CN104001507A - Deoxidation catalyst and preparation method thereof - Google Patents
Deoxidation catalyst and preparation method thereof Download PDFInfo
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- CN104001507A CN104001507A CN201310231489.9A CN201310231489A CN104001507A CN 104001507 A CN104001507 A CN 104001507A CN 201310231489 A CN201310231489 A CN 201310231489A CN 104001507 A CN104001507 A CN 104001507A
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- cordierite
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Abstract
The invention relates to a deoxidation catalyst and a preparation method thereof. Cordierite ceramic honeycomb is used as a carrier; a composite material of Al2O3, CeO2 and ZrO2 is used as a transition layer of the catalyst; and Pt, Pd and Rh are used as active ingredients of the catalyst. Every liter of the deoxidation catalyst comprises 0.05-0.2 g of Pt, 0.5-1.5 g of Pd, 0.05-0.2 g of Rh, 15-75 g of Al2O3, 3-15 g of CeO2 and 3-15 g of ZrO2. The preparation method comprises the steps of pre-treating the cordierite ceramic honeycomb carrier, then coating the composite material of Al2O3, CeO2 and ZrO2 as the transition layer of the catalyst by a dipping method; and then loading Pt, Pd and Rh as the active ingredients of the catalyst by a precipitation-adsorption method. The preparation method has the advantages of simple process and low production cost. The catalyst has stable performances and low bed pressure loss, and is convenient for use and replacement, so that the catalyst is particularly suitable for purification of hydrogen in a hydrogen production device by water electrolysis.
Description
Technical field
The present invention relates to a kind of dehydrogenation catalyst and preparation method thereof, be particularly suitable for the purifying of water electrolysis hydrogen producing industry hydrogen, belong to catalyst technical field.
Background technology
Along with the development of national economy, hydro-electrolytic hydrogen production device has been widely used in the industries such as electric power, electronics, metallurgy, chemical industry, aerospace, semiconductor, polysilicon, how to adopt economy, efficient purification style, improve the purity of hydrogen, be subject to paying close attention to more and more widely.
The low concentration oxygen that catalytic purification method removes in the hydrogen that hydro-electrolytic hydrogen production device makes is considered to one of the most effective purification style.At present, be carrier at industrial general employing alundum (Al2O3), Supported Pt Nanoparticles, palladium pellet type catalyst carry out purified treatment.The diameter of this catalyst granules is generally 3～5mm, and air speed is 5000h
-1can make purify after hydrogen in oxygen content lower than below 5ppm, but this catalyst in use beds is prone to " dead volume ", catalyst is is easily worn and torn to suspending by gas flow purging, affect deoxidation effect, and because beds resistance drop is large, increase the operating cost of cleaning equipment.Therefore, exploitation is efficient, bed resistance is little, stable performance, installation and change dehydrogenation catalyst easily and have important practical significance.
Summary of the invention
The object of this invention is to provide a kind of dehydrogenation catalyst and preparation method thereof.
The present invention is taking cordierite ceramic honeycomb as carrier, Al
2o
3, CeO
2, ZrO
2composite is catalyst transition zone, and Pt, Pd, Rh are catalyst activity component, and in every liter of this catalyst, the content of Pt, Pd, Rh is respectively 0.05～0.2 gram, 0.5～1.5 gram, 0.05～0.2 gram, Al
2o
3, CrO
2, ZrO
2content be respectively 15～75 grams, 3～15 grams, 3～15 grams.The present invention has the advantages such as technique is simple, production cost is low, and the loss of catalyst performance stabilised, bed layer pressure little, use and change conveniently, be therefore particularly suitable for the purifying of hydrogen in hydro-electrolytic hydrogen production device.
The preparation method of catalyst of the present invention, its preparation process comprises:
(1) cordierite ceramic honeycomb carrier pretreatment:
Cordierite ceramic honeycomb carrier is put into dilute hydrochloric acid solution, remove powder and impurity in surface and micropore, after pretreatment 0.5～1h, take out carrier, with distilled water clean to aqueous ph value be 7.0, then carrier is put into baking oven, at 60～100 DEG C of dry 1～2h, then at 100～150 DEG C of dry 1～2h.
