CN1736590A - Metal carrier type hydrogen-eliminating catalyst and preparation process thereof - Google Patents
Metal carrier type hydrogen-eliminating catalyst and preparation process thereof Download PDFInfo
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- CN1736590A CN1736590A CN 200510085393 CN200510085393A CN1736590A CN 1736590 A CN1736590 A CN 1736590A CN 200510085393 CN200510085393 CN 200510085393 CN 200510085393 A CN200510085393 A CN 200510085393A CN 1736590 A CN1736590 A CN 1736590A
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Abstract
The invention relates to a catalyst which is use to eliminate hydrogen in nuclear power station, particularly in the closed space such as containing vessel in nuclear power station. The catalyst comprises a sheet metallic carrier, an active component of a plurality of noble metals, and an agent of Na, K, Cr element and rare-earth metal. The experiment expresses that the metallic carrier type catalyst has high dehydrogenation efficiency, long life time, and good moisture retardant property.
Description
(1), technical field
The present invention relates to be used for the Catalysts and its preparation method of the non-active elimination hydrogen of nuclear power station, be particularly suitable for using in the confined spaces such as npp safety shell.
(2), background technology
After nuclear power plant's presurized water reactor generation loss of-coolant accident (LOCA) (LOCA), because the failure that coolant loss and emergency power cooling agent inject, fuel temperature sharply raises, and causes between the zirconium pyroreaction taking place in the entrained steam and fuel sheath in the main system.Under the major accident situation, fuel sheath might be by complete oxidation, and this reaction is exothermic reaction, and produces a large amount of hydrogen.Among the hydrogen that this reaction produced enters the containment vessel environment with steam from the main system breakage.In addition, the irradiation of water decomposes and reactor core fused mass and concrete reaction, also will produce a large amount of hydrogen.In serious accident, the rate of release of hydrogen can reach the order of magnitude of 1 Kilograms Per Second.Unless adopted some system to be under its flammability limit, otherwise the enriching quantity of hydrogen can increase greatly in the containment atmosphere, thereby in containment, generate potential explosive gas mixture to keep density of hydrogen.Ou Ran once igniting afterwards can be because of the burning of a large amount of hydrogen or the integrality that blast jeopardizes containment.
In order to prevent to form this class explosive gas mixture in containment, people have inquired into various apparatus and method.These devices for example have catalysis type or heated type recombiner, the combination of catalysis and electrodynamic type igniter or aforementioned several devices, and the lasting or deactivation processing method afterwards of containment vessel.Disappear hydrogen system such as the compound hydrogen that disappears of electric heating, heated type catalytic hydrogen-eliminating system and the electrodynamic type igniter etc. of nuclear power plant all were at the hydrogen that disappears under the design basis accident operating mode in the past, can not satisfy the hydrogen requirement that disappears under the super design reference accident conditions.Its reason has 3 points: one, need energy supply; Two, need human intervention; Three, the hydrogen treat amount is less.Another shortcoming of electrodynamic type igniter is the uncertainty to combustion zone and incendiary type.
General hydrogen-eliminating catalyst is to be carrier with the aluminium oxide, the carried noble metal active component.Such catalyst has the higher hydrogen efficiency that disappears, and still, the non-metal carrier catalyst also exists some shortcomings.The intensity of non-metal carrier catalyst is not high, and easily broken, radiating effect is bad, and catalyst surface forms localized hyperthermia easily, makes the catalyst high temperature sintering, simultaneously, if under the high situation of density of hydrogen, light the air Mixture that contains hydrogen easily.
(3), summary of the invention:
In order to overcome the shortcoming of prior art, the invention provides a kind of metal carrier type hydrogen-eliminating catalyst and preparation method thereof, metal carrier type hydrogen-eliminating catalyst intensity height provided by the invention, thermal conductivity is good, active component is uniformly dispersed, and has the advantages that low, the active height of start-up temperature, anti-poisoning capability are strong, adapt to high temperature, high humidity environment.
The present invention solves the technical scheme that its technical problem takes: hydrogen-eliminating catalyst provided by the invention is the metal carrier type catalyst, comprises caltalyst and has the mixed crystal layer of the hydrogen activity that disappears.
