CN1597104A - Integral catalyst for preparation hydrogen by methyl alcohot reformation and its preparation method - Google Patents
Integral catalyst for preparation hydrogen by methyl alcohot reformation and its preparation method Download PDFInfo
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- CN1597104A CN1597104A CNA2004100538858A CN200410053885A CN1597104A CN 1597104 A CN1597104 A CN 1597104A CN A2004100538858 A CNA2004100538858 A CN A2004100538858A CN 200410053885 A CN200410053885 A CN 200410053885A CN 1597104 A CN1597104 A CN 1597104A
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
An integrated catalyst for preparing H2 from methanol by reformation is composed of cellular ceramic carrier, the internal coated layer, and the external coated active component and cocatalyst coating. It features that its heat absorbing reaction and heat releasing reaction take place on a same catalyst bed layer, resulting in high dynamic response.
Description
Technical field
The present invention relates to a kind of preparing hydrogen by reforming methanol Catalysts and its preparation method, relate to a kind of copper zinc-base multicomponent catalyst that is used for preparing hydrogen by reforming methanol and preparation method thereof specifically.
Background technology
Along with the increasingly mature of fuel cell technology and to the meaning of environment protection, adopt the fuel cell car of fuel cell technology to be developed rapidly in recent years, the methyl alcohol vehicle-mounted hydrogen production becomes comparatively one of ideal hydrogen supply scheme.
Hydrogen production from methanol-steam reforming, because of its higher product hydrogen rate, sophisticated production technique is widely used in hydrogen manufacturing industry.But methanol steam reforming is thermo-negative reaction, and outside a large amount of heat that provides is provided.Heat generation and heat-exchanger rig have limited the miniaturization of device for producing hydrogen.In addition, also easily efflorescence in the jolting, shake of vehicle driving process of granular commercial catalysts.
Therefore develop a kind of heat that can on same catalyzer, produce directly supply water the oxidation and reformation of methanol technology and the integral catalyzer of steam reformation, become the problem that numerous scientific and technical personnel extremely pay close attention to the part methanol oxidation.
Present methanol recapitalization or catalyst for oxidation and reformation prepare by coprecipitation method basically, this preparation method has higher requirement to the control of sedimentary pH value, and the washing of precipitated liquid need expend a large amount of water, produce simultaneously a large amount of waste water again, both uneconomical also not environmental protection the more important thing is that this preparation method is difficult to make integral catalyzer.
Summary of the invention
The technical issues that need to address of the present invention are open preparing hydrogen by reforming methanol integral catalyzers and preparation method thereof, to overcome the above-mentioned defective that prior art exists, satisfy the needs of relevant field development.
Preparing hydrogen by reforming methanol integral catalyzer of the present invention comprises:
Cellular structure ceramic carrier loads on the bottom on cellular structure ceramic carrier outside surface and the micropore internal surface, loads on active ingredient and promoter coatings on the bottom;
Said bottom is one or more the aluminum oxide that has mixed in lanthanum, cerium, praseodymium, neodymium, zirconium or the titanyl compound, and the oxide compound that mixes is the 2-50% of alumina weight; The bottom charge capacity is a 10-200 grams per liter catalyzer.
Said active ingredient and promoter coatings are the aluminum oxide that contains active ingredient and promotor, wherein:
Said active ingredient is copper and zinc;
Said promotor is one or more in rare-earth oxide or the zirconium white, and its molfraction is:
1.0 parts of zinc 0.1-1.0 of copper part zirconium white 0-0.5 part rare-earth oxide 0-0.5 part, rare earth element is selected from one or more among La, Ce, Pr, Nd, Y, the Sc;
The charge capacity of active ingredient and promoter coatings is a 50-500 grams per liter catalyzer.
The preparation method of preparing hydrogen by reforming methanol integral catalyzer of the present invention comprises the steps:
(1) adopts conventional method to carry out the carrier pre-treatment, can with cellular structure ceramic carrier after deionized water wash, dehydration, in the fluidizing air atmosphere, under 120-200 ℃, dry 4-10 hour, naturally cool to room temperature;
(2) carrier coating
With above-mentioned carrier under vacuum condition, excessive one or more aluminum oxide slurries that impregnated in nitrate, acetate, muriate, vitriol or the oxide compound that is mixed with rare-earth elements of lanthanum, cerium, praseodymium, neodymium, zirconium or titanium, wherein be the 2-50% of alumina weight in the slurry with the metal oxide incorporation, after dip-coating 5-60 minute, remove the surplus slurry in the carrier duct, seasoning 4-24 hour, in the fluidizing air atmosphere, under 80-150 ℃, dry 4-10 hour, under 300-700 ℃, roasting 2-10 hour, obtain to have the support of the catalyst of bottom.
(3) under vacuum condition, support of the catalyst with bottom impregnated in and is mixed with copper, zinc, the aluminum oxide slurries of zirconium and rare earth element, the element that mixes comprises nitrate, acetate, muriate, arbitrary form in vitriol or the oxide compound, wherein rare earth element is selected from lanthanum, cerium, praseodymium, neodymium, in yttrium or the scandium one or more, after dip-coating 5-60 minute, remove the surplus slurry in the carrier duct, seasoning 4-24 hour, in the fluidizing air atmosphere, under 80-150 ℃, dry 4-10 hour, under 250-600 ℃, roasting 2-10 hour, acquisition had the catalyzer of active component coating.
