CN101690892A - Method for preparing catalyst for removing CO by selective oxidation - Google Patents
Method for preparing catalyst for removing CO by selective oxidation Download PDFInfo
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- CN101690892A CN101690892A CN200910093229A CN200910093229A CN101690892A CN 101690892 A CN101690892 A CN 101690892A CN 200910093229 A CN200910093229 A CN 200910093229A CN 200910093229 A CN200910093229 A CN 200910093229A CN 101690892 A CN101690892 A CN 101690892A
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- precious metal
- colloid
- reducing agent
- selective oxidation
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Abstract
The invention provides a method for preparing a catalyst for removing CO from a hydrogen-rich atmosphere by selective oxidation. The catalyst is characterized in that the carrier thereof adopts Al2O3 or SiO2-Al2O3 with the weight percentage of SiO2 being 3-40%; and the active component thereof is one or more than one selected from the following noble metal elements: Ru, Rh, Pd and Pt. Based on a metallic colloid method, the method of the invention for preparing the catalyst comprises the following steps: adding surfactant to the aqueous solution of metal salt of the active components in the noble metal elements; slowly adding reducing agent drop by drop while stirring intensely, so as to obtain stable noble metal colloid with the particle size thereof being 2-10nm through reduction by a reducing agent; properly regulating loading conditions and loading the noble metal colloid onto the carrier, so as to obtain a loading-type metal colloid catalyst; and subjecting the metal colloid catalyst to room-temperature airing, oven-drying and reducing, to obtain the finished catalyst.
Description
Technical field:
The present invention relates to catalyst and make the field, aim to provide the highly active of a kind of metallic colloid method preparation, be used for the Preparation of catalysts method of the rich hydrogen hydrogen source of selective oxidation removal CO.
Background of invention:
Fuel cell (Fuel Cell) is a kind of novel energy conversion device, by fuel (as H
2) electrochemical oxidation and oxidant (as O
2) electrochemical reduction directly produce electric current.Because fuel cell power generation without combustion process, is not subjected to the restriction of Carnot cycle, not only have very high energy conversion efficiency, and power generation process can not cause environmental pollution.So the cleaning that fuel cell is acknowledged as the 21 century first-selection is the energy efficiently, is applied to various aspects such as vehicle-mounted power source, surface power station and direct-type alcohol fuel battery, portable electronics.
All fuel cell operations all need fuel, so fuel source becomes one of key issue of fuel cell.By methods such as conversions of reforming gently compounds such as alcohol, natural gas, gasoline resupply fuel cell power generation after being transformed into the mixture of hydrogen or hydrogen, be the method for at present aspect, the most effective acquisition fuel, for example Proton Exchange Membrane Fuel Cells employing reformation gas is fuel.
Contain 1～2% CO in the hydrogen source fuel that reformation obtains after transforming.Chemisorbed can take place in trace amounts of CO on the anode of fuel cell, the anxious residence of battery performance descended, and therefore CO must be removed to 1 * 10
-4Below.Taked some processing methods at this problem,, improved resistivity CO as eelctro-catalyst is carried out modification, though obtained certain achievement, but still be necessary reformation gas is handled, CO concentration reduced.Usually the method that removes CO has: absorption method, Pd membrane separation process, CO methanation method and CO selective oxidation method.The absorption method finite capacity, equipment volume is huge; Pd membrane separation process cost is higher, operation (350～500 ℃) under higher temperature; The CO of methanation method 1mol consumes the H of 3mol
2, and contain CO about 20% in the reformation gas
2, methanation takes place easily, consume a large amount of H
2Thereby comparatively speaking, CO selective oxidation method is removed to 1 * 10 with 1%CO in the reformation gas
-4It below is both economical, effective method.
