CN101274282B - Method for preparing stainless steel screen anodic oxide film supported rare earth metal-precious metal catalyst - Google Patents
Method for preparing stainless steel screen anodic oxide film supported rare earth metal-precious metal catalyst Download PDFInfo
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- CN101274282B CN101274282B CN200810062376XA CN200810062376A CN101274282B CN 101274282 B CN101274282 B CN 101274282B CN 200810062376X A CN200810062376X A CN 200810062376XA CN 200810062376 A CN200810062376 A CN 200810062376A CN 101274282 B CN101274282 B CN 101274282B
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- stainless steel
- carrier
- catalyst
- rare earth
- steel cloth
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Abstract
The invention discloses a preparation method of a catalyst which loads rare earth metals and noble metals with an anodic oxide film carrier of a stainless steel wire mesh, which takes the stainless steel wire mesh that has composite oxide films adhered on the surface as a carrier, and cerium of rear earth metals as well as platinum and palladium of noble metals as active components, the contents of the active components of the catalyst are 0.75 percent of cerium oxide, 0.1 percent of platinum and 0.5 percent of palladium by weight, and the catalyst adopts the anodic oxidation preparation technique to form the anodic oxide film and adopts the steeping method to load the active components of Ce of rear earth metals and Pt, Pd of noble metals. The catalyst is used for processing volatile exhaust organic gas ( like toluol, acetone and ethyl acetate, etc. ), has ultrahigh activity and thermal stability, and is a catalyst that has application prospect.
Description
Technical field
The present invention relates to a kind of catalyst that is used to handle volatile organic waste gas (VOCs), particularly relate to carrier loaded rare earth metal-precious metal catalyst of stainless steel cloth anodized film metallic and preparation method thereof.
Background technology
Because stainless steel cloth has heat-resisting quantity, easily is processed into advantages such as different shape, can be used as a kind of novel catalyst carrier.Make stainless steel wire form one deck on the net by the anodizing technology process from growing oxide-film, the catalyst of carried noble metal preparation then, can overcome the poor heat stability that in the past adopted the activated alumina carried noble metal to make ceramic catalyst, shortcoming such as frangible is a kind of catalyst with application prospect.
Chinese patent ZL03129367.0 and 200710067768.0 relates to a kind of stainless steel anode oxide film supported precious metal catalyst preparation method, the steps include: electrochemical deoiling, descale is handled, remove dust and handle, pre-activated is handled, anodized, obtain stainless steel anode oxide film, the carried noble metal active component, above-mentioned two kinds of better, high temperature resistant, shock-resistant, anti-vibrations of stainless steel anode oxide film supported precious metal catalyst activity, Heat stability is good.Problems such as but it is narrow to exist the carrier application surface, and preparation process is many.
Chinese patent 200810059778.40 relates to the anodic oxide film supported noble metal catalyst of a kind of stainless steel metal silk screen carrier, has enlarged the carrier application surface, but the catalyst activity that obtains is not high enough.The carrier loaded rare earth metal-precious metal catalyst cost of stainless steel metal wire screen anodic oxide film is low by contrast, compare with the stainless steel anode oxide film supported precious metal catalyst of foregoing existing better VOCs clean-up effect, its catalytic performance is higher, to toluene, acetone, the complete oxidation of ethyl acetate has descended 60 ℃ respectively, 40 ℃ and 30 ℃.
Summary of the invention
The present invention seeks on above-mentioned three patent bases, to improve, optimize preparation technology and condition, further improve the low temperature active of catalyst, the preparation method of the carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film is provided, be used to handle volatile organic waste gas.
The present invention utilizes rare earth to have particular configurations of electronic shell, and cerium oxide has unique redox property, has good effect for catalyst combustion reaction; And stainless steel cloth has high stability, easily is processed into advantages such as different shape, as a kind of carrier of novel catalyst, by the rare earth metal-precious metal catalyst of anodizing and secondary dipping process preparation, is a kind of catalyst that big application prospect is arranged.
The carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film provided by the invention, be to be carrier with surface attachment complex oxide film stainless steel cloth, with rare earth metal cerium, noble metal platinum, palladium is active component, and described catalyst activity constituent content is: cerium oxide 0.75wt%, platinum 0.1wt% and palladium 0.5wt%.
