CN102658138A - Aluminum-plated metal carrier dehydrogenation catalyst and preparation method thereof - Google Patents
Aluminum-plated metal carrier dehydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN102658138A CN102658138A CN2012101499249A CN201210149924A CN102658138A CN 102658138 A CN102658138 A CN 102658138A CN 2012101499249 A CN2012101499249 A CN 2012101499249A CN 201210149924 A CN201210149924 A CN 201210149924A CN 102658138 A CN102658138 A CN 102658138A
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- carrier layer
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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
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Abstract
The invention discloses an aluminum-plated metal carrier dehydrogenation catalyst and a preparation method thereof, which belong to the field of catalyst applications. The catalyst consist of a metal carrier layer, a gamma-Al2O3 porous material layer and a catalyst layer, wherein the metal carrier layer is made of an aluminum-plated steel plate or aluminum-plated alloy; and the catalyst layer consists of a precious metal and/or aid with catalytic activity. The preparation method comprises the following steps of: cleaning and drying the metal carrier layer; completely converting an aluminum-plated layer into Al2O3 through anodic oxidation; corroding and broaching; coating or dipping a layer of active Al2O3 on the surface of the broached Al2O3; drying and sintering to obtain a gamma-Al2O3 porous material layer; coating or dipping a catalyst layer; and drying, baking and reducing to obtain the aluminum-plated metal carrier dehydrogenation catalyst. In the catalyst, the bonding strength between the catalyst layer and the metal carrier is high, and the activity of the catalyst layer is high; and the preparation method is simple, and is low in cost.
Description
Technical field
The present invention relates to a kind of al-plated metallic substrate hydrogen-eliminating catalyst and preparation method thereof, be specifically related to a kind of Catalysts and its preparation method that is used for the non-active elimination hydrogen of nuclear power station, belong to the catalyst applications field.
Background technology
After nuclear power plant's presurized water reactor generation loss of-coolant accident (LOCA) (LOCA), because the failure of coolant loss and emergency power cooling agent injection, 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 gets into 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.Only if adopted some system to be under its flammability limit to keep density of hydrogen, otherwise the enriching quantity of hydrogen can increase greatly in the containment atmosphere, thereby in containment, generates potential explosive gas mixture.Accidental afterwards once igniting can be because of the burning of a large amount of hydrogen or the integrality that blast jeopardizes containment.
In order to prevent in containment, to form this type explosive gas mixture, 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 kinds of 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 to 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 is the hydrogen-eliminating catalyst of carrier with the metal, the carried noble metal active component.Such catalyst has the higher hydrogen efficiency that disappears, and still, these metal carrier catalysts also exist some shortcomings.Because metal carrier surface atresia, smoother are difficult for the supported catalyst layer, and the coefficient of expansion of catalyst layer and metallic carrier do not match, and causes the conjugation of catalyst layer and metal carrier layer low, comes off easily; The metallic carrier specific area is less, is difficult for adsoption catalyst, and catalyst is bad in the metal carrier surface dispersiveness, so need repeatedly coated catalysts just can reach the amount of required catalyst, to reach active preferably, causes complicated process of preparation, and cost is high.
Summary of the invention
The object of the present invention is to provide a kind of al-plated metallic substrate hydrogen-eliminating catalyst and preparation method thereof; The bond strength of catalyst layer and metallic carrier is high in the said catalyst, and thermal conductivity is good, and active constituent is uniformly dispersed; Catalyst layer active good; Have the advantages that start-up temperature is low, activity is high, the mithridatism ability is strong, adapt to high temperature, high humidity environment, the preparation method is simple, and cost is low.
The object of the invention is realized by following technical scheme:
A kind of al-plated metallic substrate hydrogen-eliminating catalyst, said catalyst is by metal carrier layer, γ-Al
2O
3Porous material layer and catalyst layer are formed, γ-Al
2O
3Porous material layer is anchored on metal carrier layer, and catalyst layer applies or impregnated in γ-Al
2O
3The porous material laminar surface.
Said metallic carrier layer material is aludip or alloy plating; Be shaped as tabular or corrugated, wherein plate-like structure is imperforate plate, perforated plate or wire netting, and wave structure is imperforate plate, perforated plate or wire netting; The metallic carrier layer thickness is 0.3～1mm.
