be easily removed from the metal alloy foam to provide catalytic metal foam.
  • a method for preparing a catalytic metal foam comprising providing a molten pool of nickel-aluminum alloy; introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, leaching said body to remove the aluminum from the nickel-aluminum foam to provide catalytic nickel foam.
  • a method for preparing a catalytic metal foam comprising providing a molten pool of metal alloy consisting of a catalytic metal and at least One metal adapted to be easily removed from said metal alloy after foaming, introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, heating said body to a temperature sufiiciently high to vaporize said metal adapted to be easily removed, subjecting said body to suflicient vacuum to remove said metal adapted to be easily removed thus providing a catalytic metal foam.
  • a method for preparing a catalytic metal foam comprising providing a molten pool of a nickel-zinc alloy, introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, heating said body to a temperature sufficiently high to vaporize the zinc contained in the alloy, subjecting said body to sufficient vacuum to remove said zinc thus providing a catalytic nickel foam.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Catalysts (AREA)

Description

United States Patent METHOD FOR PREPARING A CATALYTIC METAL FOAM AND USE THEREOF William Stuart Fiedler, Madison, Wis., assignor to Bjorksten Research Laboratories, Inc., Fitchburg, Wis., a corporation of Illinois N0 Drawing. Application September 3, 1957 Serial No. 681,435
5 Claims. (Cl. 75 -20) This invention relates to a method for preparing a catalytic metal foam and to a method for utilizing said material.
Heretofore, a catalytic material in the form of a metal sponge has been prepared by leaching a 50% aluminum- 50% nickel alloy with a 25% warm caustic soda solution. The sponge thus obtained is a black pyrophoric material dispersed in a solution which when used as a catalyst provides a large surface area compared to that of catalysts previously used.
The present invention provides a method for preparing a catalytic metal foam which due its structure provides a much greater surface area than the aforementioned catalytic metal sponge.
The method of the present invention consists of melting a metal alloy consisting of nickel and a metal or metals which can be easily removed from said alloy by leaching, vaporizing or other suitable means, causing a stream of molten metal alloy to flow into a pool of metal alloy, introducing into the interior of the pool a material adapted to effect foaming of the alloy, heating the body of molten metal alloy and material adapted to effect foaming to form a body of molten metal containing discrete cellular bubbles distributed therethrough, cooling the body and then treating said body in a manner as to remove the removable metal or metals from the alloy to provide a catalytic metal foam.
The catalytic metal foam thus treated may then be utilized :to catalyze an organic reaction by the addition of said foam thereinto. The catalytic metal foam of the invention is utilized as a catalyst for hydrogenation and other reactions in which a nickel catalyst is suitable.
By metal alloy foam I mean a body consisting of gas containing discrete cells distributed in a metal matrix in a generally uniform manner, each cell being entirely enclosed and generally being not connected to any neighboring cell. Metal foam should not be confused with metal sponge which consists of interconnected cells which communicate in a metal matrix.
By catalytic metal foam, I mean a body of porous catalytic nickel which before treatment was a nickelmetal alloy foam.
An object of the present invention is a method for catalyzing an organic reaction utilizing a metal foam catalyst.
Another object is a method for preparing a metal foam catalyst.
Another object is a method for hydrogenating an organic solution by immersing in an organic solution a metal foam catalyst.
Another object is a new and novel catalytic material.
Further objects will become apparent from the following detailed description in which it is my intention to illustrate the applicability of the invention without thereby limiting its scope to less than that of all those equivalents which will be apparent to one skilled in the art.
The invention is adapted to use a metal alloy foam consisting of nickel and a metal or metals which may be 2,895,819 Patented July 21, 1959 2 easily removed from the alloy. Metals which may be used in the alloy with nickel include aluminum, magnesium, zinc and cadmium.
The alloys preferred for use in the method of the invention include those having a substantial temperature difference, preferably of 200 to 400 C., between the solid phase temperature and the liquid phase temperarture as shown in phase diagrams. However, a wide temperature difference is not always necessary. In order to obtain a superior foam 'used in preparing catalytic metal foam,'it is helpful to utilize metal wherein its solid phase may be caused to predominate to cause decreased fluidity; the metal being foamed at the .temperature at which this occurs, such temperature being between the solid and liquidphase temperatures.
While the particular nature of the material adapted to effect foamingand the apparatus for introducing the mate- -rial adapted to effect foaming are not a part of the invention, it may be mentioned that suitable materials and apparatus are .disclosed in Serial No. 637,735, filed February 1, 1957. An example of a suitable material is a hydride-containing metal powder.
The metal alloy to be usedin preparing catalytic metal foam may be melted in a suitable furnace and then may be poured into a'heated vessel where the material adapted to effect foaming may-be added.