(2) preparation of transition zone:
By Al according to a certain ratio
2o
3, CeO
2, ZrO
2powder is poured in blender, stirs with agitator, then injects while stirring deionized water to mixture and is gluey, then add rare nitric acid toward solution in, and it is between 2～3 that limit edged is stirred to pH value, for subsequent use after standing 1～2h.
(3) coating of transition zone:
Pretreated cordierite is immersed in (2) described complex solution, after 5～20s, take out, blow away solution residual in cordierite duct with compressed air, again cordierite is put into baking oven, first at 60～100 DEG C of dry 1～2h, then be dried 1～2h at 100～150 DEG C, then temperature programming to 500 DEG C roasting, and be incubated 2～4h.
(4) load of noble metal:
Preparation is containing Pt by a certain percentage, Pd, the nitrate solution of Rh, while stirring with the potassium hydroxide solution of 0.5mol/L be added dropwise in above-mentioned solution to pH value be between 8～9, make A solution, then the carrier of being prepared by (3) is put into enamel pan, toward wherein adding deionized water to till flooding carrier upper surface, A solution is poured in enamel pan, and substitutional solution three times is above is evenly distributed to A solution, under steam tracing, be heated to solution boiling 1～3h clean to noble metal absorption, bleed off solution, carrier is cooled to room temperature, then be 7.0 with washed with de-ionized water to pH value, in enamel pan, add a certain amount of reducing agent again, and substitutional solution three times is above is evenly distributed to reducing agent, after leaving standstill 1～3h, bleed off solution, then be 7.0 with washed with de-ionized water to pH value, carrier after above-mentioned carried noble metal is put into baking oven, at 60～100 DEG C of dry 1～2h, then at 100～150 DEG C of dry 1～2h, then temperature programming to 500 DEG C roasting, and be incubated 2～4h, make catalyst.
Above-mentioned carrier is cordierite ceramic honeycomb, and its appearance and size is 150 × 150 × 40～60mm and 100 × 100 × 40～60mm, and number of aperture is 200～400 hole/in
2.
The preparation method of above-mentioned a kind of deoxidier, is characterized in that reducing agent used is the one in hydrogen peroxide, hydrazine hydrate, and its mass percent that accounts for the aqueous solution is 0.5～2.0%.
A kind of dehydrogenation catalyst provided by the present invention and preparation method thereof, its advantage is: technique is simple, production cost is low, the loss of catalyst performance stabilised, bed layer pressure is little, use and change conveniently, and equipment operating cost is low, is therefore particularly suitable for the purifying of hydrogen in hydro-electrolytic hydrogen production device.
Detailed description of the invention
Embodiment 1
Get 1 liter of cordierite ceramic honeycomb carrier, its appearance and size is 100 × 100 × 50mm, and number of aperture is 200 hole/in
2, carrier is put into the dilute hydrochloric acid solution of 0.1mol/L, take out after leaving standstill 0.5h, with washed with de-ionized water to PH be after 7.0 at 80 DEG C and 120 DEG C of each dry 1h, carrier is cooling rear for subsequent use, take Al
2o
3, CrO
2, ZrO
2powder quality (excessive) is respectively 150g, 6g, 6g pours in glass beaker and mixes, inject while stirring deionized water to mixture and be gluey, then in solution, add rare nitric acid, it is between 2～3 that limit edged is stirred to pH value, for subsequent use after standing 1h, pretreated cordierite is immersed in above-mentioned complex solution, approximately after 10s, take out, blow away solution residual in cordierite duct with compressed air, again cordierite is put into baking oven, at 80 DEG C and 120 DEG C of each dry 1h, then temperature programming to 500 DEG C roasting, and be incubated 3h, Al
2o
3, CrO
2, ZrO
2content be respectively 75 grams per liters, 3 grams per liters, 3 grams per liters, preparation is respectively the H of 0.05g, 0.8g, 0.05g containing Pt, Pd, Rh
2[PtCl
6], H
2[PdCl
6], RhCl
33H
2the O aqueous solution, while stirring with the potassium hydroxide solution of 0.5mol/L be added dropwise in above-mentioned solution to pH value be between 8～9, make A solution, carrier after above-mentioned coating transition zone is put into enamel pan, toward wherein adding deionized water to carrier upper surface, then A solution is poured in enamel pan, and substitutional solution three times, under steam tracing, be heated to solution boiling 2h clean to noble metal absorption, then be 7.0 with washed with de-ionized water to pH value, in enamel pan, add reducing agent hydrogen peroxide again, and substitutional solution three times, after leaving standstill 2h, bleed off solution, then be 7.0 with washed with de-ionized water to pH value, carrier after above-mentioned carried noble metal is put into baking oven, at 80 DEG C and 120 DEG C of each dry 1h, then temperature programming to 500 DEG C roasting, and be incubated 3h, make catalyst.In every liter of catalyst, be respectively 0.05g, 0.8g, 0.05g, Al containing Pt, Pd, Rh
2o
3, CrO
2, ZrO
2content be respectively 75 grams, 3 grams, 3 grams.This catalyst is at air speed 8000h
-1, oxygen content 1% in hydrogen plays work at 90 DEG C of temperature, exports the content of oxygen lower than 5ppm 150 DEG C time.
