CN1974004A - Catalyst for low temperature elimination of CO and its prepn process - Google Patents
Catalyst for low temperature elimination of CO and its prepn process Download PDFInfo
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- CN1974004A CN1974004A CNA2006101632536A CN200610163253A CN1974004A CN 1974004 A CN1974004 A CN 1974004A CN A2006101632536 A CNA2006101632536 A CN A2006101632536A CN 200610163253 A CN200610163253 A CN 200610163253A CN 1974004 A CN1974004 A CN 1974004A
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- catalyst
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- platinum
- colloid
- low temperature
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Abstract
The present invention is catalyst for low temperature elimination of CO and its preparation process, and belongs to the field of heterogeneous catalysis technology. The catalyst has active component of metal Pt, and carrier comprising one or two oxides of metals Ni, Mg, Zn, Co, Fe, etc. The preparation process includes the following steps: basifying Pt salt/ethylene glycol solution to obtain Pt colloid; adding metal salt solution into precipitant solution to produce hydroxide precipitate; mixing the synthesized Pt colloid and the carrier hydroxide precipitate, adding deionized water to disperse the precipitate completely and treating in water bath at 70-100 deg.c for 2-4 days. The catalyst has high activity of oxidizing CO at low temperature, long service life and proper water vapor strengthened effect, and the preparation process has high Pt utilization rate, simple operation, facile carrier material and low cost.
Description
Technical field
The invention belongs to the heterogeneous catalysis technology field, particularly a kind of Catalysts and its preparation method of CO catalytic oxidation at low temperatures.
Background technology
The oxidation of the CO of low concentration is in the pollution that controls environment, vehicle exhaust is handled, air cleaning, closed CO2 laser instrument, the CO gas sensor, CO gas shield mask, etc. the aspect have important application prospects, the development owing to the cleanliness without any pollution fuel cell technology in recent years in addition, the technology that removes CO at temperate condition also has very important significance.
For a long time, people have carried out extensive studies to the CO oxidation catalyst, it is that the Hopcalite catalyst of main component at room temperature has advantages of high catalytic activity (T.H.Rogers that the nineteen twenty-one researcher finds with the copper Mn oxide, C.S.Piggot, W.H.Bahlke, J.Am.Chem.Soc.43 (1921) 1973), because it is cheap, in mine and military affairs, obtained application, yet the water-resistance of this catalyst is relatively poor, under the environment of humidification, catalytic activity descends rapidly, so its application has been subjected to very big restriction.The 1980s, Haruta utilizes coprecipitation that golden high dispersive is found that on transition metal oxide it has extraordinary CO oxidation activity, room temperature even just can be with CO complete oxidation (M.Haruta in subzero, et al, Chem.Lett.2 (1987) 405), the auri catalyst has good water-resistance (Guiying Wang simultaneously, et al, Kinetics and Catalysis 43 (2002) 433), but based on the effect of dimensional effect, the auri catalyst is in the process of high temperature preliminary treatment and normal temperature storage, gold particle is assembled easily, and causes activity of such catalysts to descend.Therefore, the stability that how to improve this class catalyst is to continue the problem that solves.
The prior art the most close with the present invention is a Chinese invention patent, and name is called " carbon monoxide oxidation and selective oxidation Catalysts and its preparation method ", and publication number is CN1745879A.Disclosed catalyst is: catalyst carrier is the transition metal oxide that alumina particle supports, and transition metal is selected from a kind of among Fe, Co, the Mn, and active component is a gold.In the preparation method, infusion process is adopted in the preparation of catalyst carrier; The active component gold deposits on the carrier with precipitation-depositional mode, and precipitating reagent is selected from NaOH, Na
2CO
3, NH
3H
2O, (NH
4)
2CO
3, KOH, K
2CO
3In a kind of.
Summary of the invention
The technical problem to be solved in the present invention provides novel high-activity, high stability platinum based catalyst of a series of CO of can be used for low temperature elimination and preparation method thereof, makes catalyst have high CO oxidation activity under low temperature (between 10～100 ℃) and has good water-resistance and stability.
Catalyst provided by the present invention is the noble metal platinum that metal oxide supports, that is, active component is a metal platinum, and carrier is one or both metal oxides in the metals such as nickel, magnesium, zinc, cobalt, iron, copper, calcium, aluminium, manganese; The mol ratio of active component platinum and carrier metal is (0.1～10): 100.
Reasonable carrier is iron oxide (Fe
2O
3), zinc oxide (ZnO) and iron oxide and aluminium oxide (Fe
2O
3-Al
2O
3).
For catalyst of the present invention is carried out reaction evaluating, adopt 0.1～1.0%CO, 5～20%O
2, 1.0～2.0%H
2O, Ar be balance gas for the reaction feed group, total flow is: 80～150ml/min, catalyst amount are 50～500mg, test.The result shows that catalyst promptly has extraordinary CO oxidation susceptibility at 298～373K, also has good water-resistance.
