CA2090930A1 - Monolithic supported catalyst, and its preparation and use - Google Patents
Monolithic supported catalyst, and its preparation and useInfo
- Publication number
- CA2090930A1 CA2090930A1 CA002090930A CA2090930A CA2090930A1 CA 2090930 A1 CA2090930 A1 CA 2090930A1 CA 002090930 A CA002090930 A CA 002090930A CA 2090930 A CA2090930 A CA 2090930A CA 2090930 A1 CA2090930 A1 CA 2090930A1
- Authority
- CA
- Canada
- Prior art keywords
- monolithic
- support material
- catalyst
- preparation
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000004744 fabric Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000011888 foil Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000000306 component Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100536883 Legionella pneumophila subsp. pneumophila (strain Philadelphia 1 / ATCC 33152 / DSM 7513) thi5 gene Proteins 0.000 description 1
- 101100240664 Schizosaccharomyces pombe (strain 972 / ATCC 24843) nmt1 gene Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 101150066242 outO gene Proteins 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Toxicology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
O.Z. 0050/43114 Abstract of the Disclosure: A process for the preparation of a monolithic supported catalyst from a metallic support material, wherein the support material, in the form of a woven metal fabric or metal foil, is succes-sively heated in air, cooled and coated under reduced pressure with active components and promoters, and the coated support material is subsequently cut, shaped and finally converted into a monolithic catalyst element.
Description
2 u ~ 3 Q
O.~. 0050/43114 Monolithic supported catalyst, and 1ts preparation and use The present in~ention relates to a proce~s for the preparation of a monolithic supported catalyst from a metallic support material, and to the uRe thereofO
A large number of monolithic supported catalyst~
are known from the prior art; these c~n be employed for a wide variety of liquid-pha~e reactions.
Thus, CH-547 120 from Gebr. Sulzer AG describes a monolithic mixing unit for carrying out chemical reactions in which it is possible for the layers forming the flow channels to be produced directly from a catalyst material or for a catalyst material to be applied to the layers, which preferably comprise a material with no holes, for example metal sheeting, or alternatively a woven or knitted metal fabric. There i8 no mention of the catalyst material or its preparation.
EP 0 201 614 from the ~ame patentee claims a reactor for carrying out heterogeneous, catalytic reac-tions which has at least one packing element whichcontains a catalyst and comprises corrugated sheets which are arranged parallel to the principal flow axis of the reactor and who~e corrugations are inclined to the principal flow axis and are tilted in the opposite direction in adjacent sheets, where at least one band-like, partially corrugated cataly~t element iB installed removably between adjacent sheets.
It i8 clear from thl~ publication how difficult it i3 to provide compo~ite elements of this type with a ~uitable catalytic coating. It i9 therefore necessary to attack the problem indirectly and to install separate catalyst elements.
EP 0 068 862 by Atomic Energy of Canada, with the title "An ordered bed packing module" describes a packing module for an ordered bed catalyst for gas-liquid trans-fer reactions, comprising alternate layers of plane and corrugated sheets coiled together to form a roll, with ~9~30 ~ 2 - O.Z. 0050/4311~
the corrugation~ extending along an axis about which the layers have been coiled together and providing unob-structed fluid passages between the plane and ~orrugated sheets, characterized in that the plane sheet comprises woven, knitted or felted cloth of a textile, wicking material which is hydrophilic with respect to the liquid of the ga~-liquid transfer reaction and will provide an uninterrupted wicking path between the ends of the roll, for the said liquid, and the corrugated sheet comprise~
an open mesh material with at least an outer surface lay~r consisting of a high molecular weight, organic, polymeric ~ubstance, which will be inherently hydrophobic with respect to the said liquid, and contains catalyst cry~tallite~ (Group VIII of the Periodic Table), the crystallites being dispersed _n the porous matrix and partially enclo~ed thereby.
An example of an organic polymeric substance given i~ polytetrafluoroethylene containing platinum crystallites on carbon particles dispersed in the porous matrix. These catalytically active Pt/C particles are applied to the hydrophobic polymer material in the form of an aqueous suspension of Pt/C powder and immobilized by drying at from 60 to 100C and subsequent sintering at 365C.
