CN101284240A - Preparation method of Yt-Pd stainless wire net catalyst - Google Patents
Preparation method of Yt-Pd stainless wire net catalyst Download PDFInfo
- Publication number
- CN101284240A CN101284240A CNA200810062150XA CN200810062150A CN101284240A CN 101284240 A CN101284240 A CN 101284240A CN A200810062150X A CNA200810062150X A CN A200810062150XA CN 200810062150 A CN200810062150 A CN 200810062150A CN 101284240 A CN101284240 A CN 101284240A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- steel cloth
- carrier
- yttrium
- solution
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 49
- 239000010935 stainless steel Substances 0.000 claims abstract description 48
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 17
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 238000005516 engineering process Methods 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 239000010970 precious metal Substances 0.000 claims description 12
- 239000000428 dust Substances 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000010407 anodic oxide Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- 239000010815 organic waste Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000007743 anodising Methods 0.000 description 3
- 229910018879 Pt—Pd Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- -1 dip time is 1h Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a method for preparing an yttrium-palladium stainless steel screen catalyst. A stainless steel screen, the surface of which is attached with a composite oxide film, is used as a carrier; rare earth metal yttrium and noble metal palladium are used as active components; the catalyst has the active component contents that the yttrium is 8wt percent and the palladium is 0.5wt percent; an anodic oxide film is formed by adopting an anodic oxidation preparation technology; a dipping method is utilized to load the active components of lanthanon Y and noble metal Pd. The catalyst is used for treating volatile organic waste gas (such as toluene, acetone, ethyl acetate, etc.), and has higher activity; because lanthanon Y is introduced and the noble metal adopts the palladium with low price, the cost is lowered, and greater application prospect is achieved.
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 one noble metal catalyst of stainless steel cloth anodized film metallic and preparation method thereof.
Background technology
Catalyst carrier is to realize an efficient key factor that purifies.In recent years, researched and developed the highly active new support of some high stabilities, wherein metallic carrier becomes a research focus, but there is smooth surface in it, and active component is difficult for the shortcoming of load.The present invention selects the carrier of stainless steel cloth as catalyst for use, adopts the anodizing technology of metal surface, makes its surface self-grown go out layer oxide film, preferably load active component yttrium and palladium.Zhi Bei catalyst Heat stability is good by this method, bullion content is few, is a kind of catalyst with application prospect.
Disclosed Chinese patent ZL03129367.0 and 200710067768.0 relates to two kinds of stainless steel anode oxide film supported precious metal catalyst preparation methods, 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 another 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 Chinese patent 200810062376.X 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, catalytic activity is higher, but because the noble metal in this catalyst (Ce-Pt-Pd/ stainless steel metal silk screen) active component adopts the Pt-Pd bi-component, cost is higher relatively, and how reducing cost and keeping activity is the problem that needs solution.
Summary of the invention
The present invention improves on above-mentioned four patent bases, and by the modulation of active component, purpose is to guarantee cheaply further to improve the low temperature active of catalyst under the prerequisite.Therefore the preparation method of the carrier loaded rare earth metal of stainless steel metal wire screen anodic oxide film-one pack system noble metal catalyst is provided, is used to handle volatile organic waste gas.
The rare earth yttrium can stabilizing catalyst activity component, can make more O
2 -Species and anion vacancy interact, thereby form the oxygen vacancy favourable to catalytic oxidation.The present invention utilizes these characteristics of rare earth yttrium; Adopting stainless steel cloth is on the original base of catalyst carrier, and the rare earth metal-one pack system noble metal catalyst by anodizing and secondary dipping process preparation has big application prospect and developing target market.
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 yttrium and precious metal palladium is active component, and described catalyst activity constituent content is: yttrium 8wt% and palladium 0.5wt%.
The carrier loaded rare earth metal-precious metal catalyst of stainless steel metal wire screen anodic oxide film provided by the invention is compared with above-mentioned four patents, the advantage that has is that the noble metal kind of load reduces to some extent, because price (Pt) is greatly between 450-550 unit/gram, and the price of palladium (Pd) differs nearly 2 times only between 160-200 unit/gram.Noble metal has in the present invention only been selected palladium for use, has reduced the comparatively consumption of expensive metal platinum of price, and range of application is more extensive.
The invention provides the preparation method of highly active Yt-Pd stainless wire net catalyst, adopt anodizing technology to form oxide-film on the net and make metal beehive carrier at stainless steel wire; Adopt dipping method supported rare earth metal Y and precious metals pd 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, with the stainless steel cloth carrier in the step 1, immersion contains in the yttrium nitrate solution of yttrium 8wt% the supported rare earth yttrium, 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 the rare earth metal yttrium;
3, with the stainless steel cloth carrier that obtains in the above-mentioned steps 2, be immersed in the chlorine palladium acid solution that contains noble metal 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 y-precious metals pd 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 500 ℃ of air atmosphere in temperature, obtains highly active Yt-Pd stainless wire net catalyst.