The Preparation of catalysts method of the CO of being used for low temperature elimination of the present invention is the colloidal deposition method.Preparation process is divided into the preparation and deposition three parts of colloid on carrier hydroxide of synthetic, the carrier hydroxide of platinum colloid:
Synthesizing of said platinum colloid is that platinum salt/ethylene glycol solution basification makes the platinum colloid;
The preparation of said carrier hydroxide is that metal salt solution is joined in the precipitant solution, and regulating PH is between 7～10, and the precipitation of hydroxide of generation is filtered, washing, and wherein precipitating reagent can be an ammoniacal liquor, sodium carbonate, NaOH;
The deposition of said colloid on carrier hydroxide, be that synthetic platinum colloid and carrier precipitation of hydroxide are mixed, and adding deionized water, stirring disperses precipitation fully, again the mixture that obtains is placed 70～100 ℃ water-bath to handle 2～4 days, then with mixture washing, suction filtration, drying; The consumption of carrier hydroxide is platinum in molar ratio: metal=(0.1～10): 100.
In the above-mentioned preparation process, synthesizing of said platinum colloid is identical with existing preparation platinum colloid process, promptly; platinum salt is dissolved in the ethylene glycol; to the ethylene glycol solution that wherein adds NaOH, stir the back under the argon shield, obtain the platinum of colloidal state 50～200 ℃ of heat treated 3 hours.
In the Preparation of catalysts process, used platinum salt can be H
2PtCl
66H
2O.
In the Preparation of catalysts process, used slaine is a nickelous sulfate, magnesium nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, calcium nitrate, aluminum nitrate, copper sulphate, one or both in the manganese nitrate.
In order to make catalyst of the present invention have the effect of better CO low temperature elimination, can also carry out activation processing again to the catalyst for preparing, said activation processing process is that catalyst is made 40～60 purpose particles, under 473～673K, handles in the oxygen atmosphere 1～10 hour.
Eliminate catalyst with the CO oxidation of other type and compare, the characteristics that catalyst of the present invention has are:
1, have very high low-temperature oxidation activity, can be between 10～100 ℃ with the CO complete oxidation in the air atmosphere.
2, the existence of steam not only can not reduce activity of such catalysts, has certain appropriate enhancement effect on the contrary.
3, life of catalyst is longer.
4, active component platinum loses hardly in the whole process of preparation of catalyst, and the noble metal utilization rate of active component is very high.
5, catalyst preparation process is simple, and carrier material is easy to get, and cost reduces.
The specific embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1, preparation Pt colloid
The 2g chloroplatinic acid is dissolved in the 100ml ethylene glycol, and to the ethylene glycol solution that wherein adds 120mlNaOH, stirring at room 1h then at 140 ℃ of heat treated 3h, can obtain the Pt of colloidal state under the argon shield, and concentration is 1.75 * 10
-2Mol/l.
Embodiment 2, preparation platinum content are 10% Pt/NiO catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the nickel sulfate solution of 0.5mol/l respectively, get the 35ml nickel sulfate solution, join in the 30ml sodium carbonate liquor, regulating PH is between 7～8.The sedimentation and filtration that generates, washing.
Get the colloid 100ml among the embodiment 1, mix, and add the 60ml deionized water, fully stir after precipitation is disperseed fully, put into 80 ℃ of water-baths and refluxed 3 days with above-mentioned precipitation.Then said mixture filtered, wash to there not being chlorion, 353K is dry down.
Catalyst can be made into 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 3 hours in the oxygen atmosphere.
Embodiment 3, preparation platinum content are 1% Pt/Fe
2O
3Catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the iron nitrate solution of 0.5mol/l respectively, get the 35ml iron nitrate solution, join in the 40ml sodium carbonate liquor, regulating PH is about 9～10.The sedimentation and filtration that generates, washing.
Get the colloid 10ml among the embodiment 1, mix, and add the 20ml deionized water, fully stir after precipitation is disperseed fully, put into 70 ℃ of water-baths and refluxed 3 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst can be made into 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 5 hours in the oxygen atmosphere.
The platinum colloid that increase or minimizing embodiment 1 make, the mol ratio that makes platinum and iron is in (0.1～10): 100 scope, prepared catalyst all have CO low temperature elimination effect preferably.
Embodiment 4, preparation platinum content are 5% Pt/MnO catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the manganese sulfate solution of 0.5mol/l respectively, get the 35ml manganese sulfate solution, join in the 40ml sodium carbonate liquor, regulating PH is about 7.5.The sedimentation and filtration that generates, washing.