These publications show how difficult it is -to apply catalytically active coatings to monolithic com-po~ite elements.
Thu~, the monolithic Katapak products mentioned by Sulzer can be converted into active catalysts by impregnation with salt solution~ of the active com-ponents. However, inconvenient and frequently unrepro-ducible impregnation steps with su~sequent drying and calcination are nece~sary. Since a wash coat is usually applied first to increase the surface area, the adhesive strength suffers in this method of producing the support with subsequent impregnation steps for the active com-ponents. The catalysts obtained are very similar to those 2~930 - 3 - o.Z. 0050/4311~
in automotive exhaust catalytic converters, in which poor adhesive ~trength, which easily results in destruction of the catalyst on mschanical load, is a known problem.
In continuous liquid-phase reactions, high abrasion reBi~tance i5 an essential prerequisite for reliable operation of ~he plant.
It i~ an object of the present invention to develop a cataly~t in the form of a monolithic unit in which the disadvantages de~cribed do not occur.
We have found that this object iq achieved by a process in which the ~upport material, in the form of a woven metal fabric or metal foil, is succeqsively heated in air, cooled and coated under reduced pressure with active component~ and promoter~, and the coated support material i9 ~ubseyuently cut, shaped and finally con-verted into a monolithic catalyst element.
In another variant, the coated ~upport material can be activated by re-heating.
The monolithic catalyst element according to the invention is employed in particular for chemical reac-tions in the gas and liquid phase.
It is known that layers having good adhesion can be produced by vacuum coating techniques.
Coatings of this type are currently uqed in many ways in the electrical industry, in tool and machine production and in the optical indu~try.
It ha~ now been found that monolithic ~upported cataly~ts can be produced by vapor-deposition or ~putter-ing of active components and promoter~ onto support~ in the form of metallic foils or woven fabrics.
Particularly suitabla example~ of the latter are the stainless ~teels having material number~ 1.4767, 1.4401, 2.4610, 1.4765, 1.4847, 1.4301 etc. since they can be surface-roughened by heating before they are coated with active components. To thi3 end, the metallic ~upports are heated in air at from 600 to 1100C, prefer-ably at from 800 to 1000C, for from 1 to 20 hour~, - 4 - O.Z. ~050/43114 preerably for from 1 to 10 hours, and then re-cooled.
This pretreatment is crl1cial for the activity of the catalyst. After this treatment at elevated temperature, the support is coated with the active component. To this end, the support is coated simultaneously or succes-sively, batchwise or continuously, with the active components and promoter~ under a reduced pressure of from 10-3 to 10-a mbar by means of an evaporation unit, for example electron beam evaporation, or a sputtering unit.
This can be followed by heating under an inert gas or air in order to activate the cataly~t.
In contrast to the previous application~ of vapor deposition in the optical and electrical industries, which require high purity of the support and depo~ition materials, a certain conden~ation temperature on the support and a certain deposition rate, since the optical, electrical and magnetic properties are extremely sensi-tive to defects in the deposited films and reproducible production of such films requires considerable effort, the aim of the process according to the invention for the preparation of catalyst layers i5 to prepare highly unordered and disturbed polycrystalline layers or clu~-ters. It i~ therefore normally not necessary for the vacuum conditions to be particularly good. Furthermore, alternate depo~ition of active components and structural promoters allows the active components to be produced in very ~inely cry~talline or cluster-like form.
In the process according to the invention, the cataly~t can be built up ~ystematically, for example in a vapor deposition unit containing a plurality of dif~
ferent evaporation source~. Thus, for example, it is possible fir~t to apply an oxide layer or, by reactive evaporation, an anchor layer to the support. Active components and promoters can be prepared on this base layer in a plurality of alternate layqrs. By admitting a reactive gas into the recipient, promoter layers of oxide~ or other compound~ can be produced. Interim - 5 - O.z. 0050/43114 heating can also be carried outO
Due to thP novel production of the woven catalyct fabric or the catalyst foils, the active component~ have such high adhesion that they can be cut, shaped and converted into monolithic catalyst elements.