Described mixed crystal layer is mainly noble metal and/or auxiliary agent with catalytic activity and forms.
Described noble metal is one or more in platinum, palladium, silver and the gold.
Described auxiliary agent is present on the catalyst with the form of oxide, at least a in Na, K, Cr and the rare earth metal, and the rare earth metal component refers generally to La, Ce, Pr, Nd.
Described caltalyst is a plate-shape metal, and its version is flat board, perforated plate, wire netting, and thickness is 0.1～2.5mm, and material is corrosion resistant plate, titanium plate, copper coin or aluminium sheet, metal surface coating Al
2O
3, SiO
2, TiO
2, SnO
2Or ceramic carrier material.
Metal carrier type hydrogen-eliminating catalyst provided by the invention can make by following step:
(1), with the metallic carrier of choosing, carry out cleaning surfaces after, in 80～120 ℃ of dry for standby; (2), with noble metal (for example Pd, Pt or Ag) salt or acids, be mixed with the solution that bullion content is 0.05～0.30g/ml.Its chemical property is looked in the adding of auxiliary agent, or independent dipping, or dissolves in active component solution and soak altogether; (3), press catalyst cupport active component aequum, the precious metal solution after an amount of dilution is mixed with carrier floods, the ratio of solution amount and carrier water absorption rate is 1.5: 1, agitation as appropriate, and 80～120 ℃ of dryings 2～5 hours, till oven dry, catalyst weightening finish≤3%; Perhaps in precious metal solution, add an amount of binding agent and make coating liquid, will apply liquid and brush on the metallic carrier, and in 80～120 ℃ of oven dry; (4), roasting at high temperature subsequently, temperature is in 300～750 ℃ of scopes, and temperature is 400～650 ℃ preferably, uses hydrogen reducing then in 230～650 ℃ of temperature ranges, used hydrogen is pure hydrogen or hydrogen nitrogen mixed gas, and the gained finished catalyst is generally light gray or Dark grey.
Experiment shows, this metal carrier type catalyst disappear hydrogen efficiency height, long service life, moisture resistance is good, mithridatism is high, is applicable to inflammable and explosive hydrogen in the confined spaces such as eliminating the npp safety shell.
(4), the specific embodiment
Hydrogen-eliminating catalyst provided by the invention is the metal carrier type catalyst, comprises caltalyst and the mixed crystal layer with the hydrogen activity that disappears.The preferred plate-shape metal of caltalyst, especially special stainless steel plate, titanium plate, copper coin, aluminium sheet and metal surface coating Al
2O
3, SiO
2, TiO
2, SnO
2Or ceramic carrier material, the version of plate-shape metal is flat board, perforated plate, wire netting etc., thickness is 0.1～2.5mm, it is active component that the mixed crystal layer contains noble metal, the noble metal composition refers in particular to one or more among Pd, Pt, Ag, the Au etc., and add and to be selected from least a as auxiliary element in Na, K, Cr and the rare earth metal, the rare earth metal component refers generally to La, Ce, Pr, Nd etc.
Active component Pt, Pd and Ag can be from different salts and acids, and reagent commonly used has: (NH
4)
2PtCl
4, H
2PtCl
66H
2O, H
2PtBr
6, K
2PtCl
4, (NH
4)
2PdCl
4, H
2PdCl
66H
2O, H
2PdBr
6, Na
2PdCl
4, K
2PdCl
4PdCl
4, PdCl
2, AgNO
3Deng.Noble metal platinum and silver have good hear resistance and anti-poisoning capability.Though the anti-poisoning capability of precious metal palladium is relatively poor, platinum is compared with silver, and it just can begin to work under lower environment temperature.Therefore, the multimetal reforming catalyst that has platinum, silver and a palladium just can start under lower environment temperature and density of hydrogen.Auxiliary agent is that the form with oxide is present on the catalyst, and its effect is that noble metal is uniformly dispersed, stops grain growth and sintering, improves the mithridatism of catalyst, heat endurance.Auxiliary agent adds with salt form usually, as: nitrate, hydrochloride, carbonate etc. resolve into oxide through heating.