Metal alloy foam suitable for use in preparing catalytic metal foam maybe produced continuously or in a batch process. For preparing catalytic metal foam in a batch process, the metal is first heated in a furnace or vessel until the metal is melted and is at a temperature desirable for foaming. The metal is poured into a heated vessel in which foaming is to take place. A material adapted to effect foaming is then fed into the molten metal until sufficient material has been added to produce a low density foam. The material is immediately exposed to additional heat to cause additional expansion of the cells within the metal alloy foam. The foam thus formed may be cooled by quenching with water and the metal alloy foam may then be treated by using a warm caustic soda solution to cause removal of the easily removable metal to provide a catalytic metal foam or the metal alloy foam maybe heated to a temperature at which the metal adapted to be easily removed from the metal alloy foam is vaporized and may then be removed by subjecting to a predetermined amount of vacuum or may be treated by any suitable means which produces the desired catalytic metal foam.
v If a continuous process is-to be employed, after the cooling of the metal alloy foam, the foam may be .continuouslytreated.
The invention also relates to a method for adding to an organic reaction, a catalytic metal foam formed by the aforedescribed method to catalyze said reaction. For example a 28% nickel-72% aluminum alloy foam may be used to prepare a metal alloy foam by melting and adding a material adapted to effect foaming. The metal alloy foam thus produced may then be leached with a 25% warm caustic soda solution. A portion of the resultant material may then be added in the form of a block to an organic solution such as benzene to cause hydrogenation of said solution. Another organic reaction which may be catalyzed by the product of my method is benzoylmethionine which is converted to benzoylaminobutyric acid.
A catalytic metal foam maybe formed from a nickelzinc alloy foam. The alloy foam is prepared by melting the alloy, adding a foaming agent, heating and then cooling. The resultant foam is then heated to a temperature below the melting temperature of the alloy and above the vaporization point of zinc so that upon subjection to a small amount of vacuum, the zinc vapors can be easily removed thusproviding a nickel catalytic foam. The resultant catalytic foam may then be used for the hydrogenation of vegetable 'oils.
The invention is furtherjillustrated by the following examples which illustrate certainxembodiments butare not to be taken as limiting the invention only to those particular embodiments illustrated,-it being understood that other embodiments and-equivalents will be apparent to those skilled in the art.
Example 1 v 784 g. aluminumxis heatedto 900 C. in a steel crucible, and at that temperature 305 g. nickel are added and allowed to dissolve. The alloy is stirred and allowed to cool to 854 C. at which time a foaming agent (20% zirconium hydride) is stirred into the mixture with an iron rod. The resultant body is cooled by quenching with water. The cooled metal alloy foam is then leached with a 25% caustic soda solution causing removal of aluminum. A /2 g. sample of the aforementioned foam is'then added to a container containing 4 liters of hexene and is subjected to 1500 lbs./sq. in. pressure provided by hydrogen. The system is allowed to run in this manner for 8 hours at which time 3.9 liters of hexane are obtained.
' Example 2 800 g. zinc are placed in a pressed steel crucible and heated to 950 C. 200 g. of'm'ckel are then added and allowed to dissolve. The alloy is stirred well and then 3.38 g. of zirconium hydride suspended in zinc powder are added and stirred therein using an ironrod. The foam is formed immediately and is cooled. The foam is then put in a pressure chamber and the foam subjected to a temperature of 900 C. and the pressure reduced from 760 mm. pressure to .1 mm. pressure of mercury to remove the zinc from the alloy. After two hours, the foam is' removed and provides a catalytic nickel foam. A /2 g. sample of the aforementioned foam is then added to a container containing 4 liters of octene and is subjected to 1500 lbs./ sq. in. pressure provided by hydrogen. The system is allowed to run in this manner for 8 hours at which time 3.9 liters of octane are obtained. I,
It may thus be seen that my invention is broad in scope and is not to be limited except'by the appended claims.
, Having thus disclosed my invention, I claim:
1. A method for preparing a catalytic metal foam comprising providing a molten pool of metal alloy consisting of a catalytic metal and at least one metal adapted to be easily removed from said metal alloy after foaming; introducing into the interior of the pool, a material adapted to effect foaming of thealloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, treating said body to remove said metal adapted to be easily removed body to remove said metal adapted to be easily removed from the metal alloy foam to provide catalytic metal foam.
3. A method for preparing a catalytic metal foam comprising providing a molten pool of nickel-aluminum alloy; introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, leaching said body to remove the aluminum from the nickel-aluminum foam to provide catalytic nickel foam.
4. A method for preparing a catalytic metal foam comprising providing a molten pool of metal alloy consisting of a catalytic metal and at least One metal adapted to be easily removed from said metal alloy after foaming, introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, heating said body to a temperature sufiiciently high to vaporize said metal adapted to be easily removed, subjecting said body to suflicient vacuum to remove said metal adapted to be easily removed thus providing a catalytic metal foam.
5. A method for preparing a catalytic metal foam comprising providing a molten pool of a nickel-zinc alloy, introducing into the interior of the pool, a material adapted to effect foaming of the alloy to form a body of molten metal alloy containing discrete cellular bubbles distributed therethrough cooling said body, heating said body to a temperature sufficiently high to vaporize the zinc contained in the alloy, subjecting said body to sufficient vacuum to remove said zinc thus providing a catalytic nickel foam.
References Cited in the file of this patent UNITED STATES PATENTS 2,299,228 Gray Oct. 20, 1942 2,365,751 Drennan Dec. 26, 1944 2,434,775 Sosnick Jan. 20, 1948 2,497,176 Mason Feb. 14, 1950 2,587,793 Waldron Mar. 4, 1952 2,751,289 Elliott June 19, 1956 OTHER REFERENCES Russian articleA.S.M. Review of Metal Literature, 1949, page 185. Note #4C-39.