The preparation method of the carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film provided by the invention adopts anodizing technology to form oxide-film on the net at stainless steel wire and makes metal beehive carrier; Adopt dipping method supported rare earth metal and noble metal active component, be prepared into catalyst.Preparation process is:
1, stainless steel cloth is processed into required specification, makes cellularly, the silk screen carrier is carried out descale handle, remove that dust is handled, pre-activated is handled, anodized, obtain stainless steel cloth combined oxidation membrane carrier;
2,, immerse in the solution of the cerous nitrate that contains the 0.75wt% cerium oxide supported rare earth cerium with the stainless steel cloth carrier in the step 1, dip time is 1h, and stainless steel carrier is taken out, and cleans, 100 ℃ of oven dry obtain the stainless steel cloth complex oxide film metallic carrier that load has rare earth metal cerium;
3, with the stainless steel cloth carrier that obtains in the above-mentioned steps 2, be immersed in the chloroplatinic acid and chlorine palladium acid solution that contains noble metal 0.1wt%Pt, 0.5wt%Pd, boil, treat solution colour by yellow transfer to colourless after, the stainless steel cloth carrier is taken out, clean, place the reducing agent of concentration 0.1wt% hydrazine hydrate, reduced 1 hour, and obtained the catalyst precursor of the carrier loaded rare earth metal-precious metal of stainless steel metal wire screen anodic oxide film;
4, the stainless wire net catalyst presoma that above-mentioned steps 3 is obtained is roasting 1 hour in the 500-800 ℃ of air atmosphere in temperature, obtains the carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film.
The descale that carries out of the present invention is handled, and stainless steel cloth is immersed in add H successively
2O, H
2SO
4, HCl, C
2H
5OH, an amount of (CH
2)
6N
4, H
2O
2In the solution 1.0-3.0 minute, described Solution H
2O, H
2SO
4, HCl, C
2H
5OH, H
2O
2Volume ratio be: 26: 1: 1: 1: 1.
The dust of removing of the present invention is handled, and under room temperature and stirring, the stainless steel cloth carrier impregnation after descale handled is 1: 0.5: 35 HNO in volume ratio
3, H
2O
2, H
2In the O solution 1-3 minute.
Pre-activated of the present invention is handled, and will be 10: 1 H except that the stainless steel cloth carrier impregnation after the dust processing in volume ratio
2SO
4, in the HCl solution 0.5-2 minute.
Anodized of the present invention is handled back stainless steel cloth carrier impregnation at H with pre-activated
2SO
4In the electrolyte solution, current density is 10-1A/dm
2, voltage is 3-5V, the time is 30 minutes.
Stainless steel metal silk screen carrier anodic oxidation film catalyst provided by the invention, active component contains rare earth metal cerium and noble metal platinum and palladium, because cerium oxide has unique redox property, good catalytic activity; Stainless steel cloth has high stability and has good heat-conducting, and easily be processed into advantages such as different shape, processing through anode oxidation process, the surface forms the metal honeycomb catalyst that complex oxide film back loading active component is made, be used to handle volatile organic waste gas (as toluene, acetone, ethyl acetate etc.), have the advantage of active height, Heat stability is good.After 500 ℃ of temperature calcination process, be 160 ℃ to the complete conversion temperature of toluene, be 220 ℃ to the complete conversion temperature of acetone, be 250 ℃ to the complete conversion temperature of ethyl acetate.Investigate to find through catalyst life: this catalyst 180 ℃ than under the low reaction temperatures, long-time its complete activity of conversion to toluene of running remained unchanged substantially through 150 hours.In similar catalysts for environmental protection, have higher catalytic activity and superior performance, market application foreground is wide.
The specific embodiment
Embodiment 1
With reference to above-mentioned preparation process
● stainless steel cloth is processed into cellular, is immersed in and adds people H successively
2O, H
2SO
4, HCl, C
2H
5OH, an amount of (CH
2)
6N
4, H
2O
2Solution in, above-mentioned Solution H
2O: H
2SO
4: HCl: C
2H
5OH: H
2O
2Volume ratio be 26: 1: 1: 1: 1, carry out descale, reaction temperature is a room temperature, stirs, the time is 1 minute.