The existing nearly 4 years history of the research of CO selective oxidation in the rich hydrogen hydrogen source.1963, Englhard company (USP3088919) found Pt/Al under rich hydrogen condition
2O
3Catalyst has the ability of higher CO selective oxidation.People such as SHOh [J.Catal, 1993,142:254] have studied a series of loaded catalysts, comprise that noble metal (Pt, Pd, Ru, Rh) and base metal (Co/Cu, Ni/Co/Fe, Ag, Cr, Fe, Mn) carry out selective oxidation to CO.It is 0.85%H that used reaction gas is formed (volume ratio)
2, 0.09%CO, 0.08%O
2, all the other are N
2Result of study shows that for noble metal, the active order of CO selective oxidation is: Ru/Al
2O
3＞Rh/Al
2O
3＞Pt/Al
2O
3＞Pd/Al
2O
3, and the catalytic activity of non-precious metal catalyst is generally relatively poor.Samsung SDI Co., Ltd provides a kind of Au catalyst that is used to remove CO.Patent CN2006100006158.5 points out that this catalyst system is simple relatively, and can remove CO efficiently under the situation of low temperature and no side reaction.But shortcoming is a gold nanotubes catalyst manufacturing cost height, and reactor adopts the recirculating system complex structure, and need add water to fuel processor.
The carrier aspect selects for use aluminium oxide to make carrier, wherein the Al of α, γ-type usually
2O
3Report more, γ-Al
2O
3The specific surface of carrier is at 100-300m
2Between/the g, the aluminium oxide of other forms all can be by γ-Al
2O
3Roasting obtains.Patent CN 1104950C, CN1319074A, US2005/02881801A1 point out, select α-Al for use
2O
3Be carrier, the crushing strength height, oxygen demand is low, only uses than requisite oxygen tolerance (O
2/ CO=0.5) excessive O seldom
2(O
2/ O=1).It is generally acknowledged α-Al
2O
3Specific surface at 3-25m
2Between/the g, purity is 99.95% when above, and the catalyst activity of preparation is better.But it adopts organic ruthenium compound (nitrosyl nitric acid ruthenium (Ru (NO) (NO
3)
x(OH)
y, x+y=3)) and as the ruthenium source, the higher and not environmental protection of cost.The people such as Maki Hoshino of Japan point out in patent US 2003/0059360A1, add CsNO in carrier
3, after dipping, drying, flooding other active components again, the element of interpolation helps oxygen and better adsorbs as a kind of " active oxygen provides material ", to promote the oxidation reaction of CO.But the catalyst that finally makes is Pt-Ru/Cs/Al
2O
3, the Preparation of catalysts process is complicated.
Summary of the invention:
The present invention is directed to problems of the prior art, provide a kind of catalyst that is used for the rich hydrogen hydrogen source of selective oxidation removal CO simply, preparation method efficiently.This catalyst has characteristics such as initial temperature is low, active height.
The present invention is a kind of Preparation of catalysts method that is used for selective oxidation removal hydrogen rich gas atmosphere CO, it is characterized in that:
Catalyst carrier is selected Al for use
2O
3Or SiO
2-Al
2O
3, and SiO
2-Al
2O
3Middle SiO
2The quality percentage composition 3～40%; Catalyst activity component is a precious metal element, is selected from wherein one or more of ruthenium, rhodium, palladium, platinum; Preparation of Catalyst adopts the metallic colloid method, promptly elder generation adds surfactant in the aqueous solution of the slaine of precious metal element active constituent, slowly drip under the vigorous stirring and add reducing agent, make the precious metal colloid that stable colloidal particle size is 2～10nm through the reducing agent reduction, the appropriate regulation loading condition, precious metal colloid is loaded on the carrier, obtain the metallic colloid catalyst of support type; Catalyst hangs, dries, reduces the catalyst that gets product through room temperature;
Described surfactant is that nonionic surface active agent is selected from Tween-80, Arlacel-20, polyvinylpyrrolidone (PVP), the mixture of one or more in the polyvinyl alcohol, preferably polyethylene pyrrolidones.
Described reducing agent is one or more the mixture in sodium borohydride, hydrazine hydrate, formaldehyde, methyl alcohol, the natrium citricum.The concentration of reducing agent is 0.01～1mol/L, and reduction temperature is 10～90 ℃, and the recovery time is 1～10hr.
