CN1238108C - Catalyzer for purifying CO under certain environmental condition - Google Patents
Catalyzer for purifying CO under certain environmental condition Download PDFInfo
- Publication number
- CN1238108C CN1238108C CN 02148901 CN02148901A CN1238108C CN 1238108 C CN1238108 C CN 1238108C CN 02148901 CN02148901 CN 02148901 CN 02148901 A CN02148901 A CN 02148901A CN 1238108 C CN1238108 C CN 1238108C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- temperature
- under
- feox
- carrier
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a catalyst for catalyzing and purifying CO under the environment temperature and the environmental moisture. The catalyst has the characteristics of low temperature activity, moisture resistance and sulfur poisoning resistance. Gold is selected as an active component of the catalyst, and a carrier is a composite oxide carrier MOx/Al2 O3, wherein MOx comprises CoOx or FeOx, NiOx, MnOx, CuOx, ZnOx, etc. CO can be completely converted to nontoxic CO2 under the condition that the CO concentration is from 50 to 20000 ppm, the gas volume air speed is from 1*10<3> to 2.5*10<4>h<-1> at ordinary pressure, the reaction temperature is from -30 to 50 DEG C, and the environment relative humidity is from 20 to 100%. The catalyst can be used for various masks and apparatuses for preventing CO and used for air purification in a room, especially a plurality of special or closed environment.
Description
Affiliated technical field
The present invention be a kind of can be under environment temperature and ambient humidity the catalyst of catalytic purification of CO.Be mainly used in mask and the device of various anti-CO, and be used for indoor especially some air cleanings special or closed environment.
Background technology
The CO purifying and catalyzing material that uses over a long period of time is Hopcalite (being mainly the composite oxides of Cu, Mn).From the situation of present China, the CO scavenging material of equipping at some big protectors mainly is Hopcalite, and the effect of this catalyst normal temperature catalysis CO is fine, but the water-resistance extreme difference is met just inefficacy of Trace water, therefore is difficult to use for a long time and preserve.
The noble metal platinum of load, palladium catalyst also are relatively effectively catalyst of catalysis CO oxidation always.Pt/SnOx[Stark D.S., Haris M.R.J.Phys.E 1988,21:715] be proved to be very effective for a long time to catalysis CO oxidation.Weak point is to give the processing more complicated, and at room temperature, can not play effective function.Recently, Dong etc. [Dong, G.L., Wang, J.G., Gao, Y.B., Chen, S.Y., Catalysis Letters, 1999,58:37] use a kind of new catalyst---the Pd/CeO of Prepared by Sol Gel Method
2-TiO
2Catalytic activity to be higher than Pd/CeO
2, Pd/SnO
2-TiO
2, Pd/ZrO
2-TiO
2, Pd/Al
2O
3-TiO
2, Pd/TiO
2It can be at 50 ℃ of CO that are catalytically conveted to CO 100%
2
The Wacker catalyst is by PdCl
2-CuCl
2A class catalyst of forming, the Wacker catalyst of load has shown activity [Park, the E.D. of good low-temperature oxidation CO, Choi, S.H., Lee, J.S., J.Phys.Chem.B:2000,104,5586], and have in the presence of water and the halogen stable, but it just reaches maximum catalytic activity at 40 ℃, and the temperature rising can cause active decline.The CO oxidation reaction is heat release, so the operating temperature of this catalyst is subjected to strict restriction [Kim K.D., Nam I.S., Chung J.S.et al, Appl.Catal.B, 1994,5:103].Au/Fe2O3, the Au catalyst that Au/NiO etc. are oxide carried has very high activity [Haruta M., Yamada N.J.Catal.1989,115:301] to CO oxidation under the room temperature.An Liduns etc. [Chinese patent application CN 00122829] load on gold on single oxide carrier, have prepared can have good catalytic activity under (relative humidity 60%～100%) under environment temperature (10～40 ℃) and the ambient humidity and can satisfy the practical catalyst that requires of breathing mask.If but gold is loaded on single carrier A l
2O
3On, generally can not get having the load gold catalyst of low temperature active, if gold is loaded on the independent transition metal oxide, the catalyst that then makes generally has suitable difficulty in realizing industrialized process.