Embodiment 2
With the same operation of embodiment 1, difference is the transition zone Al of every liter of catalyst cupport
2o
3, CrO
2, ZrO
2content be respectively 60 grams, 5 grams, 5 grams, precious metals pt, Pd, Rh are respectively 0.1g, 1.2g, 0.1g.This catalyst is at air speed 8000h
-1, in hydrogen, oxygen content is 1%, at 80 DEG C of temperature, plays work, exports the content of oxygen lower than 5ppm 150 DEG C time.
Claims (6)
1. a dehydrogenation catalyst, is characterized in that: taking cordierite ceramic honeycomb as carrier, and Al
2o
3, CeO
2, ZrO
2composite is the transition zone of catalyst, the active component that Pt, Pd, Rh are catalyst.
2. the preparation method of a kind of dehydrogenation catalyst claimed in claim 1, is characterized in that, preparation process comprises:
(1) cordierite ceramic honeycomb carrier pretreatment
Cordierite ceramic honeycomb carrier is put into dilute hydrochloric acid solution, remove powder and impurity in surface and micropore, after pretreatment 0.5～1h, take out carrier, it is neutral cleaning to the aqueous solution with distilled water, then carrier is put into baking oven, at 60～100 DEG C of dry 1～2h, then at 100～150 DEG C of dry 1～2h;
(2) preparation of transition zone
By Al according to a certain ratio
2o
3, CeO
2, ZrO
2powder is poured in blender, stirs with agitator, then injects while stirring deionized water to mixture and is gluey, then add rare nitric acid toward solution in, and it is between 2～3 that limit edged is stirred to pH value, for subsequent use after standing 1～2h;
(3) coating of transition zone
Pretreated cordierite is immersed in (2) described complex solution, after 5～20s, take out, blow away solution residual in cordierite duct with compressed air, again cordierite is put into baking oven, first at 60～100 DEG C of dry 1～2h, then be dried 1～2h at 100～150 DEG C, then temperature programming to 500 DEG C roasting, and be incubated 2～4h;
(4) load of noble metal
Preparation is containing Pt by a certain percentage, Pd, the nitrate solution of Rh, while stirring with the potassium hydroxide solution of 0.5mol/L be added dropwise in above-mentioned solution to pH value be between 8～9, make A solution, then the carrier of being prepared by (3) is put into enamel pan, toward wherein adding deionized water to till flooding carrier upper surface, A solution is poured in enamel pan, and substitutional solution three times is above is evenly distributed to A solution, under steam tracing, be heated to solution boiling 1～3h clean to noble metal absorption, bleed off solution, carrier is cooled to room temperature, then be 7.0 with washed with de-ionized water to pH value, in enamel pan, add a certain amount of reducing agent again, and substitutional solution three times is above is evenly distributed to reducing agent, leave standstill 1～3h, bleed off solution, then be 7.0 with washed with de-ionized water to pH value, carrier after above-mentioned carried noble metal is put into baking oven, at 60～100 DEG C of dry 1～2h, then at 100～150 DEG C of dry 1～2h, then temperature programming to 500 DEG C roasting, and be incubated 2～4h, make catalyst.