Said γ-Al
2O
3The porous material layer thickness is 10～100 μ m.
Said catalyst layer is made up of noble metal with catalytic activity and auxiliary agent; Wherein, noble metal is one or more among Pt, Pd, Rh, Ru, Ir, Ag and the Au, and weight is 0.3～1.5% of metal carrier layer; Auxiliary agent is present on the catalyst layer with the form of oxide, at least a in Na, K, Cr and the rare earth metal; Said rare earth metal is La, Ce, Pr, Nd; Auxiliary agent is 0.1～6.5% of a catalyst layer gross weight.
Preparation method's step of a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention is following:
(1) metal carrier layer is cleaned drying;
(2) metal carrier layer of step (1) being handled is carried out anodic oxidation, makes aluminium coated be completely oxidized to Al
2O
3, corrode reaming then, clean and drying;
(3) Al after reaming
2O
3Surface-coated or dipping active A l
2O
3Colloidal sol;
(4) the product oven dry back roasting that step (3) is obtained, the γ-Al that obtains having porous character
2O
3Carrier layer; Wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and preferred 400～500 ℃, the time is 2～6 hours;
(5) with the salt or the acids of noble metal, be mixed with the solution that bullion content is 0.05～0.30g/ml, in solution, add auxiliary agent, obtain having the solution of catalytic activity;
(6) solution with catalytic activity that step (5) is prepared applies or is impregnated into the carrier layer surface with porous character that step (4) obtains, and oven dry back roasting, and wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and preferred 400～500 ℃, the time is 2～6 hours;
(7) repeating step (6), bullion content is 0.3～1.5% of a metal carrier layer weight in catalyst layer;
(8) product that step (7) is obtained with hydrogen reducing 5～10h, obtains a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention in 230～650 ℃ of temperature ranges.
Beneficial effect
1. the Al that obtains through anodic oxidation
2O
3Layer has non-oxidizability, and corrosion resistance and higher mechanical strength can effectively improve the mechanical strength of metal carrier layer.And the Al that makes
2O
3Layer is higher with the bond strength of metal carrier layer, makes that the bond strength of catalyst layer and metal carrier layer of subsequent coated or dipping is higher.
2. good anti-strip property makes the metallic carrier laminar surface after the anodic oxidation have loose structure through reaming, can with the active A l of subsequent coated
2O
3Layer effectively combines.
3. because γ-Al
2O
3Porous material layer has higher specific surface area; Than being easier to the adsorption activity component; And it is dispersed preferably to make that noble metal catalyst has; Make to apply or the catalyst layer of dipping has higher activity and heat-resisting quantity, activity does not descend in the time of can guaranteeing under hot conditions, to use, when avoiding high temperature because the transformation of carrier sintering or crystal formation is shone into catalyst activity loses.
4. because γ-Al
2O
3Porous material layer has higher specific surface area, than being easier to the adsoption catalyst layer, makes to apply or the minimizing of dipping number of times, has reduced labour intensity, has optimized the preparation method.
5. because γ-Al
2O
3The porous character of porous material layer; Make to have higher activity by the catalyst good dispersion that applies or flood, therefore reduced the demand of noble metal amount; And the metal carrier layer cost that uses is low, makes a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention have lower cost.
The specific embodiment
Below in conjunction with specific embodiment the present invention is detailed, but is not limited thereto.
Embodiment 1
Get the aluminum-plated steel expanded metals of 5 30 * 30mm, every wire netting thickness of slab is 0.6mm, is 2g heavily, fully washs with detergent; In 120 ℃ of bakings 4 hours, the phosphoric acid with 2mol/l was electrolyte then, and graphite is negative electrode, and the aluminum-plated steel expanded metals is carried out anodic oxidation; Oxidization time is 2 hours, and voltage is 80V, and temperature is a room temperature; Current density is 3A, in order to make aluminum-plated steel expanded metals two sides oxidation effectiveness identical, uses the twin cathode method to carry out oxidation; Aluminum-plated steel expanded metals after the anodic oxidation is put into the mixed liquor of phosphoric acid, chromic acid and deionized water; Wherein, The mass ratio of each component is a phosphoric acid in the mixed liquor: chromic acid: deionized water=1: 3: 46; At room temperature corrode reaming, make the aludip net surface of surperficial mild oxidation form pit, then after deionized water for ultrasonic is cleaned three times 120 ℃ of oven dry; Al after reaming
2O
3Surface-coated layer of active Al
2O
3Colloidal sol is in 120 ℃ of bakings 2 hours, at 450 ℃ of following roastings 3 hours, gained γ-Al
2O
3The porous material layer thickness is 50 μ m, and it is subsequent use to put into drying box.