Summary of the invention
The object of the present invention is to provide under a kind of at ambient temperature (30～50 ℃) and the ambient humidity (relative humidity is 20～100%), have good purification CO activity, stable performance is with Al
2O
3Be base material, transition metal oxide is Second support, have the catalyst suitability for industrialized production prospect, that can satisfy actual operation requirements.
The technical solution adopted for the present invention to solve the technical problems is: preparation CO cleaning catalyst, and its active component is gold, carrier is complex carrier oxide M Ox/Al
2O
3, wherein the M among the MOx is Co, Ni, Fe, Mn, Cu or Zn, Au and Al
2O
3Weight ratio is 1.0: 10～10
3, MOx and Al
2O
3Weight ratio is 1.0: 0.5～10
3
The used Preparation of catalysts method of the present invention mainly adopts deposition-precipitation method.Catalyst deposit precipitation method preparation process: the complex carrier oxide of moulding is placed the active component precursor solution, under strong stirring, be added dropwise to aqueous slkali (as Na
2CO
3, K
2CO
3, NaOH, urea, ammoniacal liquor etc.).Control the temperature of solution and control certain pH value, until precipitation can obtain required catalyst through sedimentation, filtration, washing, drying, roasting or activation process fully.This catalyst is in the situation of 50～20000ppm to CO concentration, and the gas volume space velocity is 1 * 10 under normal pressure
3～2.5 * 10
4h
-1The time, reaction temperature is under 20～100% the condition, CO can be catalytically conveted to CO fully for-30～50 ℃, envionmental humidity
2
Catalyst carrier Al of the present invention
2O
3, CoO
x, NiO
x, FeO
x, MnO
x, CuO
x, ZnO
xCan be from aluminium oxide, cobalt oxide, iron oxide, nickel oxide, manganese oxide, cupric oxide, the zinc oxide of aluminium salt liquid, cobalt salt liquid, nickel salt liquid, molysite liquid, manganese saline solution, mantoquita liquid, zinc salt liquid and powder or moulding.Gold can be from salt or metal, as HAuCl
4, AuCl
3With Au etc.
Catalyst of the present invention carries out CO catalytic oxidation performance evaluation on atmospheric fixed bed reactor, raw materials used gas consists of: CO:0.2～2%, all the other are air.The CO concentration of turnover reactor is by the gas chromatographic analysis result, and the minimum detectable range of CO is measured and is 50ppm.
Compared with the prior art, the beneficial effect that the present invention has is: 1. have the activity of catalysis CO under the good environment temperature, can be low to moderate under-30 ℃ the temperature, catalysis CO changes CO fully into
22. has the ability that good anti-steam is poisoned; 3. has good sulfur poisoning-resistant ability; 4. be preformed catalyst.
The specific embodiment
Example 1: adopt deposition-precipitation method to prepare Au catalyst.Get the composite oxide carrier CoOx/Al of moulding
2O
31.0g, it is joined in the distilled water, under strong agitation, use 0.5M Na
2CO
3It is 8 that solution is regulated the pH value.Heating, and the maintenance system temperature is 70 ℃.Dropwise add 0.1M gold chloride 0.25mL then, continue to drip the Na of 0.5M simultaneously
2CO
3With maintenance system pH value is 8.React after 1 hour, filter, wash, 90 ℃ of lower dry nights, 400 ℃ of roastings, namely can get Au: CoOx: CoOx/Al then
2O
3Weight ratio is 1: 10: 200 Au/CoOx/Al
2O
3Catalyst.Finished product is coccoid, is even black.
Consist of CO:0.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 8000h
-1, this catalyst CO is converted into CO fully
2Permission minimum response temperature be-18 ℃ (255K).
Example 2: adopt example 1 described deposition-precipitation method to prepare Au catalyst.Get the composite oxide carrier CoOx/Al of moulding
2O
31.0g, it is joined in the distilled water, under strong agitation, add urea 5.0g.Add 0.1M gold chloride 0.25mL then, heating, and the maintenance system temperature is 70 ℃, reaches 8.0 until system pH.Filter, wash, 90 ℃ of lower dry nights, 400 ℃ of roastings, namely can get Au: CoOx: CoOx/Al then
2O
3Weight ratio is 1: 10: 200 Au/CoOx/Al
2O
3Catalyst.Finished product is coccoid, is even black.
When adopting unstripped gas described in the example 1 and gas volume air speed, this catalyst CO is converted into CO fully
2Permission minimum response temperature be lower than-30 ℃ (＜243K).