Claims (1)

1. A METHOD FOR PREPARING A CATALYTIC METAL FOAM COMPRISING PROVIDING A MOLTEN POOL OF METAL ALLOY CONSISTING OF A CATALYTIC METAL AND AT LEAST ONE METAL ADAPTED TO BE EASILY REMOVED FROM SAID METAL ALLOY AFTER FOAMING; INTRODUCING INTO THE INTERIOR OF THE POOL, A MATERIAL ADAPTED TO EFFECT FOAMING OF THE ALLOY TO FORM A BODY OF MOLTEN METAL ALLOY CONTAINING DISCRETE CELLULAR BUBBLES DISTRIBUTED THERETHROUGH COOLING SAID BODY, TREATING SAID BODY TO REMOVE SAID METAL ADAPTED TO BE EASILY REMOVED FROM THE METAL ALLOY FOAM TO PROVIDE CATALYTIC METAL FOAM.
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Cited By (34)

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US3236706A (en) * 1961-11-17 1966-02-22 Dow Chemical Co Method of making porous metallic article
US3300296A (en) * 1963-07-31 1967-01-24 American Can Co Method of producing a lightweight foamed metal
US3360361A (en) * 1964-08-06 1967-12-26 United States Steel Corp Method of making foamed metal
US3364018A (en) * 1963-10-17 1968-01-16 Trw Inc Porous tungsten rhenium alloy and method of making same
US3367023A (en) * 1964-05-26 1968-02-06 Foerderung Forschung Gmbh Manufacturing of a porous metallic electrode
US3476547A (en) * 1966-10-20 1969-11-04 Gen Motors Corp Method of making metal powder
US3515541A (en) * 1967-05-03 1970-06-02 Chemie Linz Ag Process for the recovery of noble metals
US3523766A (en) * 1969-01-16 1970-08-11 Harold Markus Production of cellular metals
US3533863A (en) * 1968-12-30 1970-10-13 Gen Electric Process for producing apertured body comprising casting an alloy,plastically deforming the cast alloy,and etching to remove one of alloys,and body produced thereby
US3597829A (en) * 1969-03-18 1971-08-10 Us Army Method of making a nickel hydroxide electrode
US3617364A (en) * 1968-11-12 1971-11-02 Ethyl Corp Plastic-coated metallic foams
US3773098A (en) * 1972-02-04 1973-11-20 Bjorksten J Method of static mixing to produce metal foam
US3787298A (en) * 1971-08-09 1974-01-22 Ethyl Corp Anodizing aluminum foams
US3790367A (en) * 1971-11-26 1974-02-05 Ethyl Corp Aluminum-lead metal foams
US4689316A (en) * 1986-02-04 1987-08-25 The Dow Chemical Company Method of preparing supported catalysts
US5972285A (en) * 1997-06-10 1999-10-26 Th. Goldschmidt Ag Foamable metal articles
US6444007B1 (en) * 1999-02-24 2002-09-03 Goldschmidt Ag Production of metal foams
WO2002076610A1 (en) * 2001-03-22 2002-10-03 Showa Denko K. K. Catalyst for producing both end-hydroxyl group-terminated diols, process for producing the catalyst, process for producing the diols by using the catalyst, and both end-hydroxyl group-terminated diols obtained by the process
US20040079198A1 (en) * 2002-05-16 2004-04-29 Bryant J Daniel Method for producing foamed aluminum products