A very simple monolithic catalyst is obtained if the wovan catalyst fabric or the cataly~t foil is shaped by ring gear rolling and flat and corrugated woven fabric or foil iQ rolled up to form a cylindrical monolith having identical vertical channel~. However, it i5 also possible to shape any desired static mixer from this catalyst material, ~ince the adhesion of the catalyst layer is sufficiently high.
The monolithic catalyst elements produced in this way, in the form of mixed elements, are installed in a reactor and charged with the reaction liquid to be reacted. In the ca~e of hydrogenation reactions, hydrogen or hydrogen and an inert ga are added, and optimum gas/liquid mixing is achieved by means of the ~hape of the monoliths. A very wide variety of chemical reactions can be carried out on such catalysts.
For hydrogenation reactions, for example, cata-ly~ts are employed which contain, a~ active component~, elements from Group VIII of the Periodic Table, for example Fe, Co, Ni, Ru, Rh, Pd, Pt and Ir. Po~sible promoters include Cu, Ag, Au, Zn, Sn, Bi, Sb, etc.
In this way, olefinic double bonds can selec-tively be hydrogenated by the process according to the invention using Pd catalysts.
A corre~ponding Pd cataly~t is prepared as follows:
Adhering oil and grea~e i9 removed from ~tainless steel woven fabric having the material number 1.4767 made from Fe, Cr and Al in an ultrasound bath, and the material i~ heated for 5 hours at 900C in a muffle in air. After cooling, the fabric is vapor-deposited on both sides with a 4 nm thick Pd layer in a continuous electron 2VY~3~
O.~. 0050/43114 Monolithic supported catalyst, and 1ts preparation and use The present in~ention relates to a proce~s for the preparation of a monolithic supported catalyst from a metallic support material, and to the uRe thereofO
A large number of monolithic supported catalyst~
are known from the prior art; these c~n be employed for a wide variety of liquid-pha~e reactions.
Thus, CH-547 120 from Gebr. Sulzer AG describes a monolithic mixing unit for carrying out chemical reactions in which it is possible for the layers forming the flow channels to be produced directly from a catalyst material or for a catalyst material to be applied to the layers, which preferably comprise a material with no holes, for example metal sheeting, or alternatively a woven or knitted metal fabric. There i8 no mention of the catalyst material or its preparation.
EP 0 201 614 from the ~ame patentee claims a reactor for carrying out heterogeneous, catalytic reac-tions which has at least one packing element whichcontains a catalyst and comprises corrugated sheets which are arranged parallel to the principal flow axis of the reactor and who~e corrugations are inclined to the principal flow axis and are tilted in the opposite direction in adjacent sheets, where at least one band-like, partially corrugated cataly~t element iB installed removably between adjacent sheets.
It i8 clear from thl~ publication how difficult it i3 to provide compo~ite elements of this type with a ~uitable catalytic coating. It i9 therefore necessary to attack the problem indirectly and to install separate catalyst elements.
EP 0 068 862 by Atomic Energy of Canada, with the title "An ordered bed packing module" describes a packing module for an ordered bed catalyst for gas-liquid trans-fer reactions, comprising alternate layers of plane and corrugated sheets coiled together to form a roll, with ~9~30 ~ 2 - O.Z. 0050/4311~
the corrugation~ extending along an axis about which the layers have been coiled together and providing unob-structed fluid passages between the plane and ~orrugated sheets, characterized in that the plane sheet comprises woven, knitted or felted cloth of a textile, wicking material which is hydrophilic with respect to the liquid of the ga~-liquid transfer reaction and will provide an uninterrupted wicking path between the ends of the roll, for the said liquid, and the corrugated sheet comprise~
an open mesh material with at least an outer surface lay~r consisting of a high molecular weight, organic, polymeric ~ubstance, which will be inherently hydrophobic with respect to the said liquid, and contains catalyst cry~tallite~ (Group VIII of the Periodic Table), the crystallites being dispersed _n the porous matrix and partially enclo~ed thereby.