● the stainless steel cloth of descale is immersed in HNO
3, H
2O
2Solution in, HNO
3: H
2O
2Volume ratio is to remove dust at 2: 1, and reaction temperature is a room temperature, stirs dip time 3 minutes.
● will be immersed in volume ratio except that the stainless steel cloth after the dust and be 10: 1 H
2SO
4, HCl solution in, carry out pre-activated and handle, 1 minute time.
● pretreated stainless steel cloth is immersed in H
2SO
4In the electrolyte solution, current density is 10A/dm
2, voltage is 5V, the time is 30 minutes, obtains the anodic oxidation membrane carrier.
● with the stainless steel anode oxide film carrier, be immersed in the Ce (NO of oxidation-containing cerium 0.75wt%
3)
3In the aqueous solution, after 100 ℃ of oven dry, be impregnated into solution again and contain noble metal to contain Pt be 0.1wt%, contain carried noble metal active component in the solution that Pd is 0.5wt%.Place reducing agent hydrazine hydrate (concentration is 0.1wt%) to reduce time 1h.
● with above-mentioned stainless steel anode oxide film supported rare earth metal, the catalyst precursor of noble metal, 500 ℃ of roastings 1 hour.
Above-mentioned catalyst is used to handle volatile organic waste gas, complete conversion temperature to toluene is 160 ℃, complete conversion temperature to acetone is 220 ℃, complete conversion temperature to ethyl acetate is 250 ℃, catalyst life is investigated, this catalyst 180 ℃ than under the low reaction temperatures, long-time its complete activity of conversion to toluene of running remained unchanged through 96 hours.
Embodiment 2:
Method with reference to embodiment 1 preparation
● stainless steel cloth is processed into certain specification, makes cellular.
● then cellular silk screen carrier is carried out descale and handle: press H
2O, H
2SO
4, HCl, C
2H
5OH, (CH
2)
6N
4, H
2O
2Order, add 780ml H successively
2O, 30ml H
2SO
4, 30ml HCl, 30ml C
2H
5OH, an amount of (CH
2)
6N
4, 30ml H
2O
2, wiring solution-forming.Cellular silk screen carrier is immersed in the above-mentioned solution, and dipping is 2 minutes under stirring, cleans with deionized water.
● the cellular silk screen carrier of electrochemical deoiling, descale removes the dust processing: place to contain 30mlHNO
3, 15ml H
2O
2, 955mlH
2In the mixed solution of O, stirring flooded 1 minute down, cleaned with deionized water.
● above-mentioned cellular stainless steel carrier placed contain 10mlH
2SO
4, 1mlHCl mixed solution in, pre-activated was handled 1 minute.
● will activate pretreated cellular silk screen carrier and be immersed in 1000mlH fully
2SO
4In (concentration is 10wt%) electrolyte solution, control reaction time and reaction temperature are carried out anodic oxidation, after 30 minutes, stainless steel carrier are taken out, rinse well with deionized water, and 100 ℃ of oven dry, standby.
● the cellular silk screen carrier that will prepare, 1h in the cerium nitrate solution of immersion oxidation-containing cerium 0.75wt%, 100 ℃ of oven dry, immerse again and contain in the chloroplatinic acid and chlorine palladium acid solution of noble metal 0.1wt%Pt, 0.5wt%Pd, boil, treat solution colour by yellow transfer to colourless after, the silk screen carrier is taken out, clean, be dipped in the solution that concentration is the 0.1wt% hydrazine hydrate and reduce, take out behind the 1h, clean, oven dry gets catalyst precursor.
● with the roasting 1 hour under 800 ℃ of air atmosphere conditions of this catalyst precursor, make catalyst.
The carrier loaded rare earth metal of cellular stainless steel cloth of the present invention, noble metal is made catalyst, through 400-800 ℃ of temperature range calcination process, significant change does not appear in the composite oxides particle diameter that catalyst surface is formed oxide-film, is used to handle organic exhaust gas and has higher activity, heat endurance.