The active component of metal carrier type hydrogen-eliminating catalyst provided by the invention is about 0.1 ~ 5% of catalyst weight percentage, adjuvant component is about 0.1 ~ 6.5% of catalyst weight percentage, by said ratio, the Preparation of catalysts method can adopt infusion process, hot spray process, coating process, ion-exchange etc.
Metal carrier type hydrogen-eliminating catalyst provided by the invention can make by following step:
(1) with the metallic carrier of choosing, carry out cleaning surfaces after, in 80～120 ℃ of dry for standby.
(2) with the salt or the acids of noble metal (for example Pd, Pt or Ag), be mixed with the solution that bullion content is 0.05～0.30g/ml.Its chemical property is looked in the adding of auxiliary agent, or independent dipping, or dissolves in active component solution and soak altogether.
(3) press catalyst cupport active component aequum, precious metal solution after an amount of dilution mixed with carrier flood, the ratio of solution amount and carrier water absorption rate is 1.5: 1, agitation as appropriate, and 80～120 ℃ of dryings 2～5 hours, till the oven dry (catalyst weightening finish≤3%); Perhaps in precious metal solution, add an amount of binding agent and make coating liquid, will apply liquid and brush on the metallic carrier, and in 80～120 ℃ of oven dry.
(4) roasting at high temperature subsequently, temperature is in 300～750 ℃ of scopes, and temperature is 400～650 ℃ preferably, uses hydrogen reducing then in 230～650 ℃ of temperature ranges, used hydrogen is pure hydrogen or hydrogen nitrogen mixed gas, and the gained finished catalyst is generally light gray or Dark grey.
Following example will give further instruction to Catalysts and its preparation method provided by the invention.
Example 1:
Get the spraying Al of 5 30 * 30mm
2O
3Stainless (steel) wire, fully wash with detergent, insert in the baking oven 100 ℃ of bakings 4 hours, it is standby to put into drier.
Measure the H that concentration is 0.1gPd/ml respectively
2PdCl
4The H of solution 5ml, 0.1gPt/ml
2PtCl
6Solution 10ml pours infuser into, adds the Ce (NO of 0.12gCe/ml
3)
3Behind the solution 3ml, metallic carrier put into flood, agitation as appropriate, and 120 ℃ of dryings 2 hours.At 450 ℃ of following roasting 3h, use hydrogen (air speed 1000 hours then subsequently
-1) at 450 ℃ of temperature reduction 5h, naturally cool to room temperature, taking out finished catalyst is uniform Dark grey.
5 catalyst samples of in catalyst activity is estimated flow process, packing into and making, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is about 78%.80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion still is 78%.
Example 2
Get the spraying Al of 5 30 * 30mm
2O
3Stainless (steel) wire, fully wash with detergent, insert in the baking oven 100 ℃ of bakings 4 hours, it is standby to put into drier.
Measure the H that concentration is 0.1gPd/ml respectively
2PdCl
4Solution 5ml, concentration are the H of 0.1gPt/ml
2PtCl
6The AgNO of solution 6ml and 0.15gAg/ml
3Solution 4ml pours infuser into, adds the La (NO of 0.12gCe/ml
3)
3Behind the solution 3ml, metallic carrier put into flood, agitation as appropriate, and 100 ℃ of dryings 2 hours.At 600 ℃ of following roasting 2h, use hydrogen (air speed 1000 hours-1) at 400 ℃ of temperature reduction 5h then subsequently, naturally cool to room temperature, it is light grey taking out finished catalyst.
Estimate 5 catalyst samples that flow process is packed into and made at catalyst activity, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is about 83%.80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion still is 83%.
Example 3
Get the stainless (steel) wire of 5 30 * 30mm, fully wash with detergent, insert in the baking oven 100 ℃ of bakings 4 hours, it is standby to put into drier.
Measure the H that concentration is 0.12gPd/ml respectively
2PdCl
4Solution 3ml, concentration are the H of 0.07gPt/ml
2PtCl
6The AgNO of solution 2ml and 0.19gAg/ml
3Solution 1ml stirs after the mixing, adds small amount of binder and 0.2gK again
2CO
3, stir and make coating liquid.
