CN1299826C - Noble metal carried stainless steel anodic oxide film covered catalyzer and its preparing process - Google Patents
Noble metal carried stainless steel anodic oxide film covered catalyzer and its preparing process Download PDFInfo
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- CN1299826C CN1299826C CNB031293670A CN03129367A CN1299826C CN 1299826 C CN1299826 C CN 1299826C CN B031293670 A CNB031293670 A CN B031293670A CN 03129367 A CN03129367 A CN 03129367A CN 1299826 C CN1299826 C CN 1299826C
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- stainless steel
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- oxide film
- immersed
- noble metal
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Abstract
The present invention relates to a noble metal catalyst carried with a stainless steel anodic oxide film and a preparation method thereof. The present invention is characterized in that stainless steel is used as a carrier, an anodized film is formed by an anode oxidation preparation process, and the catalyst is prepared by loading noble metal active constituents with a dipping method. The catalyst is used for processing volatile organic components (VOCs) and has the advantages of high activity and good thermal stability.
Description
Technical field
The present invention relates to a kind of catalyst that is used to handle VOC (VOCs), particularly relate to the method for stainless steel anode oxide film supported precious metal catalyst and preparation thereof.
Technical background
Be used to handle the catalysis and purification technology of VOC (VOCs) at present, adopt activated alumina is the ceramic honeycomb catalyst that second carrier-supported precious metal is made more.It is many that this catalyst is processed into shape operation such as honeycomb, the difficult repetition, and the unit volume activity is low, and consumption once is very big.Catalyst the active component sintering phenomenon can occur later through long-term the use, and activity of such catalysts is reduced, and the catalyst of sintering is difficult for regeneration generally speaking simultaneously.
Because stainless steel has excellent corrosion resistance and wearability toughness and manufacturability, exquisite appearance is widely used in every field.Anodised stainless steel generally is used to prepare colored stainless steel, and at present colored stainless steel is in large quantities as construction material, as the outer wall of skyscraper, window frame, finial, elevator cabin's interior trim etc.Also make home appliances, cooking apparatus etc. simultaneously widely, but do not utilize stainless steel after anodized as carrier, make catalyst, be used for the technology of catalytic oxidation treatment organic exhaust gas.
Summary of the invention
The purpose of this invention is to provide a kind of employing stainless steel anode oxide film supported precious metal catalyst and preparation method, be used to handle volatile organic waste gas.
Stainless steel anode oxide film supported precious metal catalyst provided by the invention, stainless steel with the surface attachment complex oxide film is a carrier, with noble metal platinum, palladium is active component, active component and carrier ratio are: containing Pt is 0.01-1.0wt%, and containing Pd is 0.05-1.0wt%/stainless steel anode oxide film carrier.
It is carrier that the present invention adopts stainless steel, adopts anodised preparation technology, covers one deck complex oxide film in the stainless steel surfaces original position, adopts dipping method carried noble metal active component to be prepared into catalyst.
The anodic oxidation membrane preparation method the steps include:
1, the stainless steel thin slice is flooded except that carrying out electrochemical deoiling in the oil solution:
2, stainless steel being carried out descale handles:
3, stainless steel carrier being removed dust handles:
4, the stainless steel carrier pre-activated is handled:
5, stainless steel carrier is immersed in the electrolyte solution fully, carries out anodized, obtain stainless steel anode oxide film.The preparation of stainless steel anode oxide film supported precious metal catalyst the steps include:
6, the stainless steel anode oxide film immersion is contained in the mixing salt solution of noble metal the carried noble metal active component:
7, the roasting regular hour under uniform temperature, air atmosphere condition, make catalyst of the present invention.
The present invention utilizes stainless steel to handle the characteristics that also easily are processed into shapes such as honeycomb at its surface generation anode oxide film through electrochemical method and makes the catalyst carrier supported precious metal catalyst, is used to handle VOC (VOCs).Active high, high temperature resistant, corrosion-resistant, shock-resistant, the anti-vibration of this stainless steel anode oxide film supported precious metal catalyst, air drag is little, Heat stability is good.
The specific embodiment
Embodiment 1
With reference to above-mentioned preparation process
The stainless steel thin slice is immersed in except that carrying out electrochemical deoiling in the oil solution, and temperature is controlled at 30-60 ℃, and the described oil solution that removes is NaOH, Na
2CO
3, Na
3PO
412H
2O and Na
2SiO
3Mixed aqueous solution, the mass ratio of each component is described in this solution: 1-4: 1: 1-4: 1-4.