An example of an organic polymeric substance given i~ polytetrafluoroethylene containing platinum crystallites on carbon particles dispersed in the porous matrix. These catalytically active Pt/C particles are applied to the hydrophobic polymer material in the form of an aqueous suspension of Pt/C powder and immobilized by drying at from 60 to 100C and subsequent sintering at 365C.
These publications show how difficult it is -to apply catalytically active coatings to monolithic com-po~ite elements.
Thu~, the monolithic Katapak products mentioned by Sulzer can be converted into active catalysts by impregnation with salt solution~ of the active com-ponents. However, inconvenient and frequently unrepro-ducible impregnation steps with su~sequent drying and calcination are nece~sary. Since a wash coat is usually applied first to increase the surface area, the adhesive strength suffers in this method of producing the support with subsequent impregnation steps for the active com-ponents. The catalysts obtained are very similar to those 2~930 - 3 - o.Z. 0050/4311~
in automotive exhaust catalytic converters, in which poor adhesive ~trength, which easily results in destruction of the catalyst on mschanical load, is a known problem.
In continuous liquid-phase reactions, high abrasion reBi~tance i5 an essential prerequisite for reliable operation of ~he plant.
It i~ an object of the present invention to develop a cataly~t in the form of a monolithic unit in which the disadvantages de~cribed do not occur.
We have found that this object iq achieved by a process in which the ~upport material, in the form of a woven metal fabric or metal foil, is succeqsively heated in air, cooled and coated under reduced pressure with active component~ and promoter~, and the coated support material i9 ~ubseyuently cut, shaped and finally con-verted into a monolithic catalyst element.
In another variant, the coated ~upport material can be activated by re-heating.
The monolithic catalyst element according to the invention is employed in particular for chemical reac-tions in the gas and liquid phase.
It is known that layers having good adhesion can be produced by vacuum coating techniques.
Coatings of this type are currently uqed in many ways in the electrical industry, in tool and machine production and in the optical indu~try.
It ha~ now been found that monolithic ~upported cataly~ts can be produced by vapor-deposition or ~putter-ing of active components and promoter~ onto support~ in the form of metallic foils or woven fabrics.
Particularly suitabla example~ of the latter are the stainless ~teels having material number~ 1.4767, 1.4401, 2.4610, 1.4765, 1.4847, 1.4301 etc. since they can be surface-roughened by heating before they are coated with active components. To thi3 end, the metallic ~upports are heated in air at from 600 to 1100C, prefer-ably at from 800 to 1000C, for from 1 to 20 hour~, - 4 - O.Z. ~050/43114 preerably for from 1 to 10 hours, and then re-cooled.
This pretreatment is crl1cial for the activity of the catalyst. After this treatment at elevated temperature, the support is coated with the active component. To this end, the support is coated simultaneously or succes-sively, batchwise or continuously, with the active components and promoter~ under a reduced pressure of from 10-3 to 10-a mbar by means of an evaporation unit, for example electron beam evaporation, or a sputtering unit.
This can be followed by heating under an inert gas or air in order to activate the cataly~t.
In contrast to the previous application~ of vapor deposition in the optical and electrical industries, which require high purity of the support and depo~ition materials, a certain conden~ation temperature on the support and a certain deposition rate, since the optical, electrical and magnetic properties are extremely sensi-tive to defects in the deposited films and reproducible production of such films requires considerable effort, the aim of the process according to the invention for the preparation of catalyst layers i5 to prepare highly unordered and disturbed polycrystalline layers or clu~-ters. It i~ therefore normally not necessary for the vacuum conditions to be particularly good. Furthermore, alternate depo~ition of active components and structural promoters allows the active components to be produced in very ~inely cry~talline or cluster-like form.
In the process according to the invention, the cataly~t can be built up ~ystematically, for example in a vapor deposition unit containing a plurality of dif~
ferent evaporation source~. Thus, for example, it is possible fir~t to apply an oxide layer or, by reactive evaporation, an anchor layer to the support. Active components and promoters can be prepared on this base layer in a plurality of alternate layqrs. By admitting a reactive gas into the recipient, promoter layers of oxide~ or other compound~ can be produced. Interim - 5 - O.z. 0050/43114 heating can also be carried outO
Due to thP novel production of the woven catalyct fabric or the catalyst foils, the active component~ have such high adhesion that they can be cut, shaped and converted into monolithic catalyst elements.