Get the colloid 50ml among the embodiment 1, mix, and add the 50ml deionized water, fully stir after precipitation is disperseed fully, put into 90 ℃ of water-baths and refluxed 4 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst can be made into 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 1 hour in the oxygen atmosphere.
Embodiment 5, preparation platinum content are 1% Pt/Al
2O
3Catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the aluminum nitrate solution of 0.5mol/l respectively, get the 35ml aluminum nitrate solution, join in the 40ml sodium carbonate liquor, regulating PH is about 7.5.The sedimentation and filtration that generates, washing.
Get the colloid 10ml among the embodiment 1, mix, and add the 20ml deionized water, fully stir after precipitation is disperseed fully, put into 100 ℃ of water-baths and refluxed 2 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst need be made 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 3 hours in the oxygen atmosphere.
Embodiment 6, preparation platinum content are 1% Pt/ZnO catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the zinc nitrate solution of 0.5mol/l respectively, get the 35ml zinc nitrate solution, join in the 40ml sodium carbonate liquor, regulating PH is about 7.5.The sedimentation and filtration that generates, washing.
Get the colloid 10ml among the embodiment 1, mix, and add the 20ml deionized water, fully stir after precipitation is disperseed fully, put into 80 ℃ of water-baths and refluxed 4 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst need be made 40～60 purpose particles before carrying out reaction evaluating, and under 473-673K, handles 4 hours in the oxygen atmosphere.
Embodiment 7, preparation platinum content are 1% Pt/Co
3O
4Catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the cobalt nitrate solution of 0.5mol/l respectively, get the 35ml cobalt nitrate solution, join in the 40ml sodium carbonate liquor, regulating PH is between 7～8.The sedimentation and filtration that generates, washing.
Get the colloid 10ml among the embodiment 1, mix, and add the 20ml deionized water, fully stir after precipitation is disperseed fully, put into 90 ℃ of water-baths and refluxed 2 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst need be made 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 3 hours in the oxygen atmosphere.
Embodiment 8, preparation platinum content are 0.1% Pt/Fe
2O
3-Al
2O
3Catalyst
Prepare the sodium carbonate liquor of 1.0mol/l and the iron nitrate solution of 0.5mol/l, the aluminum nitrate solution of 0.5mol/l respectively, get 50ml ferric nitrate and 300ml aluminum nitrate solution, join in the 500ml sodium carbonate liquor, regulating PH is between 8～9.The sedimentation and filtration that generates, washing.
Get the colloid 10ml among the embodiment 1, mix, and add the 40ml deionized water, fully stir after precipitation is disperseed fully, put into 90 ℃ of water-baths and refluxed 2 days with above-mentioned precipitation.Then with the sedimentation and filtration that generates, washing to there not being chlorion, 353K is dry down.
Catalyst need be made 40～60 purpose particles before carrying out reaction evaluating, and under 473～673K, handles 4 hours in the oxygen atmosphere.
The consumption of suitable increase platinum colloid, the mol ratio that makes platinum and iron, aluminium is in that (0.1～g): (0～50): 100 scope, prepared catalyst all have CO low temperature elimination effect preferably.
In above each embodiment, during preparation carrier hydroxide, substitute sodium carbonate with ammoniacal liquor or NaOH and also be fine.
Embodiment 9, catalyst of the present invention are used for the CO catalytic oxidation and eliminate reaction.
Reaction temperature is 298～373K, and feed composition is: 0.5%CO, 10%O
2, 1.8%H
2O, Ar are balance gas, and total flow is: 100ml/min, catalyst amount are 50-500mg.
Under above-mentioned experiment condition, investigate the catalytic activity and the life-span of catalyst, found that catalyst of the present invention just can be with the CO complete oxidation in the humid air atmosphere, wherein 1%Pt/Fe between 10～100 ℃
2O
3Catalyst is in that be lower than can be with the CO complete oxidation under 30 ℃ the temperature, and life of catalyst can reach 2,000 hours.
Claims (5)
1, a kind of catalyst that is used for the CO low temperature elimination is characterized in that, active component is a metal platinum, and carrier is one or both metal oxides in nickel, magnesium, zinc, cobalt, iron, copper, calcium, aluminium, the manganese; The mol ratio of active component platinum and carrier metal is (0.1～10): 100.
According to the described catalyst that is used for the CO low temperature elimination of claim 1, it is characterized in that 2, said carrier is iron oxide, zinc oxide and iron oxide and aluminium oxide.
