CN100423839C - Method for supporting catalyst on the metal base - Google Patents
Method for supporting catalyst on the metal base Download PDFInfo
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- CN100423839C CN100423839C CNB2006100731750A CN200610073175A CN100423839C CN 100423839 C CN100423839 C CN 100423839C CN B2006100731750 A CNB2006100731750 A CN B2006100731750A CN 200610073175 A CN200610073175 A CN 200610073175A CN 100423839 C CN100423839 C CN 100423839C
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Abstract
The invention relates to a preparing method of a metal carrier catalyst coating, wherein, the metal carrier catalyst coating which has an alloy metal high temperature treated as a substrate firstly loads a first layer alumina sol AlOOH, after drying loads a second layer Al2O3 paste, then drying and calcining to obtain a firmly coating; or loads mixed paste comprised by Al2O3 and the other metal oxide required by reaction on the dried AlOOH coat to obtain a catalyst active coat after drying and calcining; or an active coating for especial reaction is obtained by further loading paste which is the other metal oxide required by reaction on the second Al2O3 paste coat, and then drying and calcining. Then the active components are loaded on the obtained catalyst coating, after drying and calcining to prepare the metal carrier catalyst. The coating and the metal carrier of the invention are combined firmly. The invention can prepare the composite coating metal carrier catalyst based on different reaction requirement and the process and device for preparing is simple.
Description
Technical field
The present invention relates to a kind of on metallic matrix the method for supported catalyst, solved between metallic matrix and the catalytic active component coating in conjunction with the firmness problem, thereby can go out required metal carrier catalyst at different prepared in reaction.
Background technology
Since West Germany VDM company at first was applied to metal beehive and wire netting chip carrier catalyst purifying vehicle exhaust from the 1970s and 1980s in last century, metal carrier catalyst and technology had obtained huge technological progress in the motor vehicle tail-gas purifying field.
Metallic carrier self has a lot of advantages, characteristics such as, percent opening height thin as good, the anti-mechanical shock ability of heat-conductive characteristic height, easily processing, wall, be particularly suitable in the environment of strong heat absorption, exothermic reaction system and sharp pounding, using, and provide convenience for the system integration.Therefore metal carrier catalyst all has good application prospects in the reaction systems such as high-temperature catalytic field of hydrogenation such as methanation, Fischer-Tropsch synthesis (Fischer Tropsch reaction), lique faction of coal, nitrogen oxide elimination in high-temperature catalytic oxidation field as the oxidation of catalytic combustion, ammonia.
But because the thermal coefficient of expansion of metallic matrix and coating differs bigger, the firmness of the two combination is relatively poor, is the major obstacle of metal carrier catalyst practical application, also is the main direction of studying at present.The preparation method of existing patent, bibliographical information mainly is divided into following 3 classes.
1. metallic carrier is handled direct load aluminum oxide coating layer without special surface.CN1226465A, US 3920583, and US 4196099, and US 6540843 is direct load alumina slurry coating in the metal surface, and the coating firmness that obtains is not enough, peels off easily.
CN 1226465A is immersed in γ-Al to the OCr19A15 or the OCr25A15 metallic carrier plate of band burr
2O
3In the emulsion, 400-600 ℃ of insulation 3-5h in electric furnace cools off with stove then.But the grain graininess that coating granule and oxidation on metal surface form after the emulsion roasting differs bigger, and coating and metallic matrix are in conjunction with firm inadequately.
US 3920583 selects for use the FeCrAlY alloy as carrier, claim Cr up to 15%, Al0.5-12%, Y0.1-3%, load is by 1-5 μ m γ-Al then
2O
3The mixture of the alumina gel of powder, wetting agent, 10nm etc. is at 1000 ℃ of roasting 1h.Be used as vent gas treatment after the load platinum.
US 4196099 has proposed the preparation method that on metallic carrier load contains the chromium aluminum oxide coating layer.At first prepared Alseal-500 in the patent: the phosphoric acid by 300g boehmite and 558ml75% makes aluminum phosphate solution, and thin up is that 60% back adds 12g CrO to the aluminum phosphate mass content
3, in the solution of gained, add aluminium powder then.Load one deck Alseal-500 at first on chromium steel, dry back obtains the metal/ceramic coating, this coating can strengthen the high temperature oxidation resistance of metal, make the nickel chromium triangle metal 1200 ℃ available down, be used for vehicle exhaust and handle.