The load capacity of described catalyst activity component precious metal element is 0.1～10.0wt%, and preferred catalyst activity component precious metal element is selected from wherein one or more of ruthenium, rhodium, platinum; Load capacity is preferably 0.5～5wt%.
After described precious metal colloid load is finished, dry in oxygen-free atmosphere, the temperature of oven dry is 80 ℃～180 ℃.
Described finished catalyst is used for the carbon monoxide of the rich hydrogen hydrogen source of selective oxidation removal, and applying working condition is: volume is formed: CO=1%, CO
2=20%, O
2=2%, all the other are H
2, air speed 5000h
-1
The present invention adds the aqueous solution of surfactant in the solution of precious metal salt, add reducing agent under the vigorous stirring, obtains metallic colloid after reduction is finished, and metallic colloid is loaded on the carrier, is prepared into finished catalyst, specifically may further comprise the steps:
(a) in precious metal salt solution, add aqueous surfactant solution, after vigorous stirring mixes it, slowly drip the reducing agent reduction, form the metallic colloid of stable colloidal particle size 2～10nm.
(b) metallic colloid with step a preparation loads on the carrier.
(c) catalyst of step b preparation is dried in oxygen-free atmosphere, bake out temperature is 80～180 ℃.
The catalyst of producing with the method can be used for multiple heterogeneous catalytic reaction, for example hydrogenation and oxidation reaction.According to the present invention, the catalyst of being produced by this method can be used for the CO in the rich hydrogen hydrogen source of selective oxidation removal.
Technology of the present invention only is used for the catalyst of the rich hydrogen hydrogen source of selective oxidation removal CO with 3 quick and cheap producing of processing step, simultaneously to Catalytic Layer thickness and position-controllable.
Technology outlet CO content of the present invention can drop to below the 10ppm, and initial reaction temperature is minimum to reach 100 ℃.
Owing to have significantly improved metal dispersion and uniformity, metal particle size obviously reduces with active metals surface area bigger, and catalyst of the present invention has high activity.
Description of drawings:
Fig. 1 is the sample catalyst activity rating result curve figure of embodiment 1 and embodiment 2.
Fig. 2 is the sample catalyst activity rating result curve figure of embodiment 3 and embodiment 4.
Fig. 3 is the sample catalyst activity rating result curve figure of comparative example 1 and comparative example 2.
The specific embodiment:
The present invention further specifies its preparation and using method by following embodiment, but does not constitute limiting the scope of the invention.
Embodiment 1:
With containing the RuCl that is equivalent to 0.8gRu
3Solution 45ml adds the PVP solution 20ml of 10g/L in the above-mentioned solution, stirs 1hr, dropwise adds the NaBH of 6.0g/L
4Aqueous solution 20ml obtains the ruthenium metallic colloid that PVP protects after the reduction.This metallic colloid is loaded on the 100g alumina support, and 110 ℃ of oven dry 4hr finally make 0.8% Ru/Al
2The O3 catalyst.
Catalyst performance evaluation:
Reactor: fixed bed reactors
Loaded catalyst: 50ml
Air speed: 5000h
-1
Gas volume is formed: CO=1%, CO
2=20%, O
2=2%, all the other are H
2
Fig. 1 and table 1 are seen in the catalyst activity evaluation.
Embodiment 2:
The metallic colloid preparation is with containing the RuCl that is equivalent to 1.6gRu
3Solution, all the other catalyst preparation step are with embodiment 1.
This catalyst is to test as the method among the embodiment 1, and its evaluation result is seen Fig. 1 and table 1.
Embodiment 3:
The metallic colloid preparation is with containing the chlorine palladium acid solution that is equivalent to 0.8gPd, and all the other catalyst preparation step are with embodiment 1.
This catalyst is to test as the method among the embodiment 1, and its evaluation result is seen Fig. 2 and table 1.
Embodiment 4:
The metallic colloid preparation is with containing the platinum acid chloride solution that is equivalent to 0.8gPt, and all the other catalyst preparation step are with embodiment 1.