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, and wherein, the concentration of noble metal is 0.1g/ml, adds the Ce (NO of 0.12gCe/ml
3)
3Behind the solution 3ml, will be coated with active A l
2O
3Metallic carrier put into infuser and flood, and 120 ℃ of dryings 4 hours.Then 450 ℃ of following roastings 3 hours, repeated impregnations, and oven dry back roasting 3 times, at this moment, the gained noble metal (Pd, Pt) gross weight is 0.5% of a metal carrier layer, auxiliary agent Ce content is 0.1% of catalyst layer gross weight, then 450 ℃, air speed 1000 hours
-1With hydrogen reducing 5 hours, naturally cool to room temperature under the condition, promptly obtain a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention, wherein, γ-Al in the said catalyst
2O
3Porous material layer is anchored on metal carrier layer, and catalyst layer impregnated in γ-Al
2O
3The porous material laminar surface.
5 catalyst samples of in catalyst activity is estimated flow process, packing into and processing, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, promptly hydrogen is through catalyst sample, with airborne oxygen reaction generation water, obtaining hydrogen conversion was 85% under catalytic action, 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 83%.
Embodiment 2
Get the aluminum-plated steel expanded metals of 5 30 * 30mm, every wire netting thickness of slab is 0.6mm, is 2g heavily, fully washs with detergent; In 100 ℃ of bakings 6 hours, the phosphoric acid with 2mol/l was electrolyte then, and graphite is negative electrode, and the aluminum-plated steel expanded metals is carried out anodic oxidation; Oxidization time is 2 hours, and voltage is 80V, and temperature is a room temperature; Current density is 3A, in order to make aluminum-plated steel expanded metals two sides oxidation effectiveness identical, uses the twin cathode method to carry out oxidation; Aluminum-plated steel expanded metals after the anodic oxidation is put into the mixed liquor of phosphoric acid, chromic acid and deionized water; Wherein, The mass ratio of each component is a phosphoric acid in the mixed liquor: chromic acid: deionized water=1: 3: 46; At room temperature corrode reaming, make the aludip net surface of surperficial mild oxidation form pit, then after deionized water for ultrasonic is cleaned three times 120 ℃ of oven dry; Al after reaming
2O
3Surface impregnation layer of active Al
2O
3Colloidal sol is in 100 ℃ of bakings 3 hours, at 500 ℃ of following roastings 2.5 hours, gained γ-Al
2O
3The porous material layer thickness is 50 μ m, and it is subsequent use to put into drying box.
Measure the H that concentration is 0.1gPd/ml respectively
2PdCl
4The H of solution 5ml, 0.1gPt/ml
2PtCl
6The AgNO of solution 6ml and 0.15gAg/ml
3Solution 4ml pours infuser into, and wherein, the concentration of noble metal is 0.11g/ml, adds the Ce (NO of 0.12gCe/ml
3)
3Behind the solution 3ml, will be impregnated with active A l
2O
3Metallic carrier put into infuser and flood, and 100 ℃ of dryings 5 hours.Then 500 ℃ of following roastings 2.5 hours, repeated impregnations, and oven dry back roasting 3 times, at this moment, (Ag) gross weight is 0.5% of a metal carrier layer to noble metal for Pd, Pt, and auxiliary agent Ce content is 0.1% of catalyst layer gross weight.Then 500 ℃, air speed 1000 hours
-1With hydrogen reducing 5 hours, naturally cool to room temperature under the condition, promptly obtain a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention, wherein, γ-Al in the said catalyst
2O
3Porous material layer is anchored on metal carrier layer, and catalyst layer impregnated in γ-Al
2O
3The porous material laminar surface.