US 6540843 at first prepares colloidal sol as binding agent (for example boehmite adds the colloidal sol that excessive acid obtains), then binding agent and metal oxide mixing is obtained slurry.Metallic carrier obtains the metallic carrier coating through the slurry that surperficial removal of impurities, dry load afterwards prepare above after the drying and roasting.
2. electroplate or anodizing.CN 1235066A, CN 1351905A, US 4472533, US 4918042, US 5208206 have adopted plating or anodised method to prepare metallic carrier.Electroplate or anodic oxidation in electrolyte difficult in maintenance, process of surface treatment complexity, and plating or anodic oxidation all can be accompanied by the generation of electrolyte waste liquid, forms great environmental pollution.Along with the gradually intensification of people to environmental consciousness, these methods have been not suitable for practical application.
CN 1235066A at first advances the 1-10h anodic oxidation to aluminium sheet, carries out hydration-treated and roasting then.Flood the catalyst that the active component solution drying and roasting just can obtain the incorporate purifying motor tail gas of metallic walls and Catalytic Layer again.
CN 1351905A carries out anodic oxidation with metal foil makes its surface generate the oxide-film transition zone, and electrolyte is the oxalic acid of 2-8% (percentage by weight), oxidation voltage 8-12V, oxidization time 5-120s.Flood aluminium colloidal sol then, obtain in conjunction with firm coating.
US 4472533 aluminium or aluminium alloy are made matrix, then matrix as anode, in diluted acid, boric acid, carry out dc anodizing.Removing surface acidity is electrolyte (selecting corresponding sulfate according to required catalytic metal) with the nickelous sulfate under the faintly acid afterwards then, handles under alternating current and obtains containing nickel coating.Clean acid afterwards as catalyst.
US 4918042 adopts spraying or electro-plating method load zirconium and aluminium (load simultaneously of zirconium and aluminium or first load zirconium back loading aluminium) in siderochrome or Aludirome surface, load alumina slurry then, 600 ℃ of roasting 1h of 200 ℃ of dryings, load active component platinum and rhodium are used for vent gas treatment again.
US 5208206 at first electroplates layer of aluminum, 900 ℃ of following fusion 30min of vacuum then at the FeCrAl alloy surface.After the cooling at first load contain 5-10 μ m Al
2O
33H
2The slurry of O particle (slurry), 650 ℃ of roasting 2.5h obtain 3-10 μ m aluminum oxide coating layer behind the 200-250 ℃ of dry 2h.Load contains 25-60 μ m γ-Al again
2O
3The slurry of particle, 650 ℃ of roasting 2.5h obtain 30-50 μ m aluminum oxide coating layer.
3. high temperature oxidation process is carried out in the metal surface.CN 1351906A, CN 1593756A adopt the method for high-temperature oxydation that preliminary treatment is carried out in the metal surface.The high-temperature oxydation pretreatment operation is simple, and can form the good transition zone of one deck in the metal surface.But CN 1351906A preparation process complexity, and just load layer of aluminum colloidal sol.CN 1593756A directly loads on alumina slurry on the metallic carrier, and preparation coating firmness is on the low side.
CN 1351906A Aludirome is at 900 ℃ of following roasting 10-24h, with the dipping of the alloy after oxidation aluminium colloidal sol, the concentration of control colloidal sol is 1.10-1.20g/ml, through at least 4 dippings, 3 times add thermal decomposition and be respectively 200 ℃, 30min, 300 ℃, 30min, 400 ℃, 30min, when the weightening finish of weight alloy percentage reaches 10-20%, final 550 ℃ of roasting 2-4h.One deck alumina sol coating that shortcoming has been a load, and preparation process is more loaded down with trivial details.
CN 1593756A at first the nickel chromium triangle metal beehive at 300-400 ℃ of oxidation 1-3h, load γ-Al then
2O
3, the mixed slurry formed such as cerium oxide, zirconia, lanthana, yttrium oxide and active component palladium oxide, platinum oxide, behind the drying and roasting as three-way catalyst.
On the whole, the metallic carrier coating of more existing patents preparation only limits to aluminum oxide coating layer or the aluminum oxide coating layer of a small amount of other metal oxides that mix, and coating and metallic carrier adhesion are less than normal, preparation process complexity, higher, the contaminated environment of cost.