This catalyst is to test as the method among the embodiment 1, and its evaluation result is seen Fig. 2 and table 1.
Comparative example 1
Adopt conventional dipping method to prepare catalyst.With containing the RuCl3 solution 45ml that is equivalent to 0.8gRu, load on the 100g alumina support, 110 ℃ of dry 4hr in the baking oven, vapour phase reduction in the reduction reaction container is washed to no Cl
-, finally make 0.8% Ru/Al2O3 catalyst.
This catalyst is to test as the method among the embodiment 1, and its evaluation result is seen Fig. 3 and table 1.
Comparative example 2:
The dipping solution preparation is equivalent to 0.8g chlorine palladium acid solution with containing, and all the other catalyst preparation step are with comparative example 1.
This catalyst is to test as the method among the embodiment 1, and its evaluation result is seen Fig. 3 and table 1.
The contrast of the minimum outlet of table 1 CO content
| Project | Minimum outlet CO content (ppm) |
| |
?3.8 |
| Embodiment 2 | ?2.5 |
| Embodiment 3 | ?6.0 |
| Embodiment 4 | ?11.5 |
| Comparative example 1 | ?145 |
| Comparative example 2 | ?456 |
Claims (2)
1. Preparation of catalysts method that is used for selective oxidation removal hydrogen rich gas atmosphere CO is characterized in that:
Catalyst carrier is selected Al for use
2O
3Or SiO
2-Al
2O
3, and SiO
2-Al
2O
3Middle SiO
2The quality percentage composition 3～40%; Catalyst activity component is a precious metal element, is selected from wherein one or more of ruthenium, rhodium, palladium, platinum; Preparation of Catalyst adopts the metallic colloid method, promptly elder generation adds surfactant in the aqueous solution of the slaine of precious metal element active constituent, slowly drip under the vigorous stirring and add reducing agent, make the precious metal colloid that stable colloidal particle size is 2～10nm through the reducing agent reduction, the appropriate regulation loading condition, precious metal colloid is loaded on the carrier, obtain the metallic colloid catalyst of support type; Catalyst hangs, dries, reduces the catalyst that gets product through room temperature;
Described surfactant is that nonionic surface active agent is selected from Tween-80, Arlacel-20, polyvinylpyrrolidone PVP, the mixture of one or more in the polyvinyl alcohol;
Described reducing agent is one or more the mixture in sodium borohydride, hydrazine hydrate, formaldehyde, methyl alcohol, the natrium citricum; The concentration of reducing agent is 0.01～1mol/L, and reduction temperature is 10～90 ℃, and the recovery time is 1～10hr;
The load capacity of described catalyst activity component precious metal element is 0.1～10.0wt%;
After described precious metal colloid load is finished, dry in oxygen-free atmosphere, the temperature of oven dry is 80 ℃～180 ℃;
Described finished catalyst is used for the carbon monoxide of the rich hydrogen hydrogen source of selective oxidation removal, and applying working condition is: volume is formed: CO=1%, CO
2=20%, O
2=2%, all the other are H
2, air speed 5000h
-1
2. according to the described preparation method of claim 1, it is characterized in that:
Described surfactant is that nonionic surface active agent is selected from polyvinylpyrrolidone;
Described catalyst activity component precious metal element is selected from wherein one or more of ruthenium, rhodium, platinum; The load capacity of precious metal element is 0.5～5wt%.