A very simple monolithic catalyst is obtained if the wovan catalyst fabric or the cataly~t foil is shaped by ring gear rolling and flat and corrugated woven fabric or foil iQ rolled up to form a cylindrical monolith having identical vertical channel~. However, it i5 also possible to shape any desired static mixer from this catalyst material, ~ince the adhesion of the catalyst layer is sufficiently high.
The monolithic catalyst elements produced in this way, in the form of mixed elements, are installed in a reactor and charged with the reaction liquid to be reacted. In the ca~e of hydrogenation reactions, hydrogen or hydrogen and an inert ga are added, and optimum gas/liquid mixing is achieved by means of the ~hape of the monoliths. A very wide variety of chemical reactions can be carried out on such catalysts.
For hydrogenation reactions, for example, cata-ly~ts are employed which contain, a~ active component~, elements from Group VIII of the Periodic Table, for example Fe, Co, Ni, Ru, Rh, Pd, Pt and Ir. Po~sible promoters include Cu, Ag, Au, Zn, Sn, Bi, Sb, etc.
In this way, olefinic double bonds can selec-tively be hydrogenated by the process according to the invention using Pd catalysts.
A corre~ponding Pd cataly~t is prepared as follows:
Adhering oil and grea~e i9 removed from ~tainless steel woven fabric having the material number 1.4767 made from Fe, Cr and Al in an ultrasound bath, and the material i~ heated for 5 hours at 900C in a muffle in air. After cooling, the fabric is vapor-deposited on both sides with a 4 nm thick Pd layer in a continuous electron 2VY~3~
- 6 - O.~. 0050/43114 beam vapor-deposition unit (layer thickness measured using piezoelectric quartz). Part of the woven cataly~t fabric obtained in this way is shaped by ring gear rolling, and the ~orrugated piece of fabric i~ then rolled up with a flat piece of woven fabxic. The cylindrical monolithic catalyst obtained in this way, having the same diameter as the hydrogenation reactor, is installed in the latter and charged with the hydrogen-ation solution and hydrogen. At a volume hourly space velocity of 20 m3/m2 x h optimum di~tribution o~ ga~ and liquid and excellent exchange with the catalyst surface are obtained, which is evident from a high space-time yield.
Claims (3)
1. A process for the preparation of a monolithic supported catalyst from a metallic support material, wherein the support material, in the form of a woven metal fabric or metal foil, is successively heated in air, cooled and coated under reduced pressure with active components and promoters, and the coated support material is subsequently cut, shaped and finally converted into a monolithic catalyst element.
2. A process as claimed in claim 1, wherein the coated support material is activated by re-heating.
3. A process as claimed in claim 1, wherein the monolithic catalyst element is employed for chemical reactions in the gas or liquid phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4209631A DE4209631A1 (en) | 1992-03-25 | 1992-03-25 | Monolithic supported catalyst, process for its preparation and its use |
| DEP4209631.6 | 1992-03-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2090930A1 true CA2090930A1 (en) | 1993-09-26 |
Family
ID=6454943
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002090930A Abandoned CA2090930A1 (en) | 1992-03-25 | 1993-03-03 | Monolithic supported catalyst, and its preparation and use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0564830B1 (en) |
| JP (1) | JP3335408B2 (en) |
| CA (1) | CA2090930A1 (en) |
| DE (2) | DE4209631A1 (en) |
| DK (1) | DK0564830T3 (en) |
| ES (1) | ES2078077T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6998366B2 (en) | 1999-12-28 | 2006-02-14 | Basf Aktiengesellschaft | Thin layer catalysts based on Raney alloys, and method for the production thereof |