US20060243094A1 (en) * 2005-04-29 2006-11-02 Bryant J D Method for producing foamed aluminum products by use of selected carbonate decomposition products
US20060277253A1 (en) * 2005-06-01 2006-12-07 Ford Daniel E Method and system for administering network device groups
US20110239890A1 (en) * 2010-04-06 2011-10-06 Spritzer Michael H Thermite-Metal Foam
CN103966473A (en) * 2013-02-06 2014-08-06 艾蓝腾欧洲有限公司 Surface Modified Metallic Foam Body, Process For Its Production And Use Thereof
WO2017192042A1 (en) 2016-05-03 2017-11-09 Sintef Tto As Method for manufacturing a porous foam support, and porous foam supports for catalytic reactors, adsorption processes and energy storage
WO2018054754A1 (en) 2016-09-23 2018-03-29 Basf Se Method for the hydrogenation of organic compounds in the presence of co and a fixed catalyst bed which contains monolithic shaped catalyst body
WO2018054755A1 (en) 2016-09-23 2018-03-29 Basf Se Method for providing a catalytically active fixed bed for hydrogenating organic compounds
WO2018054740A1 (en) 2016-09-23 2018-03-29 Basf Se Method for providing a fixed catalyst bed containing a doped structured shaped catalyst body
WO2018054759A1 (en) 2016-09-23 2018-03-29 Basf Se Method for activating a fixed catalyst bed which contains monolithic shaped catalyst bodies or consists of monolithic shaped catalyst bodies
WO2019057533A1 (en) 2017-09-20 2019-03-28 Basf Se METHOD FOR PRODUCING A CATALYST SHAPED BODY
US11090637B2 (en) 2016-09-30 2021-08-17 Evonik Operations Gmbh Fixed catalyst bed comprising metal foam bodies
US11260375B2 (en) * 2016-09-30 2022-03-01 Evonik Operations Gmbh Process and catalyst for preparing 1,4-butanediol
US11401224B2 (en) 2018-02-14 2022-08-02 Evonik Operations Gmbh Method for the preparation of C3—C12-alcohols by catalytic hydrogenation of the corresponding aldehydes
US20220251682A1 (en) * 2021-02-09 2022-08-11 Toyota Jidosha Kabushiki Kaisha Method for manufacturing metal foam
US11819832B2 (en) 2019-09-25 2023-11-21 Evonik Operations Gmbh Catalytic reactor

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US2497176A (en) * 1946-06-12 1950-02-14 Standard Oil Dev Co Hydrogenation catalyst
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Cited By (46)

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Publication number Priority date Publication date Assignee Title
US3236706A (en) * 1961-11-17 1966-02-22 Dow Chemical Co Method of making porous metallic article
US3300296A (en) * 1963-07-31 1967-01-24 American Can Co Method of producing a lightweight foamed metal
US3364018A (en) * 1963-10-17 1968-01-16 Trw Inc Porous tungsten rhenium alloy and method of making same
US3367023A (en) * 1964-05-26 1968-02-06 Foerderung Forschung Gmbh Manufacturing of a porous metallic electrode
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