Summary of the invention
The purpose of this invention is to provide a kind of on metallic matrix the method for supported catalyst.The present invention prepares the metallic carrier preparation method of composite coating that its coating firmness height of catalyst, environmental friendliness, preparation technology are simple, can be applied to the number of chemical reaction.
For achieving the above object, the preparation method of metal carrier catalyst coating provided by the invention may further comprise the steps:
(1) metallic carrier makes the metal surface generate corresponding oxide grain and the certain roughness of formation in 880-1050 ℃ of following oxidation 0.5-10h;
(2) load aluminium Sol A lOOH and dry on the metallic matrix after the oxidation; Aluminium Sol A lOOH concentration is 0.6-2.0molL
-1, the pH value is 2-4, the thickness of coating is 3-10 μ m;
(3) load Al on the aluminium collosol coating
2O
3Slurry is also dry; Al
2O
3Slurry pH value is 2-4, and coating layer thickness is 10-50 μ m, 40-120 ℃ of following dry 0.5-2h, and 500-900 ℃ of following roasting time 2-5h gets composite coating;
(4) load active component on composite coating is prepared metal carrier catalyst behind the drying and roasting.
Described preparation method, wherein metallic carrier is FeCrAl, FeCrAlY or 1Ni9Cr18Ti sheet metal.
Described preparation method, aluminium Sol A lOOH concentration is 0.8-1.5molL in the step 2
-1
Described preparation method, in the step 3 on the aluminium collosol coating Al of load
2O
3Slurry is by Al
2O
3Add the binding agent mixing and ball milling and form, wherein Al
2O
3With the binding agent mol ratio be 2: 1-19: 1, described binding agent is Al
2O
3H
2O, aluminium colloidal sol, Ludox, zirconium colloidal sol or titanium colloidal sol.
Described preparation method, wherein Al
2O
3Slurry is by Al
2O
3, binding agent, one or several the reaction required other metal oxides or salt mixing and ball milling form.
Described preparation method, burning thing wherein or salt are CeO
2-ZrO
2, Ce (NO
3)
36H
2O is or/and Zr (NO
3)
45H
2O.
Described preparation method, the roasting in the step 3 is to be warmed up to 500-900 ℃ of following roasting 2-4h with 1-15 ℃/min.
Detailed says, the invention provides a kind of surface treatment method of alloying metal, handles through proper temperature and time, makes the metal surface generate corresponding oxide and the certain roughness of formation.For example the suitable treatment temperature of FeCrAl alloy is 880-1050 ℃ of high-temperature oxydation 0.5-10h; The suitable treatment temperature of 1Ni9Cr18Ti is 800-900 ℃ of roasting 2-5h.
The invention provides a kind of metal carrier load composite coating preparation technology.Specific embodiment is: high temperature surface preparation → load sol layer → drying → load Al
2O
3Required coating of metal oxides → roasting is specifically reacted in slurry coating → drying → load.Al wherein
2O
3Can mixing and ball milling with the required metal oxide of concrete reaction, two slurry coating load step are combined into a step.
The invention provides a kind of on metallic carrier the method for load aluminium colloidal sol tie coat, aluminium Sol A lOOH concentration is 0.6-2.0molL
-1, preferred 0.8-1.5molL
-1, viscosity is 0.010-0.086Pas, and the pH value is between 2-4, and drying mode is 0.5-2h between 40-120 ℃, and the thickness of aluminium collosol coating is between 3-10 μ m.
The invention provides a kind of on metallic carrier aluminium collosol coating load Al
2O
3The method of slurry coating, Al
2O
3Slurry is by γ-Al
2O
3And binding agent (Al for example
2O
3H
2O, aluminium colloidal sol, Ludox, zirconium colloidal sol or titanium colloidal sol) mixing and ball milling forms, Al wherein
2O
3With the binding agent mol ratio be 2: 1-19: 1, Al
2O
3PH value of slurry is between 2-4, and drying mode is 0.5-2h between 40-120 ℃, Al
2O
3The thickness of slurry coating is between 10-50 μ m.
The invention provides the method for a kind of metallic carrier coating roasting, be warmed up to 500-900 ℃ of following roasting 2-4h, can effectively reduce the generation of coating crack with 1-15 ℃/min.
The invention provides a kind of method of other coating of metal oxides of load, at dried Al
2O
3On the slurry coating basis, load is added the slurry that binding agent is formed by one or several other metal oxides as required, then at 40-120 ℃ of dry 1-2h, and 500-900 ℃ of following roasting 2-4h.