| US7041847B2 (en) | 2001-01-31 | 2006-05-09 | Basf Aktiengesellschaft | Method for cleaning crude terephthalic acid and catalysts suitable for the same and containing carbon fibers |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4407486A1 (en) * | 1994-03-07 | 1995-09-14 | Basf Ag | Process for the preparation of 1,2-butylene oxide |
| KR100483637B1 (en) * | 1996-06-17 | 2005-06-17 | 바스프 악티엔게젤샤프트 | Catalytic Distillation Process |
| DE19624130A1 (en) * | 1996-06-17 | 1997-12-18 | Basf Ag | Process for catalytic distillation |
| DE19636064A1 (en) * | 1996-09-05 | 1998-03-12 | Basf Ag | Hydrogenation process |
| DE19815639A1 (en) * | 1998-04-07 | 1999-10-14 | Basf Ag | Process for the production of sugar alcohols |
| DE10050709A1 (en) * | 2000-10-13 | 2002-04-25 | Basf Ag | Structured catalyst support, useful for the hydrogenation of aromatic compounds, contains a promoter comprising a Group I, II or IV metal or Group I-IV or VI metal and sulfur, selenium and carbon |
| DE10123066A1 (en) | 2001-05-11 | 2002-11-14 | Basf Ag | Process for the production of higher alpha, beta-unsaturated alcohols |
| JP4781642B2 (en) * | 2004-06-07 | 2011-09-28 | 花王株式会社 | Method for producing aldehyde |
| DE102008002535A1 (en) | 2007-06-25 | 2009-01-02 | Basf Se | Producing vicinal dioxo compounds, preferably glyoxal, useful as cross linker functionalized polymers, comprises gas phase oxidation of vicinal dihydroxy compounds in presence of gases containing oxygen on a catalyst comprising e.g. gold |
| JP5468104B2 (en) * | 2012-04-25 | 2014-04-09 | 石田 幸男 | Wiring board manufacturing method and wiring board |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR870000844B1 (en) * | 1981-03-10 | 1987-04-25 | 후꾸다 이꾸마사 | Process of continously producing plate-shaped catalyst and system therefor |
| JPH0657320B2 (en) * | 1987-07-31 | 1994-08-03 | マツダ株式会社 | Exhaust gas purification catalyst manufacturing method |
| US4931421A (en) * | 1988-06-27 | 1990-06-05 | Motonobu Shibata | Catalyst carriers and a method for producing the same |
| JPH0299144A (en) * | 1988-10-07 | 1990-04-11 | Babcock Hitachi Kk | Plate-shaped catalyst and preparation thereof |
| FI84562C (en) * | 1990-01-16 | 1991-12-27 | Neste Oy | FARING EQUIPMENT FOR THE FRAME STATION OF HETEROGENE CATALYSTATORS. |
| JPH05154381A (en) * | 1991-04-26 | 1993-06-22 | Nippon Steel Corp | Exhaust gas purifying catalyst forming process |
-
1992
- 1992-03-25 DE DE4209631A patent/DE4209631A1/en not_active Withdrawn
-
1993
- 1993-03-03 CA CA002090930A patent/CA2090930A1/en not_active Abandoned
- 1993-03-05 JP JP04478493A patent/JP3335408B2/en not_active Expired - Fee Related
- 1993-03-09 DE DE59300732T patent/DE59300732D1/en not_active Expired - Fee Related
- 1993-03-09 DK DK93103719.6T patent/DK0564830T3/en active
- 1993-03-09 EP EP93103719A patent/EP0564830B1/en not_active Expired - Lifetime
- 1993-03-09 ES ES93103719T patent/ES2078077T3/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6998366B2 (en) | 1999-12-28 | 2006-02-14 | Basf Aktiengesellschaft | Thin layer catalysts based on Raney alloys, and method for the production thereof |
| US7041847B2 (en) | 2001-01-31 | 2006-05-09 | Basf Aktiengesellschaft | Method for cleaning crude terephthalic acid and catalysts suitable for the same and containing carbon fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4209631A1 (en) | 1993-09-30 |
| JP3335408B2 (en) | 2002-10-15 |
| EP0564830A2 (en) | 1993-10-13 |
| EP0564830B1 (en) | 1995-10-11 |
| EP0564830A3 (en) | 1993-11-10 |
| DE59300732D1 (en) | 1995-11-16 |
| ES2078077T3 (en) | 1995-12-01 |
| JPH0639297A (en) | 1994-02-15 |
| DK0564830T3 (en) | 1995-12-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |