CN101181680A - Anti-steam catalyst for selective oxidation of carbon monoxide and preparation method thereof - Google Patents
Anti-steam catalyst for selective oxidation of carbon monoxide and preparation method thereof Download PDFInfo
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- CN101181680A CN101181680A CNA2007101588932A CN200710158893A CN101181680A CN 101181680 A CN101181680 A CN 101181680A CN A2007101588932 A CNA2007101588932 A CN A2007101588932A CN 200710158893 A CN200710158893 A CN 200710158893A CN 101181680 A CN101181680 A CN 101181680A
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- carbon monoxide
- selective oxidation
- steam
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to an efficient steam resistant carbon monoxide selective oxidation catalyst. The catalyst adopts one of carbon black, alumina and silicon oxide as a carrier, precious metal platinum is taken as an active constituent to form a supported platinum catalyst, and a hydrophobic treatment is conducted on the supported platinum catalyst. The carbon monoxide can still be effectively removed by hydrophobic treated catalyst under conditions of vapor and a small quantity of oxygen. The catalyst can be applied to a proton exchange membrane fuel cell generating system which adopts reformed gas as hydrogen source, while carbon monoxide in reformed gas which is toxic to electro catalyst of fuel cell is removed; the catalyst can also be applied to other situations required carbon monoxide dispelling like: selective oxidative removal of carbon monoxide in hydrogen rich stream, selective oxidative removal of carbon monoxide in nitrogen, carbon monoxide removal in exhaust gas and carbon monoxide removal in hydrocarbon gases.
Description
Technical field
The present invention relates to catalyst technical field, relate in particular to carbon monoxide (CO) the selective oxidation catalyst of the loaded anti-steam type of used in proton exchange membrane fuel cell.
Background technology
At present fuel cell is because its high energy conversion efficiency, characteristics such as environmentally friendly are subjected to extensive attention, and characteristics such as Proton Exchange Membrane Fuel Cells also has that room temperature starts fast, no electrolyte loss, life-span are long are considered to the optimal candidate power supply of removable power supply.Proton Exchange Membrane Fuel Cells is fuel with hydrogen, at present, provides in the method for hydrogen fuel the method for useful preparing hydrogen by reforming methanol to portable Proton Exchange Membrane Fuel Cells.In this method, the methanol recapitalization technology comprises: steam reforming, partial oxidation are reformed and three kinds of methods of self-heating recapitalization, because the method difference, the composition of reformation gas is also different.Usually, contain the hydrogen of 45%-75% in the reformation gas, the carbon dioxide of 15%-25%, the carbon monoxide of 1%-10%, the steam of 10%-20% and the nitrogen of 0-20% (being percent by volume).Because carbon monoxide has poisoning effect to the eelctro-catalyst Pt/C of fuel cell, reformation gas needed before entering fuel cell usually through the transformationreation of carbon monoxide steam, carbonomonoxide concentration in the reformation gas is reduced to 1%, and then the scope that adopts methods such as selective oxidation, absorption further carbonomonoxide concentration to be reduced to Proton Exchange Membrane Fuel Cells can to bear (＜10ppm).
The removal of carbon monoxide technology mainly contains at present:
1) absorption method: absorption method is to adopt the adsorbent that can adsorb carbon monoxide at normal temperatures that the carbon monoxide in the gaseous mixture is adsorbed on the adsorbent, after carbon monoxide absorption reached capacity, the carbon monoxide that needs will be adsorbed on the adsorbent at a certain temperature removed.The deficiency of this method is: when removing carbon monoxide in the reformation gas by absorption method, because reformation gas carbon monoxide content is many, the carbon monoxide adsorption capacity of adsorbent is limited, adopts this method system bulk can be very big, simultaneously the carbon monoxide of absorption is deviate to need to consume certain energy from adsorbent.In addition, because reformation gas contains a large amount of steam, influence the adsorption capacity of adsorbent, therefore in fuel cell system, absorption method is not suitable for removing the carbon monoxide in the reformation gas.
2) palladium membrane separation process: adopt Metal Palladium and alloy film thereof optionally to allow hydrogen molecule pass through, and block other gas, obtain highly purified hydrogen.The deficiency of this method is: water in the reformation gas and carbon monoxide have certain influence to palladium film purification efficiency.On the other hand, because the running temperature of Proton Exchange Membrane Fuel Cells is no more than 80 ℃, and the operating temperature that the palladium film separates is at 350-500 ℃, the pressure reduction higher (1-2MPa) of operation, therefore need after supercooling, just can enter battery through the hydrogen after separating, consumed energy and reforming system also to be difficult to reach the palladium film and purify needed pressure.
3) pressure swing adsorption method: pressure swing adsorption method can removal of carbon monoxide, and the deficiency of this method is: containing saturation water in the reformation gas can influence absorption, simultaneously owing to need hydrogen purge in the operation of transformation absorption, thereby can waste hydrogen.In addition, transformation absorption need be than higher pressure reduction, and the pressure of reforming system also is difficult to reach requirement.
4) carbon monoxide methanation: the carbon monoxide methanation is to remove carbon monoxide, and the deficiency of this method is: the reaction of this method is to be based upon under the prerequisite that consumes hydrogen, removes 1 mole of carbon monoxide and will consume 3 mol of hydrogen.Methanation reaction also can take place in 20% the carbon dioxide (volume) reformed simultaneously in the gas, thereby can further consume a large amount of hydrogen, has reduced the efficient of hydrogen manufacturing.
5) selectivity oxidizing carbon monoxide: generally believe that at present selectivity oxidizing carbon monoxide is the most feasible method in the method that purifies carbon monoxide.This method is that utilization adding oxygen in reformation gas is oxidized to carbon dioxide with the carbon monoxide in the reformation gas.
In the technology of selectivity oxidizing carbon monoxide, prior art generally adopts alumina carrier, molecular sieve carrier, metal oxide carrier.Active component employing noble metal such as platinum, ruthenium, rhodium, palladium, gold etc.Also have and adopt non-noble metal and adopt noble metal to add non-noble metal.The deficiency of prior art is: though it is more to be used for the catalyst type of selectivity oxidizing carbon monoxide, major part can not be applicable to the environment of water, and this is because the existence of steam is very big to the influence of catalyst activity, can cause the conversion ratio of carbon monoxide lower.And contain saturated steam in the reformation gas, cause the catalyst of existing selectivity oxidizing carbon monoxide to be difficult in reformation gas, use.
Summary of the invention
The object of the present invention is to provide catalyst for selectivity oxidizing carbon monoxide of a kind of anti-steam type and preparation method thereof, make this catalyst under the condition that has steam to exist, have advantages of high catalytic activity.
For achieving the above object, technical scheme of the present invention is: a kind of anti-steam catalyst for selective oxidation of carbon monoxide, catalyst is loaded platinum catalyst, it is characterized in that described anti-steam catalyst for selective oxidation of carbon monoxide also comprises the water-repelling agent polytetrafluoroethylene (PTFE), loaded platinum catalyst is dispersed in the water-repelling agent polytetrafluoroethylene (PTFE).
Anti-steam catalyst for selective oxidation of carbon monoxide of the present invention is characterized in that the content range of the noble metal platinum in the described catalyst is: 0.2%-10%wt; The content range of water-repelling agent polytetrafluoroethylene (PTFE) is: 5-50%wt.
Anti-steam catalyst for selective oxidation of carbon monoxide of the present invention, the carrier that it is characterized in that described loaded platinum catalyst are any one in carbon black, aluminium oxide, the silica.
The preparation method of anti-steam catalyst for selective oxidation of carbon monoxide of the present invention, comprise loaded platinum catalyst preparation process, the preparation method who it is characterized in that described anti-steam catalyst for selective oxidation of carbon monoxide also comprises loaded platinum catalyst is carried out the hydrophobization treatment step, the hydrophobization treatment step is as follows: loaded platinum catalyst is impregnated in the container that ptfe emulsion is housed and stirs, until emulsion is stirred into gel state, with the shape moulding on demand of this gel, after oven dry under 100 ℃～150 ℃ low temperature, put into roaster 330-380 ℃ of scope roasting 30～60 minutes, be cooled to the catalyst for selectivity oxidizing carbon monoxide that room temperature promptly obtains anti-steam type then.
The present invention has following advantage:
1, by adding hydrophobic polytetrafluoroethylene (PTFE), strengthened the water repelling property of catalyst, made catalyst under the condition that has steam to exist, have advantages of high catalytic activity, and can under high-speed, move.
2, the present invention is simple, and is applied widely.It is in the Proton Exchange Membrane Fuel Cells electricity generation system of hydrogen source that this catalyst can be applied to reformation gas, remove CO gas poisonous in the reformation gas to fuel cell electro-catalyst, simultaneously also can be used for the occasion that other needs removal of carbon monoxide, as: in the hydrogen rich gas atmosphere selective oxidation of carbon monoxide remove, in the nitrogen selective oxidation of carbon monoxide remove, in the waste gas carbon monoxide remove and hydrocarbon gas in the removing of carbon monoxide.
The specific embodiment
Embodiment 1
(patent No.: it is 5% Pt/C catalyst that the method 99112700.5) prepares platinum load amount to adopt patent " a kind of fuel cell with the preparation method of carbon platinum-carrying electrocatalyst ".Take by weighing Pt/C catalyst 1.2 grams of above-mentioned 5% platinum content, the adding mass percent is 20% ptfe emulsion 4 grams, continue again after stirring to stir behind complete gel, after oven dry under 120 ℃ of low temperature, in the high-temperature roasting stove,, promptly obtain containing the catalyst of 40% polytetrafluoroethylene (PTFE) after the cooling in 340 ℃ of roasting temperatures 40 minutes.This catalyst is carried out following performance test: it is the reaction tube of 10mm that the catalyst that obtains is placed diameter, investigate its catalytic performance under different air speeds, test condition is: temperature of reactor is 80 ℃, and the reformation gas phase is to humidity 100%, and reformation gas is formed: 30ppmCO+25%CO
2+ 0.35%O
2+ 50%H
2+ 24.65%N
2The GC-14C gas-chromatography is adopted in the detection of carbonomonoxide concentration in the tail gas.Test result is as follows: when the reformation gas phase is 100% to humidity, prepared catalyst has good catalytic activity, as air speed≤5000h
-1The time, do not detect carbon monoxide in the tail gas.When air speed is 5500h
-1The time, carbonomonoxide concentration is 1.9ppm in the tail gas, this moment, the carbon monoxide conversion ratio was 94%.Explanation is 80 ℃ in temperature, and the reformation gas phase is to humidity 100%, and reformation gas consists of 30ppmCO+25%CO
2+ 0.35%O
2+ 50%H
2+ 24.65%N
2Condition under, air speed is 5500h
-1When following, the catalyst of preparation has the effect of good removal of carbon monoxide.
Embodiment 2
Employing is impregnated into chloroplatinic acid on the carrier, passes through drying and roasting then, and reduction (400-600 ℃) obtains the method for carrier platinum catalyst under hydrogen, and preparation platinum load amount is loaded platinum/aluminium oxide catalyst of 5%.Take by weighing loaded platinum/aluminium oxide catalyst 1.2 grams of above-mentioned 5% platinum content, the adding mass percent is 20% ptfe emulsion 4 grams, after stirring, continue to stir behind complete gel, behind 120 ℃ of following low temperature dryings, in the high-temperature roasting stove,, promptly obtain containing the catalyst of 40% polytetrafluoroethylene (PTFE) after the cooling in 340 ℃ of roasting temperatures 40 minutes.This catalyst is carried out following performance test: it is the reaction tube of 10mm that the catalyst that obtains is placed diameter, investigate its catalytic performance under different air speeds, test condition is: temperature of reactor is 130 ℃, and the reformation gas phase is to humidity 20%, and reformation gas is formed: 850ppmCO+25%CO
2+ 0.8%O
2+ 50%H
2+ 24.2%N
2The GC-14C gas-chromatography is adopted in the detection of carbonomonoxide concentration in the tail gas.Test result is as follows: temperature of reactor is 130 ℃, and reformation gas air speed is at 3000h
-1The time, the carbon monoxide conversion ratio still keeps 100%, and along with air speed further increases, carbonomonoxide concentration increases gradually in the reaction end gas, when air speed reaches 4000h
-1The time, carbonomonoxide concentration is 4.5ppm in the reaction end gas, under this concentration, fuel battery performance has certain decline, but influences less.When air speed reaches 4500h
-1After, in the reaction end gas carbonomonoxide concentration up to 23ppm, head and shoulders above the concentration range that can bear of Proton Exchange Membrane Fuel Cells.Explanation is 130 ℃ in temperature, and the reformation gas phase is to humidity 20%, and reformation gas consists of 850ppmCO+25%CO
2+ 0.8%O
2+ 50%H
2+ 24.2%N
2Condition under, air speed is at 4000h
-1When following, the catalyst of preparation has the effect of good removal of carbon monoxide.Be higher than 4500h in air speed
-1After, the catalyst of preparation can not be used for Proton Exchange Membrane Fuel Cells.