Coating of the present invention and metallic carrier can be according to the differential responses needs in conjunction with firmly, and preparation is in conjunction with firm composite coating metal carrier catalyst, and manufacture craft and equipment require simple.
Aluminium colloidal sol/the Al of the present invention's preparation
2O
3Slurry coating has formed progressively transition, in conjunction with firm composite coating.According to GB GB 5210-85 " determination method of coating adhesion is drawn back method ", recording coating adhesion is 21.8MPa.
Aluminium colloidal sol/the Al of the present invention's preparation
2O
3, metal oxide mixed slurry coating, formed progressively transition, in conjunction with firm composite coating, according to GB GB 5210-85 " determination method of coating adhesion is drawn back method ", recording coating adhesion is 18.5MPa.
Aluminium colloidal sol/the Al of the present invention's preparation
2O
3Slurry/metal oxide paste coating has formed progressively transition, in conjunction with firm composite coating, and according to GB GB 5210-85 " determination method of coating adhesion is drawn back method ", recording coating adhesion is 15.8MPa.
The Al of the present invention's preparation
2O
3/ CeO
2-ZrO
2/ Ir metallic matrix methanol steam reforming catalyst is compared with ceramic honeycomb catalyst, have more stable temperature of reaction system, and catalyst has good stable.
Novelty of the present invention and creativeness are:
1) a kind of preparation technology of metal carrier catalyst coating has been proposed: high temperature surface preparation → load aluminium sol layer → drying → load Al
2O
3Required coating of metal oxides → roasting is specifically reacted in slurry coating → drying → load.Be coated with the mutual scattering and permeating of interlayer through behind the drying and roasting, obtain the composite coating of strong bonded.Al wherein
2O
3Can mixing and ball milling with the required metal oxide of concrete reaction, two slurry coating load step are combined into a step.
2) at different alloying metals, select different optimum temperatures and time to handle, generate corresponding oxide in the metal surface and form certain roughness, help adhering to of collosol coating.
3) load of aluminium colloidal sol and alumina slurry just can reach required load capacity, has simplified preparation process technology.Can change the load capacity of aluminium colloidal sol and alumina slurry and coating of metal oxides thereof simultaneously according to different reaction requirement.
4) the metallic carrier preparation technology of Ti Chuing other metal oxide active coatings outside can the load alumina have been expanded the range of application of metallic carrier.
Description of drawings
Fig. 1 is the conversion ratio schematic diagram of metal beehive of the present invention and ceramic honeycomb catalyst.
A is the metal beehive conversion ratio to the R-t curve of time among the figure, and b is the ceramic honeycomb conversion ratio to the R-t curve of time, and c is the metal beehive temperature of reaction system to the T-t curve of time, and d is the T-t curve of ceramic honeycomb temperature of reaction system to the time.
Reactor used in the evaluation is the quartz glass tube of internal diameter 15mm, and the reaction liquid air speed is 1.25h
-1, water alcohol is than being 1.5.
The specific embodiment
Embodiment 1:
Metal surface preliminary treatment:, clean 10min in deionized water for ultrasonic then, to remove oil, oxide and some impurity on the metal surface with FeCrAl sheet metal ultrasonic cleaning 30min in acetone.120 ℃ of dry backs are carried out roasting 10h to sheet metal under 950 ℃ of high temperature.
The preparation of aluminium colloidal sol: the 24g boehmite is dissolved in the 200ml deionized water, and the reaction that is hydrolyzed forms AlOOH, adds nitric acid behind the stirring certain hour, and control pH value stirs ageing 24h 24, obtains the aluminium colloidal sol of stable transparent.
Al
2O
3The preparation of slurry: with 3gAl
2O
3H
2O, 27g γ-Al
2O
3With 70ml deionized water mixing and ball milling 18h, obtain Al
2O
3Slurry adds nitric acid and regulates Al
2O
3PH value of slurry is at 2-4.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h is load Al then
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Embodiment 2:
Metal surface preliminary treatment:, clean 10min in deionized water for ultrasonic then, to remove oil, oxide and some impurity on the metal surface with FeCrAl sheet metal ultrasonic cleaning 30min in acetone.120 ℃ of dry backs are carried out roasting 10h to sheet metal under 880 ℃ of high temperature.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
Coating load: with embodiment 1.