Coating liquid is brushed on the standby stainless (steel) wire, insert 120 ℃ of oven dry of baking oven 15 minutes,, use hydrogen (air speed 1000 hours then subsequently at 580 ℃ of following roasting 2h
-1) at 460 ℃ of temperature reduction 5h, naturally cooling to room temperature, the taking-up finished catalyst is a Dark grey.
5 catalyst samples of in catalyst activity is estimated flow process, packing into and making, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is about 81%.80 ℃, relative humidity 100%, normal pressure, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, obtaining hydrogen conversion is 80%.
Claims (7)
1, a kind of metal carrier type hydrogen-eliminating catalyst is characterized in that: it is the metal carrier type catalyst, comprises caltalyst and the mixed crystal layer with the hydrogen activity that disappears.
2, metal carrier type hydrogen-eliminating catalyst according to claim 1 is characterized in that: described mixed crystal layer is mainly noble metal and/or auxiliary agent with catalytic activity and forms.
3, metal carrier type hydrogen-eliminating catalyst according to claim 2 is characterized in that: described noble metal is one or more in platinum, palladium, silver and the gold.
4, metal carrier type hydrogen-eliminating catalyst according to claim 2, it is characterized in that: described auxiliary agent is present on the catalyst with the form of oxide, at least a in Na, K, Cr and the rare earth metal, the rare earth metal component refers generally to La, Ce, Pr, Nd.
5, according to claim 1,2 or 5 described metal carrier type hydrogen-eliminating catalysts, it is characterized in that: the weight of described mixed crystal layer is 0.1～5% of caltalyst weight, and auxiliary agent is 0.1～6.5% of a catalyst weight.
6, metal carrier type hydrogen-eliminating catalyst according to claim 1, it is characterized in that: described caltalyst is a plate-shape metal, and its version is flat board, perforated plate, wire netting, and thickness is 0.1～2.5mm, material is corrosion resistant plate, titanium plate, copper coin or aluminium sheet, metal surface coating Al
2O
3, SiO
2, TiO
2, SnO
2Or ceramic carrier material.
7, a kind of method for preparing metal carrier type hydrogen-eliminating catalyst is characterized in that: make by following step: (1), with the metallic carrier of choosing, carry out cleaning surfaces after, in 80～120 ℃ of dry for standby; (2), with noble metal (for example Pd, Pt or Ag) salt or acids, be mixed with the solution that bullion content is 0.05～0.30g/ml.Its chemical property is looked in the adding of auxiliary agent, or independent dipping, or dissolves in active component solution and soak altogether; (3), press catalyst cupport active component aequum, the precious metal solution after an amount of dilution is mixed with carrier floods, the ratio of solution amount and carrier water absorption rate is 1.5: 1, agitation as appropriate, and 80～120 ℃ of dryings 2～5 hours, till oven dry, catalyst weightening finish≤3%; Perhaps in precious metal solution, add an amount of binding agent and make coating liquid, will apply liquid and brush on the metallic carrier, and in 80～120 ℃ of oven dry; (4), roasting at high temperature subsequently, temperature is in 300～750 ℃ of scopes, and temperature is 400～650 ℃ preferably, uses hydrogen reducing then in 230～650 ℃ of temperature ranges, used hydrogen is pure hydrogen or hydrogen nitrogen mixed gas, and the gained finished catalyst is generally light gray or Dark grey.