Stainless steel thin slice behind the electrochemical deoiling is immersed in component H
2O, H
2SO
4, HCl, C
2H
5OH, H
2O
2Volume ratio be: 1: 0.1-0.5: 0.1-0.5: 0.1-0.5: 0.1-0.5 and an amount of (CH
2)
6N
4Mixed solution in, carry out descale, reaction temperature is 10-40 ℃, stirs, the time is 3-5 minute.
The stainless steel thin slice of descale is immersed in HNO
3And H
2In the O solution, the volume ratio of component is in the solution: 1: 0.1-1 removes dust, and reaction temperature is 10-40 ℃, and stirring dip time is 0.5-5.0 minute.
To be immersed in H except that the stainless steel thin slice of dust
2SO
4In HCl solution, the volume ratio of component is in the solution: 1: 0.1-0.5, and to carry out pre-activated and handle, the time is 0.5-20 minute.
Pretreated stainless steel thin slice is immersed in H
2SO
4In the electrolyte solution, current density is 1-5A/dm
2, voltage is 5-30V, the time is 30-120 minute, obtains original position and covers complex oxide film.
Is 0.01-1.0wt% with the stainless steel anode oxide film carrier impregnation containing Pt, contains carried noble metal active component in the solution that Pd is 0.01-1.0wt%.Placing reducing agent is that a kind of reducing agent of hydrazine hydrate (concentration is 0.1-1.0wt%), hydrogen or carbon monoxide reduces, and the described recovery time is 2-4 hour.
With the catalyst precursor of above-mentioned stainless steel anode oxide film carried noble metal, be roasting in the 500-1000 ℃ of air atmosphere in temperature, roasting time is 2-4 hour, can obtain stainless steel anode oxide film supported precious metal catalyst of the present invention.
Embodiment 2:
Specific embodiment of the preparation of stainless steel anode oxide film supported precious metal catalyst the steps include:
(1) the stainless steel thin slice is processed into certain specification, is immersed in and contains 80g NaOH, 40g Na
2CO
3, 80g Na
3PO
412 H
2O and 40g Na
2SiO
3Mixed solution in, carry out electrochemical deoiling.The oil removing time decides on deoiling effect, takes out, and is clean with deionized water rinsing.
(2) then stainless steel being carried out descale handles: press H
2O, H
2SO
4, HCl, C
2H
5OH, (CH)
6N
4, H
2O
2Order, add 500ml H successively
2O, 100ml H
2SO
4, 150ml HCl, 60ml C
2H
5OH, an amount of (CH
2)
6N
4With 125ml H
2O
2, wiring solution-forming.Stirring flooded 3 minutes down, cleaned with deionized water.
(3) stainless steel carrier of electrochemical deoiling, descale removes the dust processing: place to contain 20ml HNO
3With 10ml H
2O
2Mixed solution in, stirring is dipping 1 minute down, cleans with deionized water.
(4) stainless steel carrier is placed contain 10ml H
2SO
4In the mixed solution of 1ml HCl, pre-activated was handled 1 minute.
(5) will activate pretreated stainless steel carrier and be immersed in 500ml H fully
2SO
4In (concentration is 30wt%) electrolyte solution, control reaction time and reaction temperature are carried out anodic oxidation, after 40 minutes, stainless steel carrier are taken out, rinse well with deionized water, and 100 ℃ of oven dry, standby.
(6) as required, be processed into the waveform striped with above-mentioned stainless steel carrier, stand-by.
(7) with the stainless steel carrier for preparing, immersion contains in the mixing salt solution of noble metal 0.1wt%Pt and 0.5wt%Pd, boil, treat solution colour by yellow transfer to colourless after, stainless steel carrier is taken out, clean, soak and place the 0.3wt% hydrazine hydrate solution, take out after 2 hours, clean, oven dry gets catalyst precursor.
(8) with this catalyst precursor under 500-1000 ℃ of temperature, air atmosphere condition roasting 2-4 hour, make catalyst.
Stainless steel carrier carried noble metal of the present invention is made catalyst, handles through 500-1000 ℃ of high-temperature roasting, and the composite oxides particle diameter that catalyst surface is formed oxide-film still remains on micron order, is used to handle VOCs and has higher activity, heat endurance.As the complete oxidation temperature of handling toluene is 200 ℃ of (air speed 10000h
-1, toluene concentration 6.5g/m
3).