Embodiment 3:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: the 12g boehmite is dissolved in the 150ml deionized water, and the reaction that is hydrolyzed forms AlOOH, adds nitric acid behind the stirring certain hour, and control pH value stirs ageing 24h at 2-4, obtains the aluminium colloidal sol of stable transparent.
Al
2O
3The preparation of slurry: with embodiment 1.
Coating load: with embodiment 1.
Embodiment 4:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with 3gAl
2O
3H
2O, 27g γ-Al
2O
3With 100ml deionized water mixing and ball milling 18h, obtain Al
2O
3Slurry adds nitric acid and regulates Al
2O
3PH value of slurry is at 2-4.
Coating load: with embodiment 1.
Embodiment 5:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 120 ℃ of dry 1h is load Al then
2O
3Slurry behind 120 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Embodiment 6:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h is load Al then
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 900 ℃ with 5 ℃/min, roasting 2h.
Embodiment 7:
The metal surface preliminary treatment: with FeCrAlY, the 1Ni9Cr18Ti sheet metal is ultrasonic cleaning 30min in acetone, cleans 10min in deionized water for ultrasonic then, to remove oil, oxide and some impurity on the metal surface.120 ℃ of dry backs are carried out roasting 2h to sheet metal under 850 ℃ of high temperature.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
Coating load: with embodiment 1.
Embodiment 8:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
CeO
2-ZrO
2The preparation of slurry: 24gCeO
2-ZrO
2, 35mlCe-Zr colloidal sol mixing and ball milling 18h, add nitric acid and regulate CeO
2-ZrO
2PH value of slurry is at 2-4.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h is load Al then
2O
3Slurry, 40 ℃ of dry 2h back loading CeO
2-ZrO
2Slurry is warmed up to 500 ℃ with 5 ℃/min behind 40 ℃ of dry 2h, roasting 2h.
Embodiment 9:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3And CeO
2-ZrO
2The preparation of mixed slurry: with 3gAl
2O
3H
2O, 27g γ-Al
2O
3, 15g CeO
2-ZrO
2With 70ml deionized water mixing and ball milling 18h, obtain mixed slurry, add nitric acid and regulate Al
2O
3PH value of slurry is at 2-4.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h is load Al then
2O
3And CeO
2-ZrO
2Mixed slurry is warmed up to 500 ℃ with 5 ℃/min behind 40 ℃ of dry 2h, roasting 2h.
Embodiment 10:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3And CeO
2-ZrO
2The preparation of mixed slurry: with 3gAl
2O
3H
2O, 27g γ-Al
2O
3, 32.1g Ce (NO
3)
36H
2O, 7.9g Zr (NO
3)
45H
2O and 70ml deionized water mixing and ball milling 18h obtain mixed slurry, add nitric acid and regulate Al
2O
3PH value of slurry is at 2-4.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h is load Al then
2O
3And CeO
2-ZrO
2Mixed slurry is warmed up to 500 ℃ with 5 ℃/min behind 40 ℃ of dry 2h, roasting 2h.
Embodiment 11:
Metal surface preliminary treatment: get
15 * 25mm 400cpsi (400 hole/square inch) FeCrAl metal beehive, ultrasonic cleaning 30min in acetone cleans 10min in deionized water for ultrasonic, then to remove oil, oxide and some impurity on the metal surface.120 ℃ of dry backs are carried out roasting 10h to sheet metal under 950 ℃ of high temperature.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
CeO
2-ZrO
2The preparation of slurry; With embodiment 8.
Coating load: with embodiment 8
Active constituent loading: through the load Al of preparation after the above-mentioned steps
2O
3/ CeO
2-ZrO
2The metal beehive of coating is at the chloro-iridic acid (H of 16mg/ml
2IrC16) dipping 1min takes out in the aqueous solution, and 120 ℃ of dry backs are warmed up to 500 ℃ of roasting 2h with 5 ℃/min.
Comparative Examples 12:
Metal surface preliminary treatment: with FeCrAl sheet metal ultrasonic cleaning 30min in acetone, then at ultrasonic washing with clean water 10min, to remove oil, oxide and some impurity on the metal surface.The load coating is prepared in 120 ℃ of dry backs.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
The coating load: at first load aluminium colloidal sol on the sheet metal of removing surface impurity, 40 ℃ of dry 1h are load Al then
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Comparative Examples 13:
Metal surface preliminary treatment: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
Coating load: load Al on the sheet metal behind the high-temperature oxydation
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Comparative Examples 14:
Metal surface preliminary treatment: with embodiment 1.