Example 3: with 1.0g FeOx/Al
2O
3Carrier joins in the distilled water, adopts example 2 described deposition-precipitation methods to prepare Au: FeOx: FeOx/Al
2O
3Weight ratio is 1: 10: 200 Au/FeOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
When adopting unstripped gas described in the example 1 and gas volume air speed, this catalyst CO is converted into CO fully
2Permission minimum response temperature be lower than-30 ℃ (＜243K).
Example 4: with 1.0g MnOx/Al
2O
3Carrier joins in the distilled water, adopts example 2 described deposition-precipitation methods to prepare Au: MnOx: MnOx/Al
2O
3Weight ratio is 1: 10: 200 Au/MnOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
When adopting unstripped gas described in the example 1 and gas volume air speed, this catalyst CO is converted into CO fully
2Permission minimum response temperature be lower than-30 ℃ (＜243K).
Example 5: with 1.0gNiOx/Al
2O
3Carrier joins in the distilled water, adopts example 2 described deposition-precipitation methods to prepare Au: NiOx: NiOx/Al
2O
3Weight ratio is 1: 10: 200 Au/NiOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
When adopting unstripped gas described in the example 1 and gas volume air speed, this catalyst CO is converted into CO fully
2Permission minimum response temperature be lower than 28 ℃ (311K).
Example 6: with 1.0g CuOx/Al
2O
3Carrier joins in the distilled water, adopts example 2 described deposition-precipitation methods to prepare Au: CuOx: CuOx/Al
2O
3Weight ratio is 1: 10: 200 Au/CuOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
When adopting unstripped gas described in the example 1 and gas volume air speed, this catalyst CO is converted into CO fully
2Permission minimum response temperature be lower than-23 ℃ (250K).
Example 7: adopt example 3 described deposition-precipitation methods to prepare Au: FeOx: FeOx/Al
2O
3Weight ratio is 1: 10: 200 Au/FeOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
Consist of CO:2% at unstripped gas, O
2: 20.2%, N
2: 77.8% (percent by volume), gas volume air speed are 8000h
-1, this catalyst CO is converted into CO fully
2Permission minimum response temperature be-22 ℃ (251K).
Example 8: adopt example 3 described deposition-precipitation methods to prepare Au: FeOx: FeOx/Al
2O
3Weight ratio is 1: 10: 200 Au/FeOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
Adopt unstripped gas and gas volume air speed 11000h described in the example 1
-1The time, under 20 ℃, this catalyst CO is converted into CO fully
2Surpass 170 hours, activity of such catalysts can not detectedly change, can not detected CO concentration in the tail gas.
Example 9: adopt example 3 described deposition-precipitation methods to prepare Au: FeOx: FeOx/Al
2O
3Weight ratio is 1: 10: 200 Au/FeOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
Adopt the H that is furnished with 15ppm described in the example 1 in the unstripped gas
2S is at 8000h
-1The gas volume air speed under carry out sulfur poisoning-resistant experiment, at room temperature (20 ℃) carry out the CO catalytic oxidation of 100min continuously, activity of such catalysts can not detectedly change, can not detected CO concentration in the tail gas.
Example 10: adopt example 3 described deposition-precipitation methods to prepare Au: FeOx: FeOx/Al
2O
3Weight ratio is 1: 1O: 200 Au/FeOx/Al
2O
3Catalyst.This catalyst finished product is coccoid, is even black.
Consist of CO:O.5% at unstripped gas, O
2: 21%, N
2: 78.5% (percent by volume), gas volume air speed are 8000h
-1, relative humidity is 100% (20 ℃), the gas volume air speed is 8000h
-1, successive reaction 100min, activity of such catalysts can not detectedly change, can not detected CO concentration in the tail gas.