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 0.5-2.5A/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 yttrium and precious metal palladium.Rare earth yttrium energy stabilizing catalyst activity component, the price of palladium is lower by nearly 50% than platinum, stainless steel metal silk screen carrier is through the processing of 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.), has active height, the advantage that cost is low.After 500 ℃ of temperature calcination process, be 200 ℃ to the complete conversion temperature of toluene, be 260 ℃ to the complete conversion temperature of acetone, be 280 ℃ to the complete conversion temperature of ethyl acetate.In similar catalysts for environmental protection, have cost performance preferably, have market application foreground.
The specific embodiment:
With reference to above-mentioned preparation process
● stainless steel cloth is processed into required 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 0.5-2.5A/dm
2, voltage is 1.5-5.0V, the time is 30 minutes, obtains the anodic oxidation membrane carrier.
● with the stainless steel anode oxide film carrier, immerse in the yttrium nitrate solution contain yttrium 8wt% after 1 hour, oven dry is immersed in and contains carried noble metal active component in the boiling water 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, after 500 ℃ of temperature calcination process, is 200 ℃ to the complete conversion temperature of toluene, is 260 ℃ to the complete conversion temperature of acetone, is 280 ℃ to the complete conversion temperature of ethyl acetate.
Claims (5)
1, a kind of preparation method of Yt-Pd stainless wire net catalyst, it is characterized in that with surface attachment complex oxide film stainless steel cloth be carrier, with the rare earth metal yttrium, precious metal palladium is an active component, active component content is: yttrium 8wt% and palladium 0.5wt%, adopt anodic oxidation preparation technology to form anode oxide film, adopt dipping method supported rare earth element Y and precious metals pd active component, preparation process is as follows:
● 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;
● with the acquisition stainless steel cloth carrier in the step 1, immersion contains in the yttrium nitrate solution of yttrium 8wt%, and dip time is 1 hour, and the stainless steel cloth carrier is taken out, and cleans 100 ℃ of oven dry, the stainless steel cloth combined oxidation membrane carrier of acquisition supported rare earth metallic yttrium;
● with the stainless steel cloth carrier that obtains in the above-mentioned steps 2, be immersed in the chlorine palladium acid solution that contains 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 Yt-Pd stainless wire net catalyst presoma;
● the stainless wire net catalyst presoma that above-mentioned steps 3 is obtained is roasting 1 hour in 500 ℃ of air atmosphere in temperature, obtains Yt-Pd stainless wire net catalyst.
2, according to the described Preparation of catalysts method of claim 1, it is characterized in that described descale handles, stainless steel cloth is immersed in adds 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, described Solution H
2O, H
2SO
4, HCl, C
2H
5OH, H
2O
2Volume ratio be: 26: 1: 1: 1: 1.
3, according to the described Preparation of catalysts method of claim 1, it is characterized in that the described dust processing that removes, under room temperature and stirring, with the stainless steel cloth carrier impregnation in volume ratio be: 1: 0.5: 35 HNO
3, H
2O
2, H
2In the O solution 1.0 minutes.
4, according to the described Preparation of catalysts method of claim 1, it is characterized in that described pre-activated processing, with the stainless steel cloth carrier impregnation in volume ratio be: 10: 1 H
2SO
4, in the HCl solution 0.5-2.0 minute.
5, according to the described Preparation of catalysts method of claim 1, it is characterized in that described anodized, is 10% H at mass fraction with the stainless steel cloth carrier impregnation
2SO
4In the electrolyte solution, current density is 0.52.5A/dm
2, voltage is 1.5-5.0V, the time is 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810062150XA CN101284240B (en) | 2008-06-03 | 2008-06-03 | Preparation method of Yt-Pd stainless wire net catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810062150XA CN101284240B (en) | 2008-06-03 | 2008-06-03 | Preparation method of Yt-Pd stainless wire net catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101284240A true CN101284240A (en) | 2008-10-15 |
| CN101284240B CN101284240B (en) | 2010-07-14 |
Family
ID=40056783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810062150XA Expired - Fee Related CN101284240B (en) | 2008-06-03 | 2008-06-03 | Preparation method of Yt-Pd stainless wire net catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101284240B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985179A (en) * | 2010-06-29 | 2013-03-20 | 巴布考克日立株式会社 | Method for producing metal substrate for flue 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 |
-
2008
- 2008-06-03 CN CN200810062150XA patent/CN101284240B/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102985179A (en) * | 2010-06-29 | 2013-03-20 | 巴布考克日立株式会社 | Method for producing metal substrate for flue gas denitration catalyst |
| CN102985179B (en) * | 2010-06-29 | 2014-11-05 | 巴布考克日立株式会社 | Method for producing metal substrate for flue 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101284240B (en) | 2010-07-14 |
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Granted publication date: 20100714 Termination date: 20110603 |