Al
2O
3The preparation of slurry: with 27g γ-Al
2O
3With 200ml 1.6molL
-1Aluminium colloidal sol mixing and ball milling 18h, obtain mixed slurry, add nitric acid and regulate Al
2O
3PH value of slurry is at 2-4.
Coating load: load Al on the sheet metal behind the high-temperature oxydation
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Comparative Examples 15:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
Al
2O
3The preparation of slurry: with embodiment 1.
The coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h are warmed up to 500 ℃ of roasting 2h, load Al then with 5 ℃/min
2O
3Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Comparative Examples 16:
Metal surface preliminary treatment: with embodiment 1.
The preparation of aluminium colloidal sol: with embodiment 1.
CeO
2-ZrO
2The preparation of slurry: with embodiment 3.
Coating load: load aluminium colloidal sol on the sheet metal behind the high-temperature oxydation at first, 40 ℃ of dry 1h back loading CeO
2-ZrO
2Slurry behind 40 ℃ of dry 2h, is warmed up to 500 ℃ with 5 ℃/min, roasting 2h.
Comparative Examples 17:
Get
15 * 25mm 400cpsi (400 hole/square inch) cordierite ceramic honeycomb is used 3%HNO
3Washed with de-ionized water is used in preliminary treatment 12 hours, and in 120 ℃ of oven dry 12 hours, 900 ℃ of roastings 2 hours were standby.
CeO
2-ZrO
2The preparation of slurry: with embodiment 8.
Coating load: the pretreated ceramic honeycomb load C eO of process
2-ZrO
2Slurry, 120 ℃ of dry backs are warmed up to 500 ℃ of roasting 2h with 5 ℃/min.
Active constituent loading: through the load C eO of preparation after the above-mentioned steps
2-ZrO
2The metal beehive of coating is at the chloro-iridic acid (H of 16mg/ml
2IrCl6) dipping 1min takes out in the aqueous solution, and 120 ℃ of dry backs are warmed up to 500 ℃ of roasting 2h with 5 ℃/min.
Sheet metal coating to the foregoing description gained is carried out ultrasonic, thermal shock experiment, and the adhesion between testing coating and metallic matrix, and data rows is in table 1.
The ceramic honeycomb catalyst of the metal beehive of above-mentioned example 10 preparations and Comparative Examples 17 preparations with 4% hydrazine hydrate (N
2H
2) reductase 12 4 hours, be washed till neutrality with deionized water, after the drying, in the methanol steam reforming reaction system, estimate.Gained result such as Fig. 1.
Table 1
Ultrasonic thermal shock
Coating adhesion/MPa
Expulsion rate/% expulsion rate/%
Embodiment 1:2.50 1.22 21.8
Embodiment 2 2.60 1.25 21.0
Embodiment 3 2.65 1.27 20.6
Embodiment 4 2.68 1.29 20.4
Embodiment 5 2.85 1.32 19.8
Embodiment 6 2.20 1.20 22.4
Embodiment 7 2.50 1.22 21.8
Embodiment 8 3.86 1.48 15.8
Embodiment 9 2.95 1.35 18.5
Embodiment 10 2.95 1.35 18.5
Comparative Examples 12 85.55 42.14-
Comparative Examples 13 70.63 30.65-
Comparative Examples 14 45.24 25.36-
Comparative Examples 15 27.58 13.54-
Comparative Examples 16 24.63 12.43-
Annotate:
1. ultrasonic power: in SK3200HP (operating frequency 59kHz, power 135W), be medium, calculate ultrasonic expulsion rate after the ultrasonic 20min with the deionized water.
2. thermal shock mode: 800 ℃ of following insulation 10min, it is dry to put into the cold water back then, records the coating shedding rate after 10 times repeatedly.
3. coating adhesion experimental data is according to GB GB 5210-85 " determination method of coating adhesion is drawn back method " test gained.