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|---|---|---|---|
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920197A (en) * | 2010-08-31 | 2010-12-22 | 苏州大学 | Catalyst for preparing ether alcohol by ether aldehyde hydrogenation reaction and preparation method thereof |
| CN102921431A (en) * | 2012-10-19 | 2013-02-13 | 大连凯特利催化工程技术有限公司 | Catalyst used in oxidative desorption of carbon monoxide in hydrogen and preparation method for catalyst |
| CN103084174A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Methanation catalyst for carbon oxide removing, preparation method and applications thereof |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN103537281A (en) * | 2013-10-14 | 2014-01-29 | 中国科学院生态环境研究中心 | Special-structured oxide-loaded precious metal catalyst synthesis method and application |
| CN106799227A (en) * | 2017-01-18 | 2017-06-06 | 中国科学院福建物质结构研究所 | A kind of catalyst of selective oxidation CO, its preparation method and application |
| CN106824179A (en) * | 2017-01-18 | 2017-06-13 | 中国科学院福建物质结构研究所 | A kind of hybrid material, its preparation method and application |
| CN111905755A (en) * | 2020-07-16 | 2020-11-10 | 浙江恒澜科技有限公司 | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof |
| CN111974382A (en) * | 2019-05-22 | 2020-11-24 | 中国科学院大连化学物理研究所 | Application of low-temperature CO oxidation or ADN decomposition platinum-based catalyst |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
-
2009
- 2009-09-23 CN CN200910093229A patent/CN101690892A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920197A (en) * | 2010-08-31 | 2010-12-22 | 苏州大学 | Catalyst for preparing ether alcohol by ether aldehyde hydrogenation reaction and preparation method thereof |
| CN101920197B (en) * | 2010-08-31 | 2012-07-25 | 苏州大学 | Catalyst for preparing ether alcohol by ether aldehyde hydrogenation reaction and preparation method thereof |
| CN103084174A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Methanation catalyst for carbon oxide removing, preparation method and applications thereof |
| CN102921431A (en) * | 2012-10-19 | 2013-02-13 | 大连凯特利催化工程技术有限公司 | Catalyst used in oxidative desorption of carbon monoxide in hydrogen and preparation method for catalyst |
| CN102921431B (en) * | 2012-10-19 | 2014-08-06 | 大连凯特利催化工程技术有限公司 | Catalyst used in oxidative desorption of carbon monoxide in hydrogen and preparation method for catalyst |
| CN103111292A (en) * | 2013-01-22 | 2013-05-22 | 北京格林凯默科技有限公司 | Simple preparation method of palladium-based catalyst and palladium-based catalyst prepared by using same |
| CN103394373A (en) * | 2013-04-27 | 2013-11-20 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN103394373B (en) * | 2013-04-27 | 2015-12-23 | 南京工业大学 | Preparation method of hydrogenation catalyst |
| CN103537281B (en) * | 2013-10-14 | 2015-09-30 | 中国科学院生态环境研究中心 | The preparation method and use of the oxide carried noble metal catalyst of a kind of special construction |
| CN103537281A (en) * | 2013-10-14 | 2014-01-29 | 中国科学院生态环境研究中心 | Special-structured oxide-loaded precious metal catalyst synthesis method and application |
| CN106799227A (en) * | 2017-01-18 | 2017-06-06 | 中国科学院福建物质结构研究所 | A kind of catalyst of selective oxidation CO, its preparation method and application |
| CN106824179A (en) * | 2017-01-18 | 2017-06-13 | 中国科学院福建物质结构研究所 | A kind of hybrid material, its preparation method and application |
| CN106824179B (en) * | 2017-01-18 | 2019-06-21 | 中国科学院福建物质结构研究所 | A kind of hybrid material, preparation method and application |
| CN106799227B (en) * | 2017-01-18 | 2019-07-30 | 中国科学院福建物质结构研究所 | A kind of catalyst, preparation method and the application of selective oxidation CO |
| CN111974382A (en) * | 2019-05-22 | 2020-11-24 | 中国科学院大连化学物理研究所 | Application of low-temperature CO oxidation or ADN decomposition platinum-based catalyst |
| CN111905755A (en) * | 2020-07-16 | 2020-11-10 | 浙江恒澜科技有限公司 | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof |
| CN111905755B (en) * | 2020-07-16 | 2022-07-05 | 浙江恒逸石化研究院有限公司 | Catalyst for hydrogenation of 2,2,4, 4-tetramethyl-1, 3-cyclobutanedione and preparation method and application thereof |
| CN114797464A (en) * | 2022-06-01 | 2022-07-29 | 宁波工程学院 | Device and method for online elimination of CO based on plasma technology |
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