Claims (2)
1. a catalyst that purifies CO is characterized in that the active component of catalyst is gold, and carrier is composite oxides MOx/Al
2O
3, MOx is CoO
x, FeO
x, NiO
x, MnO
x, CuO
xOr ZnO
x, the weight ratio of Au and MOx is 1.0: 1～20, MOx and Al
2O
3Weight ratio be 1.0: 0.5～10
3
2. catalyst according to claim 1 is characterized in that Au and Al in the catalyst
2O
3Weight ratio is 1.0: 10～10
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148901 CN1238108C (en) | 2002-11-08 | 2002-11-08 | Catalyzer for purifying CO under certain environmental condition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02148901 CN1238108C (en) | 2002-11-08 | 2002-11-08 | Catalyzer for purifying CO under certain environmental condition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1498680A CN1498680A (en) | 2004-05-26 |
| CN1238108C true CN1238108C (en) | 2006-01-25 |
Family
ID=34233391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02148901 Expired - Fee Related CN1238108C (en) | 2002-11-08 | 2002-11-08 | Catalyzer for purifying CO under certain environmental condition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1238108C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389873C (en) * | 2004-07-21 | 2008-05-28 | 安立敦 | Load type gold catalyst with stabilized catalyzing performance and its preparation process |
| CN100998940B (en) * | 2006-01-10 | 2012-05-30 | 中国人民解放军63971部队 | Preparation method of CO catalytic material |
| CN101199928B (en) * | 2006-12-15 | 2010-09-15 | 中国人民解放军63971部队 | Process for preparing nanometer gold catalysts adding modification agent |
| CN101648136B (en) * | 2009-09-18 | 2012-08-22 | 哈尔滨工程大学 | Catalyst for eliminating carbon monoxide in damp air and preparation method thereof |
| CN108940296B (en) * | 2018-08-02 | 2021-04-30 | 沈炳龙 | Application of Co-Mo-Ni/TiO2-Al2O3 catalyst in CO removal |
| CN115722231A (en) * | 2022-09-09 | 2023-03-03 | 中国人民解放军军事科学院防化研究院 | Preparation method of supported nano-gold catalyst |
-
2002
- 2002-11-08 CN CN 02148901 patent/CN1238108C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1498680A (en) | 2004-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101143321B (en) | Low temperature co oxidation non-noble metal catalyst | |
| CN101204655B (en) | Process for preparing nanometer gold catalyst | |
| CN102114428B (en) | Monolithic catalyst used for oxidizing CO and methanal under ordinary temperature and preparation method thereof | |
| CN100998940B (en) | Preparation method of CO catalytic material | |
| CA1163615A (en) | Catalyst for purifying exhaust gases and method for manufacturing same | |
| CA2061066A1 (en) | Conversion of carbon monoxide using mixed transition metal oxide catalysts | |
| CN1714930A (en) | Formaldehyde gas cyaniding catalyst under the room temperature condition | |
| KR20070096119A (en) | Particulate matter oxidation catalyst and filter | |
| CN1238108C (en) | Catalyzer for purifying CO under certain environmental condition | |
| CN111013602A (en) | Formed Mn/Co-based catalyst capable of decomposing formaldehyde at room temperature and preparation method and application thereof | |
| CN104162440A (en) | Preparation method for high-water-resistance copper, manganese and tin composite oxide CO low-temperature oxidization catalyst | |
| CN100368089C (en) | One-step method for preparing compound oxide supported nano noble metal catalyst | |
| CN112337481A (en) | Catalyst capable of removing hydrogen cyanide and ammonia gas simultaneously and preparation method and application thereof | |
| CN101698149B (en) | Supported gold-PGM alloy catalyst with stable storage property and preparation method thereof | |
| CN104014353A (en) | Palladium chloride-cupric chloride catalyst applied to normal-temperature catalytic oxidation of carbon monoxide and preparation | |
| CN1132683C (en) | Practical low-temperature CO oxidizing catalyst | |
| JP3374999B2 (en) | Exhaust gas purification catalyst | |
| CN110038558B (en) | Preparation method and application of low-precious-metal-content high-activity catalyst | |
| CN116422352A (en) | Preparation method and application of phosphotungstic acid modified iron-based MOF derivative material | |
| JP3251009B2 (en) | Exhaust gas purification catalyst | |
| CN1259131C (en) | Method for preparing novel load type nanometer gold catalyzer | |
| CN111569873B (en) | Denitration catalyst | |
| CN113648990A (en) | Preparation method and application of iron pillared montmorillonite-loaded Mn-Ce-Sm composite catalyst | |
| JP2001104781A (en) | Material for removing nitrogen oxide and method for removing it | |
| CN110961117A (en) | Cu-Mn-O-SiO2-Al2O3Preparation method and application of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060125 Termination date: 20101108 |