Embodiment 3
Anodic oxidation membrane preparation method electrochemical deoiling formula of liquid of the present invention:
| Reagent | Concentration (g/l) |
| NaOH Na 2CO 3 Na 3PO 4·12H 2O Na 2SiO 3 | 80-120 40-60 80-100 40-90 |
Embodiment 4
Anodic oxidation membrane preparation method descale formula of liquid of the present invention
| Reagent | Concentration (ml/l) |
| H 2O | 500-1000 |
| H 2SO 4 HCl H 2O 2 C 2H 5OH (CH) 6N 4 | 100-120 150-170 125-140 60-75 is an amount of |
Embodiment 5
Anodic oxidation membrane preparation method of the present invention removes the dust formula of liquid
| Reagent | Concentration (ml/l) |
| HNO 3 H 2O 2 | 20-40 10-25 |
Embodiment 6
Anodic oxidation membrane preparation method pre-activated prescription for the treatment of liquid of the present invention
| Reagent | Concentration (ml/l) |
| H 2SO 4 HCl | 10-50 1-20 |
Claims (1)
1, a kind of preparation method of stainless steel anode oxide film supported precious metal catalyst is characterized in that directly covering one deck complex oxide film with the anodizing technology original position at stainless steel surfaces, and preparation process is:
The stainless steel thin slice is immersed in except that carrying out electrochemical deoiling in the oil solution, and temperature is controlled at 30-60 ℃, and the described oil solution that removes is NaOH, Na
2CO
3, Na
3PO
412H
2O and Na
2SiO
3Mixed aqueous solution, the mass ratio of each component is described in this solution: 1-4: 1: 1-4: 1-4;
Stainless steel thin slice behind the electrochemical deoiling is immersed in component H
2O, H
2SO
4, HCl, C
2H
5OH, H
2O
2Volume ratio be: 1: 0.1-0.5: 0.1-0.5: 0.1-0.5: 0.1-0.5 and an amount of (CH
2)
6N
4Mixed solution in, carry out descale, reaction temperature is 10-40 ℃, stirs, the time is 3-5 minute;
The stainless steel thin slice of descale is immersed in HNO
3And H
2In the O solution, remove dust, the volume ratio of component is 1 in the solution: 0.1-1, and reaction temperature is 10-40 ℃, stirring dip time is 0.5-5.0 minute;
To be immersed in H except that the stainless steel thin slice of dust
2SO
4In HCl solution, carry out pre-activated and handle, the component volume ratio is 1 in the solution: 0.1-0.5, the time is 0.5-20 minute;
Pretreated stainless steel thin slice is immersed in H
2SO
4In the electrolyte solution, current density is 1-5A/dm
2, voltage is 5-30V, the time is 30-120 minute, obtains original position and covers complex oxide film;
Is 0.01-1.0wt% with the stainless steel anode oxide film carrier impregnation containing Pt, contain carried noble metal active component in the solution that Pd is 0.01-1.0wt%, placing concentration is that a kind of reducing agent of hydrazine hydrate, hydrogen or the carbon monoxide of 0.1-1.0wt% reduces, and the time is 2-4 hour;
With the catalyst precursor of above-mentioned stainless steel anode oxide film carried noble metal, be roasting in the 500-1000 ℃ of air atmosphere in temperature, roasting time is 2-4 hour, can obtain stainless steel anode oxide film supported precious metal catalyst of the present invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031293670A CN1299826C (en) | 2003-06-16 | 2003-06-16 | Noble metal carried stainless steel anodic oxide film covered catalyzer and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031293670A CN1299826C (en) | 2003-06-16 | 2003-06-16 | Noble metal carried stainless steel anodic oxide film covered catalyzer and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1565742A CN1565742A (en) | 2005-01-19 |
| CN1299826C true CN1299826C (en) | 2007-02-14 |
Family
ID=34469304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031293670A Expired - Fee Related CN1299826C (en) | 2003-06-16 | 2003-06-16 | Noble metal carried stainless steel anodic oxide film covered catalyzer and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1299826C (en) |
Families Citing this family (3)
| 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 |
| 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 |
| CN113481530A (en) * | 2021-07-28 | 2021-10-08 | 澳门大学 | Stainless steel-based catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4934474A (en) * | 1972-08-02 | 1974-03-29 | ||
| US4918042A (en) * | 1987-07-09 | 1990-04-17 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| CN2214530Y (en) * | 1994-12-27 | 1995-12-06 | 上海久新搪瓷厂新桥分厂 | Automotive tail gas purifier |
-
2003
- 2003-06-16 CN CNB031293670A patent/CN1299826C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4934474A (en) * | 1972-08-02 | 1974-03-29 | ||
| US4918042A (en) * | 1987-07-09 | 1990-04-17 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| CN2214530Y (en) * | 1994-12-27 | 1995-12-06 | 上海久新搪瓷厂新桥分厂 | Automotive tail gas purifier |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1565742A (en) | 2005-01-19 |
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Granted publication date: 20070214 |