5 catalyst samples of in catalyst activity is estimated flow process, packing into and processing, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, promptly hydrogen is through catalyst sample, with airborne oxygen reaction generation water, obtaining hydrogen conversion was 80% under catalytic action, 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 78%.
Embodiment 3
Get the aluminum-plated steel expanded metals of 5 30 * 30mm, every wire netting thickness of slab is 0.6mm, is 2g heavily, fully washs with detergent; In 80 ℃ of bakings 6 hours, the phosphoric acid with 2mol/l was electrolyte then, and graphite is negative electrode, and the aluminum-plated steel expanded metals is carried out anodic oxidation; Oxidization time is 2 hours, and voltage is 80V, and temperature is a room temperature; Current density is 3A, in order to make aluminum-plated steel expanded metals two sides oxidation effectiveness identical, uses the twin cathode method to carry out oxidation; Aluminum-plated steel expanded metals after the anodic oxidation is put into the mixed liquor of phosphoric acid, chromic acid and deionized water; Wherein, The mass ratio of each component is a phosphoric acid in the mixed liquor: chromic acid: deionized water=1: 3: 46; At room temperature corrode reaming, make the aludip net surface of surperficial mild oxidation form pit, then after deionized water for ultrasonic is cleaned three times 120 ℃ of oven dry; Al after reaming
2O
3Surface-coated layer of active Al
2O
3Colloidal sol is in 80 ℃ of bakings 5 hours, at 400 ℃ of following roastings 4 hours, gained γ-Al
2O
3The porous material layer thickness is 50 μ m, and it is subsequent use to put into drying box.
Measure the H that concentration is 0.12gPd/ml respectively
2PdCl
4The H of solution 3ml, 0.07gPt/ml
2PtCl
6The AgNO of solution 2ml and 0.19gAg/ml
3Solution 1ml pours infuser into, and wherein, the concentration of noble metal is 0.12g/ml, adds 0.2gK
2CO
3, stir and process coating liquid.Coating liquid brushed be coated with active A l
2O
3Metallic carrier on, and 80 ℃ of dryings 2 hours.400 ℃ of following roastings 4 hours, repeat to brush, also dry back roasting 3 times then, at this moment, (Ag) gross weight is 0.5% of a metal carrier layer to noble metal for Pd, Pt, and auxiliary agent K content is 0.1% of catalyst layer gross weight.Then 500 ℃, air speed 1000 hours
-1With hydrogen reducing 5 hours, naturally cool to room temperature under the condition, promptly obtain a kind of al-plated metallic substrate hydrogen-eliminating catalyst of the present invention, wherein, γ-Al in the said catalyst
2O
3Porous material layer is anchored on metal carrier layer, and catalyst layer impregnated in γ-Al
2O
3The porous material laminar surface.
5 catalyst samples of in catalyst activity is estimated flow process, packing into and processing, at normal temperatures and pressures, air speed 20000 hours
-1, density of hydrogen is the hydrogen activity evaluation that disappears under 2% condition, promptly hydrogen is through catalyst sample, with airborne oxygen reaction generation water, obtaining hydrogen conversion was 83% under catalytic action, 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 81%.
The present invention includes but be not limited to above embodiment, every any replacement or local improvement of being equal to of under the principle of spirit of the present invention, carrying out all will be regarded as within protection scope of the present invention.
Claims (4)
1. al-plated metallic substrate hydrogen-eliminating catalyst, it is characterized in that: said catalyst is by metal carrier layer, γ-Al
2O
3Porous material layer and catalyst layer are formed, γ-Al
2O
3Porous material layer is anchored on metal carrier layer, and catalyst layer applies or impregnated in γ-Al
2O
3The porous material laminar surface;
Said metallic carrier layer material is aludip or alloy plating; Be shaped as tabular or corrugated, wherein plate-like structure is imperforate plate, perforated plate or wire netting, and wave structure is imperforate plate, perforated plate or wire netting; The metallic carrier layer thickness is 0.3～1mm;
Said γ-Al
2O
3The porous material layer thickness is 10～100 μ m;
Said catalyst layer is made up of noble metal with catalytic activity and auxiliary agent; Wherein, noble metal is one or more among Pt, Pd, Rh, Ru, Ir, Ag and the Au, and weight is 0.3～1.5% of metal carrier layer; Auxiliary agent is present on the catalyst layer with the form of oxide, at least a in Na, K, Cr and the rare earth metal; Said rare earth metal is La, Ce, Pr, Nd; Auxiliary agent is 0.1～6.5% of a catalyst layer gross weight.