Claims (1)
1. the preparation method of the carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film, it is characterized in that the stainless steel cloth with the surface attachment complex oxide film is a carrier, with rare earth metal cerium, noble metal platinum, palladium is active component, described activity of such catalysts constituent content is: cerium oxide 0.75wt%, platinum 0.1wt% and palladium 0.5wt%, adopt anodic oxidation preparation technology to form anode oxide film, adopt dipping method supported rare earth Elements C e and precious metals pt, the Pd active component, preparation process is as follows:
1) stainless steel cloth is processed into required specification, the silk screen carrier is carried out descale handle, remove dust processing, pre-activated processing, anodized, obtain stainless steel cloth combined oxidation membrane carrier, the described descale that carries out is handled, and stainless steel cloth is immersed in add H successively
2O, H
2SO
4, HCl, C
2H
5OH, an amount of (CH
2)
6N
4, H
2O
2Solution in 1.0-3.0 minute, H in the described solution
2O, H
2SO
4, HCl, C
2H
5OH, H
2O
2Volume ratio be 26: 1: 1: 1: 1; The described dust of removing is handled, and under room temperature and stirring, is 1: 0.5: 35 HNO in volume ratio with the stainless steel cloth carrier impregnation
3, H
2O
2, H
2In the O solution 1.0 minutes; Described pre-activated is handled, and is 10: 1 H in volume ratio with the stainless steel cloth carrier impregnation
2SO
4, in the HCl solution 0.5-2.0 minute; Described anodized, with the stainless steel cloth carrier impregnation at electrolyte solution H
2SO
4In, current density is 10-1A/dm
2, voltage is 1.5-5.0V, the time is 30 minutes;
2) with the stainless steel cloth carrier that obtains in the step 1), immersion contains supported rare earth metallic cerium in the solution of cerous nitrate of 0.75wt% cerium oxide, dip time is 1 hour, the stainless steel cloth carrier is taken out, clean, 100 ℃ of oven dry obtain the stainless steel cloth combined oxidation membrane carrier that load has rare earth metal cerium;
3) with above-mentioned steps 2) the middle stainless steel cloth carrier that obtains, be immersed in the solution of the chloroplatinic acid that contains noble metal 0.1wt%Pt and 0.5wt%Pd and the acid of chlorine palladium, boil, treat solution colour by yellow transfer to colourless after, the stainless steel cloth carrier is taken out, clean, place the reducing agent of concentration 0.1wt% hydrazine hydrate, reduced 1 hour, and obtained the catalyst precursor of the carrier loaded rare earth metal-precious metal of stainless steel metal wire screen anodic oxide film;
4) with above-mentioned steps 3) in the stainless wire net catalyst presoma that obtains, be roasting 1 hour in the 500-800 ℃ of air atmosphere in temperature, obtain the carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810062376XA CN101274282B (en) | 2008-05-13 | 2008-05-13 | Method for preparing stainless steel screen anodic oxide film supported rare earth metal-precious metal catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810062376XA CN101274282B (en) | 2008-05-13 | 2008-05-13 | Method for preparing stainless steel screen anodic oxide film supported rare earth metal-precious metal catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101274282A CN101274282A (en) | 2008-10-01 |
| CN101274282B true CN101274282B (en) | 2010-07-14 |
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|---|---|---|---|
| CN200810062376XA Expired - Fee Related CN101274282B (en) | 2008-05-13 | 2008-05-13 | Method for preparing stainless steel screen anodic oxide film supported rare earth metal-precious metal catalyst |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5615058B2 (en) * | 2010-06-29 | 2014-10-29 | バブコック日立株式会社 | Method for producing metal substrate for exhaust gas denitration catalyst |
| CN103769164B (en) * | 2014-01-10 | 2016-01-20 | 浙江工业大学 | A kind of stainless steel cloth load platinum catalyst and application thereof |
| CN103933996B (en) * | 2014-04-22 | 2016-05-25 | 华东理工大学 | Anodic oxidation and plating combination preparation Co/Al2O3The method of/stainless steel integrated formula catalyst |
| CN109351182A (en) * | 2018-11-27 | 2019-02-19 | 蓝天环保设备工程股份有限公司 | A kind of Sinter-plate Filter with VOCs remove |
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Granted publication date: 20100714 Termination date: 20110513 |