Claims (6)
1. the preparation method of a metal carrier catalyst coating may further comprise the steps:
(1) metallic carrier makes the metal surface generate corresponding oxide grain and the certain roughness of formation in 880-1050 ℃ of following oxidation 0.5-10h; Wherein metallic carrier is FeCrAl, FeCrAlY or 1Ni9Cr18Ti sheet metal;
(2) load aluminium Sol A lOOH and dry on the metallic matrix after step 1 oxidation processes to form the aluminium collosol coating; Aluminium Sol A lOOH concentration is 0.6-2.0molL
-1, the pH value is 2-4, the thickness of coating is 3-10 μ m;
(3) load Al on the aluminium collosol coating
2O
3Slurry is also dry to form composite coating; Al
2O
3Slurry pH value is 2-4, and coating layer thickness is 10-50 μ m, 40-120 ℃ of following dry 0.5-2h, and 500-900 ℃ of following roasting time 2-5h gets composite coating;
(4) load active component on composite coating is prepared metal carrier catalyst behind the drying and roasting.
2. preparation method as claimed in claim 1, aluminium Sol A lOOH concentration is 0.8-1.5molL in the step 2
-1
3. preparation method as claimed in claim 1, in the step 3 on the aluminium collosol coating Al of load
2O
3Slurry is by Al
2O
3Add the binding agent mixing and ball milling and form, wherein Al
2O
3With the binding agent mol ratio be 2: 1-19: 1, described binding agent is Al
2O
3H
2O, aluminium colloidal sol, Ludox, zirconium colloidal sol or titanium colloidal sol.
4. as claim 1 or 3 described preparation method, wherein Al
2O
3Slurry is by Al
2O
3, binding agent, one or several the reaction required other metal oxides or salt mixing and ball milling form.
5. preparation method as claimed in claim 4, metal oxide wherein or salt are CeO
2-ZrO
2, Ce (NO
3)
36H
2O is or/and Zr (NO
3)
45H
2O.
6. preparation method as claimed in claim 1, the roasting in the step 3 is to be warmed up to 500-900 ℃ of following roasting 2-4h with 1-15 ℃/min.
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| CN102049312B (en) * | 2009-10-27 | 2012-11-21 | 中国石油化工股份有限公司 | Preparation method of catalytic combustion catalyst |
| CN102059123B (en) * | 2010-12-12 | 2012-07-25 | 西北有色金属研究院 | Sintering FeCrAl metal fiber porous carrier catalyst and preparation method thereof |
| DE102011083054A1 (en) * | 2011-09-20 | 2013-03-21 | Hamburg Innovation Gmbh | Process for the photocatalytically active coating of surfaces |
| CN102671716B (en) * | 2012-05-23 | 2014-07-09 | 江苏高淳陶瓷股份有限公司 | High temperature-resisting active coating and preparation method thereof |
| CN103084218A (en) * | 2013-01-28 | 2013-05-08 | 江苏帕艾尼尔科技有限公司 | Method for loading coating on sponge metal and coating prepared by same |
| CN103801328B (en) * | 2014-02-17 | 2016-04-13 | 南京劲鸿茂科技有限公司 | The tai-gas clean-up catalyst of the soft carrier matrix of a kind of wire |
| CN106914240A (en) * | 2015-12-25 | 2017-07-04 | 上海华谊能源化工有限公司 | A kind of catalyst of CO gas phase couplings synthesis of oxalate and preparation method and application |
| AU2017349184B2 (en) * | 2016-10-27 | 2019-11-21 | Shell Internationale Research Maatschappij B.V. | A fischer-tropsch catalyst body |
| WO2019133367A2 (en) * | 2017-12-30 | 2019-07-04 | Saint-Gobain Ceramics & Plastics, Inc. | Mixture for making a catalyst carrier and process for making the mixture |
| CN111868307A (en) * | 2018-02-14 | 2020-10-30 | 百拉得动力系统公司 | Membrane electrode assembly with supported metal oxide |
| CN110219031B (en) * | 2019-06-06 | 2020-12-08 | 北京航空航天大学 | Anodic oxidation electrolyte and method, and aluminum or aluminum alloy with anodic oxidation film |
| CN112536053B (en) * | 2019-09-23 | 2023-09-08 | 中国石油化工股份有限公司 | Catalyst for preparing phthalic anhydride from o-xylene and preparation method thereof |
| CN111545252A (en) * | 2020-05-25 | 2020-08-18 | 大唐国际化工技术研究院有限公司 | Protection method of methanation catalyst |
| CN114618505A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Supported oxide film and preparation method and application thereof |
| CN112999987B (en) * | 2021-04-03 | 2022-05-10 | 华东理工大学 | Electric heating integral metal-based catalytic reactor and preparation method thereof |
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