2. the preparation method of an al-plated metallic substrate hydrogen-eliminating catalyst as claimed in claim 1, it is characterized in that: said method step is following:
(1) metal carrier layer is cleaned drying;
(2) metal carrier layer of step (1) being handled is carried out anodic oxidation, makes aluminium coated be completely oxidized to Al
2O
3, corrode reaming then, clean and drying;
(3) Al after reaming
2O
3Surface-coated or dipping active A l
2O
3Colloidal sol;
(4) the product oven dry back roasting that step (3) is obtained, the γ-Al that obtains having porous character
2O
3Carrier layer; Wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and the time is 2～6 hours;
(5) with the salt or the acids of noble metal, be mixed with the solution that bullion content is 0.05～0.30g/ml, in solution, add auxiliary agent, obtain having the solution of catalytic activity;
(6) solution with catalytic activity that step (5) is prepared applies or is impregnated into the carrier layer surface with porous character that step (4) obtains, and oven dry back roasting, and wherein bake out temperature is 80～120 ℃, and the time is 2～6 hours; Sintering temperature is 300～750 ℃, and the time is 2～6 hours;
(7) repeating step (6), bullion content is 0.3～1.5% of a metal carrier layer weight in catalyst layer;
(8) product that step (7) is obtained with hydrogen reducing 5～10h, obtains a kind of al-plated metallic substrate hydrogen-eliminating catalyst in 230～650 ℃ of temperature ranges.
3. the preparation method of a kind of al-plated metallic substrate hydrogen-eliminating catalyst according to claim 2 is characterized in that: the sintering temperature in the said step (4) is 400～500 ℃.
4. the preparation method of a kind of al-plated metallic substrate hydrogen-eliminating catalyst according to claim 2 is characterized in that: the sintering temperature in the said step (6) is 400～500 ℃.
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|---|---|---|---|
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Cited By (6)
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| CN107930646A (en) * | 2017-11-22 | 2018-04-20 | 南通斐腾新材料科技有限公司 | A kind of preparation method and application of turbulent structure metallic catalyst |
| CN108364698A (en) * | 2018-01-03 | 2018-08-03 | 中广核研究院有限公司 | The small space of nuclear power station disappears hydrogen methods and system |
| CN108863075A (en) * | 2018-07-20 | 2018-11-23 | 吴伟华 | A kind of enamel coating and application method |
| CN109482234A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
| CN109482205A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | Catalyst for normal paraffin isomerization and preparation method thereof |
| CN110662605A (en) * | 2017-05-30 | 2020-01-07 | 先技精工(日本)有限公司 | Method for producing catalyst or adsorbent carrier, and catalyst or adsorbent carrier |
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| CN110662605A (en) * | 2017-05-30 | 2020-01-07 | 先技精工(日本)有限公司 | Method for producing catalyst or adsorbent carrier, and catalyst or adsorbent carrier |
| CN109482234A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
| CN109482205A (en) * | 2017-09-12 | 2019-03-19 | 中国石油化工股份有限公司 | Catalyst for normal paraffin isomerization and preparation method thereof |
| CN109482234B (en) * | 2017-09-12 | 2021-09-07 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN109482205B (en) * | 2017-09-12 | 2021-10-08 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN107930646A (en) * | 2017-11-22 | 2018-04-20 | 南通斐腾新材料科技有限公司 | A kind of preparation method and application of turbulent structure metallic catalyst |
| CN108364698A (en) * | 2018-01-03 | 2018-08-03 | 中广核研究院有限公司 | The small space of nuclear power station disappears hydrogen methods and system |
| CN108364698B (en) * | 2018-01-03 | 2020-05-22 | 中广核研究院有限公司 | Hydrogen elimination method and system for small space of nuclear power station |
| CN108863075A (en) * | 2018-07-20 | 2018-11-23 | 吴伟华 | A kind of enamel coating and application method |
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|---|---|
| CN102658138B (en) | 2014-03-12 |
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