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|---|---|---|---|
| CNB2005100853931A CN100371073C (en) | 2005-07-27 | 2005-07-27 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
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|---|---|---|---|
| CNB2005100853931A CN100371073C (en) | 2005-07-27 | 2005-07-27 | Metal carrier type hydrogen-eliminating catalyst and preparation process thereof |
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| CN1736590A true CN1736590A (en) | 2006-02-22 |
| CN100371073C CN100371073C (en) | 2008-02-27 |
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|---|---|---|---|---|
| CN101711987B (en) * | 2009-11-11 | 2012-05-30 | 浙江工业大学 | Dehydrogenation catalyst and method for preparing same |
| CN102658168A (en) * | 2012-05-15 | 2012-09-12 | 中国船舶重工集团公司第七一八研究所 | Dehydrogenation catalyst taking Fe-Cr-Al alloy as metal carrier and preparation method thereof |
| CN102658138A (en) * | 2012-05-15 | 2012-09-12 | 中国船舶重工集团公司第七一八研究所 | Aluminum-plated metal carrier dehydrogenation catalyst and preparation method thereof |
| CN102671675A (en) * | 2012-06-05 | 2012-09-19 | 四川材料与工艺研究所 | Preparation method of catalytic board based on passive hydrogen recombiner of nuclear power plant |
| CN102744062A (en) * | 2012-07-12 | 2012-10-24 | 中国核动力研究设计院 | Passive hydrogen recombiner catalytic plate for nuclear power plant and hydrogen recombiner composed of catalytic plate |
| CN102928463A (en) * | 2012-10-19 | 2013-02-13 | 中国船舶重工集团公司第七一八研究所 | Concentration measuring system of hydrogen in containment vessel |
| CN103033591A (en) * | 2012-12-20 | 2013-04-10 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN103272586A (en) * | 2013-04-19 | 2013-09-04 | 四川材料与工艺研究所 | Preparation method for platinum membrane catalytic plate based on passive hydrogen and oxygen recombiner |
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| CN1113693C (en) * | 2001-07-27 | 2003-07-09 | 湖北省化学研究所 | Dehydrogenating catalyst containing more rare-earth elements for CO2 gas used to synthesize urea |
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| CN101711987B (en) * | 2009-11-11 | 2012-05-30 | 浙江工业大学 | Dehydrogenation catalyst and method for preparing same |
| CN102658168B (en) * | 2012-05-15 | 2014-05-28 | 中国船舶重工集团公司第七一八研究所 | Dehydrogenation catalyst taking Fe-Cr-Al alloy as metal carrier and preparation method thereof |
| CN102658168A (en) * | 2012-05-15 | 2012-09-12 | 中国船舶重工集团公司第七一八研究所 | Dehydrogenation catalyst taking Fe-Cr-Al alloy as metal carrier and preparation method thereof |
| CN102658138A (en) * | 2012-05-15 | 2012-09-12 | 中国船舶重工集团公司第七一八研究所 | Aluminum-plated metal carrier dehydrogenation catalyst and preparation method thereof |
| CN102671675A (en) * | 2012-06-05 | 2012-09-19 | 四川材料与工艺研究所 | Preparation method of catalytic board based on passive hydrogen recombiner of nuclear power plant |
| CN102671675B (en) * | 2012-06-05 | 2014-01-29 | 四川材料与工艺研究所 | Preparation method of catalytic board based on passive hydrogen recombiner of nuclear power plant |
| CN102744062A (en) * | 2012-07-12 | 2012-10-24 | 中国核动力研究设计院 | Passive hydrogen recombiner catalytic plate for nuclear power plant and hydrogen recombiner composed of catalytic plate |
| CN102744062B (en) * | 2012-07-12 | 2014-11-26 | 中国核动力研究设计院 | Passive hydrogen recombiner catalytic plate for nuclear power plant and hydrogen recombiner composed of catalytic plate |
| CN102928463A (en) * | 2012-10-19 | 2013-02-13 | 中国船舶重工集团公司第七一八研究所 | Concentration measuring system of hydrogen in containment vessel |
| CN103033591A (en) * | 2012-12-20 | 2013-04-10 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN103033591B (en) * | 2012-12-20 | 2015-02-18 | 中国船舶重工集团公司第七一八研究所 | System and method for testing catalyst dehydrogenation performance |
| CN103272586A (en) * | 2013-04-19 | 2013-09-04 | 四川材料与工艺研究所 | Preparation method for platinum membrane catalytic plate based on passive hydrogen and oxygen recombiner |
| CN103272586B (en) * | 2013-04-19 | 2014-08-06 | 四川材料与工艺研究所 | Preparation method for platinum membrane catalytic plate based on passive hydrogen and oxygen recombiner |
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