3. catalyst according to claim 1, its carrier is cordierite ceramic honeycomb, and its appearance and size is 150 × 150 × 40～60mm and 100 × 100 × 40～60mm, and number of aperture is 200～400 hole/in
2.
4. catalyst according to claim 1, is characterized in that the content of Pt, Pd, Rh in every liter of catalyst is respectively 0.05～0.2 gram, 0.5～1.5 gram, 0.05～0.2 gram.
5. catalyst according to claim 1, is characterized in that Al in every liter of catalyst
2o
3, CeO
2, ZrO
2content be respectively 15～75 grams, 3～15 grams, 3～15 grams.
6. the preparation method of a kind of deoxidier according to claim 2, is characterized in that reducing agent used is the one in hydrogen peroxide, hydrazine hydrate, and its mass percent that accounts for the aqueous solution is 0.5～2.0%.
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|---|---|---|---|
| CN201310231489.9A CN104001507B (en) | 2013-06-09 | 2013-06-09 | A kind of dehydrogenation catalyst and preparation method thereof |
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|---|---|---|---|
| CN201310231489.9A CN104001507B (en) | 2013-06-09 | 2013-06-09 | A kind of dehydrogenation catalyst and preparation method thereof |
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| CN104001507A true CN104001507A (en) | 2014-08-27 |
| CN104001507B CN104001507B (en) | 2016-12-28 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876050A (en) * | 2017-11-10 | 2018-04-06 | 杭州尹力环保科技有限公司 | A kind of catalyst for purifying organic waste gas and preparation method thereof |
| CN108031472A (en) * | 2017-12-01 | 2018-05-15 | 杭州尹力环保科技有限公司 | A kind of Pd-Pt catalyst for purifying organic waste gas and preparation method thereof |
| CN116586120A (en) * | 2023-01-19 | 2023-08-15 | 长江三星能源科技股份有限公司 | Preparation method of multifunctional catalyst for hydrogen production purification and prepared catalyst |
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|---|---|---|---|---|
| CN1360972A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院大连化学物理研究所 | Wave absorbing catalyst and its prepn and application in purifying automobile tail gas |
| CN1473651A (en) * | 2002-08-07 | 2004-02-11 | 昆明贵研催化剂有限责任公司 | Noble metal-rare-earth catalyst for purifying waste gas and its preparation |
| US6852666B1 (en) * | 1999-05-07 | 2005-02-08 | Faurecia Systemes D'echappement | Purifying composition with NOx treatment and internal combustion engine exhaust gases |
| CN101224424A (en) * | 2008-02-04 | 2008-07-23 | 北京英泰世纪环境科技有限公司 | Double layer noble metal active component catalyst and preparing method thereof |
-
2013
- 2013-06-09 CN CN201310231489.9A patent/CN104001507B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6852666B1 (en) * | 1999-05-07 | 2005-02-08 | Faurecia Systemes D'echappement | Purifying composition with NOx treatment and internal combustion engine exhaust gases |
| CN1360972A (en) * | 2000-12-27 | 2002-07-31 | 中国科学院大连化学物理研究所 | Wave absorbing catalyst and its prepn and application in purifying automobile tail gas |
| CN1473651A (en) * | 2002-08-07 | 2004-02-11 | 昆明贵研催化剂有限责任公司 | Noble metal-rare-earth catalyst for purifying waste gas and its preparation |
| CN101224424A (en) * | 2008-02-04 | 2008-07-23 | 北京英泰世纪环境科技有限公司 | Double layer noble metal active component catalyst and preparing method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107876050A (en) * | 2017-11-10 | 2018-04-06 | 杭州尹力环保科技有限公司 | A kind of catalyst for purifying organic waste gas and preparation method thereof |
| CN108031472A (en) * | 2017-12-01 | 2018-05-15 | 杭州尹力环保科技有限公司 | A kind of Pd-Pt catalyst for purifying organic waste gas and preparation method thereof |
| CN116586120A (en) * | 2023-01-19 | 2023-08-15 | 长江三星能源科技股份有限公司 | Preparation method of multifunctional catalyst for hydrogen production purification and prepared catalyst |
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| CN104001507B (en) | 2016-12-28 |
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