3, a kind of Preparation of catalysts method that is used for the CO low temperature elimination of claim 1 is characterized in that, preparation process is divided into the preparation and the deposition of colloid on carrier hydroxide of synthetic, the carrier hydroxide of platinum colloid:
Synthesizing of said platinum colloid is that platinum salt/ethylene glycol solution basification makes the platinum colloid;
The preparation of said carrier hydroxide is that metal salt solution is joined in the precipitant solution, and regulating PH is between 7～10, and the precipitation of hydroxide of generation is filtered, washing, and precipitating reagent wherein is an ammoniacal liquor, sodium carbonate, NaOH;
The deposition of said colloid on carrier hydroxide, be that synthetic platinum colloid and carrier precipitation of hydroxide are mixed, and adding deionized water, stirring disperses precipitation fully, again the mixture that obtains is placed 70～100 ℃ water-bath to handle 2～4 days, then with mixture washing, suction filtration, drying; The consumption of carrier hydroxide is platinum in molar ratio: metal=(0.1～10): 100.
4, according to the described Preparation of catalysts method that is used for the CO low temperature elimination of claim 3, it is characterized in that, also will carry out the activation processing process, said activation processing process is that catalyst is made 40～60 purpose particles, under 473～673K, handled in the oxygen atmosphere 1～10 hour.
5, according to claim 3 or the 4 described Preparation of catalysts methods that are used for the CO low temperature elimination, it is characterized in that said platinum salt is H
2PtC
L66H
2O; Said slaine is one or both in nickelous sulfate, magnesium nitrate, zinc nitrate, cobalt nitrate, ferric nitrate, calcium nitrate, copper sulphate, the manganese nitrate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101632536A CN100522351C (en) | 2006-12-15 | 2006-12-15 | Catalyst for low temperature elimination of CO and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101632536A CN100522351C (en) | 2006-12-15 | 2006-12-15 | Catalyst for low temperature elimination of CO and its preparation process |
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| Publication Number | Publication Date |
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| CN1974004A true CN1974004A (en) | 2007-06-06 |
| CN100522351C CN100522351C (en) | 2009-08-05 |
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Cited By (8)
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|---|---|---|---|---|
| CN101722009B (en) * | 2008-10-24 | 2012-10-24 | 中国石油化工股份有限公司 | Nano-gold catalyst for deeply removing carbon monoxide, preparing method and application thereof |
| RU2500469C1 (en) * | 2012-11-22 | 2013-12-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Nanostructured catalyst for after-burning of carbon monooxide |
| CN104043460A (en) * | 2014-06-11 | 2014-09-17 | 华东理工大学 | Preparation method for nickel oxide loaded palladium catalyst and application to room-temperature CO catalytic oxidation |
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| CN113877605A (en) * | 2021-02-09 | 2022-01-04 | 中国石油大学(华东) | Catalyst for oxidizing CO at low temperature and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101722009B (en) * | 2008-10-24 | 2012-10-24 | 中国石油化工股份有限公司 | Nano-gold catalyst for deeply removing carbon monoxide, preparing method and application thereof |
| RU2500469C1 (en) * | 2012-11-22 | 2013-12-10 | федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Российский государственный технический университет (Новочеркасский политехнический институт)" | Nanostructured catalyst for after-burning of carbon monooxide |
| CN104043460A (en) * | 2014-06-11 | 2014-09-17 | 华东理工大学 | Preparation method for nickel oxide loaded palladium catalyst and application to room-temperature CO catalytic oxidation |
| CN105032385A (en) * | 2015-07-08 | 2015-11-11 | 华中科技大学 | Preparation method for metal oxide/platinum nanoparticle composite catalyst |
| CN105032385B (en) * | 2015-07-08 | 2017-09-12 | 华中科技大学 | A kind of preparation method of metal oxide/Pt nanoparticle composite catalyst |
| CN106391007A (en) * | 2016-09-12 | 2017-02-15 | 吉林大学 | Catalyst for catalytic removal of carbon monoxide and formaldehyde under conditions of ambient temperature and humidity and preparation method of catalyst |
| CN106391007B (en) * | 2016-09-12 | 2019-03-22 | 吉林大学 | It is a kind of for catalytic removal carbon monoxide and the catalyst of formaldehyde and preparation method thereof under the conditions of ambient temperature and moisture |
| CN112371121A (en) * | 2020-12-01 | 2021-02-19 | 吉林大学 | Catalyst for eliminating formaldehyde and carbon monoxide at room temperature and preparation method thereof |
| CN112675875A (en) * | 2021-01-21 | 2021-04-20 | 浙江工业大学 | Catalyst for preparing deuterated methanol and preparation method thereof |
| CN113877605A (en) * | 2021-02-09 | 2022-01-04 | 中国石油大学(华东) | Catalyst for oxidizing CO at low temperature and preparation method thereof |
| CN113877605B (en) * | 2021-02-09 | 2024-02-02 | 中国石油大学(华东) | Catalyst for low-temperature oxidation of CO and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100522351C (en) | 2009-08-05 |
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