Claims (4)
1. anti-steam catalyst for selective oxidation of carbon monoxide, catalyst is loaded platinum catalyst, it is characterized in that described anti-steam catalyst for selective oxidation of carbon monoxide also comprises the water-repelling agent polytetrafluoroethylene (PTFE), loaded platinum catalyst is dispersed in the water-repelling agent polytetrafluoroethylene (PTFE).
2. anti-steam catalyst for selective oxidation of carbon monoxide according to claim 1 is characterized in that the content range of the noble metal platinum in the described catalyst is: 0.2%-10%wt; The content range of water-repelling agent polytetrafluoroethylene (PTFE) is: 5-50%wt.
3. anti-steam catalyst for selective oxidation of carbon monoxide according to claim 1, the carrier that it is characterized in that described loaded platinum catalyst are any one in carbon black, aluminium oxide, the silica.
4. the preparation method of the described anti-steam catalyst for selective oxidation of carbon monoxide of claim 1, comprise loaded platinum catalyst preparation process, the preparation method who it is characterized in that described anti-steam catalyst for selective oxidation of carbon monoxide also comprises loaded platinum catalyst is carried out the hydrophobization treatment step, the hydrophobization treatment step is as follows: loaded platinum catalyst is impregnated in the container that ptfe emulsion is housed and stirs, until emulsion is stirred into gel state, with the shape moulding on demand of this gel, after oven dry under 100 ℃～150 ℃ low temperature, put into roaster 330-380 ℃ of scope roasting 30～60 minutes, be cooled to room temperature then and promptly obtain anti-steam catalyst for selective oxidation of carbon monoxide.
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| CN2007101588932A CN101181680B (en) | 2007-12-14 | 2007-12-14 | Anti-steam catalyst for selective oxidation of carbon monoxide and preparation method thereof |
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| CN2007101588932A CN101181680B (en) | 2007-12-14 | 2007-12-14 | Anti-steam catalyst for selective oxidation of carbon monoxide and preparation method thereof |
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| CN101181680B CN101181680B (en) | 2010-12-08 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850272A (en) * | 2010-06-22 | 2010-10-06 | 中国工程物理研究院核物理与化学研究所 | Method for preparing hydrophobic catalyst by freezing molding |
| CN101591578B (en) * | 2009-07-10 | 2012-08-22 | 北京溯希至清科技有限公司 | Process for extracting natural gas from coke-oven gas |
| CN106238068A (en) * | 2016-07-31 | 2016-12-21 | 山西大学 | A kind of Pd Cu/ charcoal doping Attapulgite Catalyst and preparation method thereof |
| CN107694564A (en) * | 2017-11-23 | 2018-02-16 | 苏州祥派智能科技有限公司 | A kind of catalyst of decomposing formaldehyde and preparation method thereof |
-
2007
- 2007-12-14 CN CN2007101588932A patent/CN101181680B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591578B (en) * | 2009-07-10 | 2012-08-22 | 北京溯希至清科技有限公司 | Process for extracting natural gas from coke-oven gas |
| CN101850272A (en) * | 2010-06-22 | 2010-10-06 | 中国工程物理研究院核物理与化学研究所 | Method for preparing hydrophobic catalyst by freezing molding |
| CN101850272B (en) * | 2010-06-22 | 2011-12-14 | 中国工程物理研究院核物理与化学研究所 | Method for preparing hydrophobic catalyst by freezing molding |
| CN106238068A (en) * | 2016-07-31 | 2016-12-21 | 山西大学 | A kind of Pd Cu/ charcoal doping Attapulgite Catalyst and preparation method thereof |
| CN106238068B (en) * | 2016-07-31 | 2018-08-24 | 山西大学 | A kind of Pd-Cu/ charcoals doping Attapulgite Catalyst and preparation method thereof |
| CN107694564A (en) * | 2017-11-23 | 2018-02-16 | 苏州祥派智能科技有限公司 | A kind of catalyst of decomposing formaldehyde and preparation method thereof |
| CN107694564B (en) * | 2017-11-23 | 2023-10-03 | 苏州吉派供应链管理有限公司 | Catalyst for decomposing formaldehyde and preparation method thereof |
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| CN101181680B (en) | 2010-12-08 |
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Effective date of registration: 20230117 Address after: 213000 No. 17, beitanghe East Road, Tianning District, Changzhou City, Jiangsu Province Patentee after: Jiangsu Zhirui Bocheng Energy Technology Co.,Ltd. Address before: Dalian high tech park, 116025 Liaoning province Qixianling Torch Road No. 1 building A Room 401 Patentee before: Sunrise Power Co.,Ltd. |