Catalyzer of the present invention can be used for the hydrogen through reforming oxidized methyl alcohol reaction, during use, need carry out catalyst activation, with above-mentioned catalyzer, be in the mobile atmosphere of 10-100% in density of hydrogen, under 100-500 ℃, in-situ activation 1-10 hour, promptly can be used for the preparing hydrogen by reforming methanol process.
When copper provided by the invention, zinc-base multicomponent catalyst are applied to the hydrogen through reforming oxidized methyl alcohol reaction, because of its bi-functional, can make heat absorption and thermopositive reaction carry out at same beds, this coupled catalyzed reaction effect, not only made full use of reaction heat, saved energy, and the direct heat transmission of heat release and heat absorption can produce quick startup and outstanding dynamic response effect.
The low temperature active of preparing hydrogen by reforming methanol integral catalyzer provided by the invention is good, and carbon monoxide concentration is low in the hydrogen, the catalyst strength height, and dynamic response is fast, is particularly suitable for vehicle-mounted and small-sized on-the-spot hydrogen supply device and uses.
Embodiment
Embodiment 1
Get one be of a size of Φ 19 * 30, hole count is 47 holes/cm
2Garden cylindricality cordierite ceramic honeycomb carrier, after deionized water wash, dehydration, in the fluidizing air atmosphere, under 120 ℃, dry 4 hours, under 500 ℃, roasting 2 hours naturally cooled to room temperature with this carrier.
Will be after the degassing of pretreated carrier, vacuumizing, impregnated in the solid content that has added lanthanum, cerium and titanium and be 25% alumina slurry, it is as follows that the weight percent of each component is formed (in oxide compound) in the slurry:
γ-Al
2O
3????????????????????????????????????88％
La
2O
3(adding) 5% with the water-soluble back of lanthanum nitrate
CeO
2(adding) 5% with the water-soluble back of cerous nitrate
TiO
2(adding) 2% with metatitanic acid
After the dip-coating 10 minutes, remove the surplus slurry in the carrier duct, seasoning 6 hours, in the fluidizing air atmosphere, under 80 ℃, dry 6 hours, under 500 ℃, roasting 4 hours obtained to have the support of the catalyst of precoated layer.
The support of the catalyst that will have precoated layer is after the degassing, vacuumizing, and the solid content of excessive dip-coating interpolation copper, zinc, zirconium and lanthanum is 30% alumina slurry, and it is as follows that the weight percent of each component is formed (in oxide compound) in the slurry:
γ-Al
2O
3????????????????????????????????????????72％
CuO (adding) 15% with the water-soluble back of cupric nitrate
ZnO (adding) 7% with the water-soluble back of zinc nitrate
ZrO
2(adding) 3% with the water-soluble back of zirconium nitrate
La
2O
3(adding) 3% with the water-soluble back of lanthanum nitrate
Flood after 10 minutes, remove the surplus slurry in the carrier duct, seasoning 6 hours, in the fluidizing air atmosphere, under 80 ℃, dry 6 hours, under 450 ℃, roasting 4 hours, acquisition has the catalyst precursor of active component coating.
With above-mentioned catalyst precursor with active component coating, place embodiment 5 described reactors, in density of hydrogen is 40% mobile atmosphere, under 350 ℃, activate 3 hours, promptly make activated state oxidation and reformation of methanol integral catalyzer of the present invention.
Embodiment 2
The oxidation and reformation of methanol integral catalyzer adopts the preparation method identical with embodiment 1, but zirconic content doubles in the activated coating, and promptly 6%, γ-Al
2O
3Content be kept to 69%, and other component concentration is constant.
Embodiment 3
The oxidation and reformation of methanol integral catalyzer adopts the preparation method identical with embodiment 1, but zirconic content is zero in the activated coating, CeO
2Content be 6%, and other component concentration is constant.
Embodiment 4
The oxidation and reformation of methanol integral catalyzer adopts the preparation method identical with embodiment 1, but the weight percent of each component composition (in oxide compound) is as follows in the activated coating:
γ-Al
2O
3????????????????????????????????????64％
CuO (adding) 22% with the water-soluble back of cupric nitrate
ZnO (adding) 10% with the water-soluble back of zinc nitrate
ZrO
2(adding) 4% with the water-soluble back of zirconium nitrate
Embodiment 5
It is that the stainless steel tubular type reactor of 20mm carries out activity rating that the catalyzer of getting embodiment 1 preparation places internal diameter.Appreciation condition: the vaporization temperature of reaction mass maintains 200 ℃, and temperature of reaction is 200-250 ℃, normal pressure, with the mixed solution of micro pump feeding first alcohol and water, feeding rate is 0.25ml/min, and water alcohol mol ratio is 1: 1, use the pneumatic pump bubbling air, making oxygen alcohol mol ratio is 0.22.After the stable reaction, sampling analysis.Reaction product is after condensation, and gas-phase product carries out on-line analysis with two placed in-line gas-chromatographies.At first after the gac packed column separates, by the concentration of the gas chromatographic detection hydrogen that has thermal conductivity detector (TCD) etc.Gas chromatographic detection CO through having methanation convertor and hydrogen flame detector (FID), CO then
2Deng concentration.The concentration of unreacted methanol is by the gas chromatographic detection that has GDX-401 packed column and hydrogen flame detector (FID) in the liquid product that condensation is collected.Evaluation result sees Table 1
| Temperature of reaction (℃) | Methanol conversion (%) | CO 2Selectivity (%) | CO concentration (%) |
| ????250 | ????96 | ????98.4 | ????0.35 |
| ????225 | ????88 | ????99.2 | ????0.15 |
| ????200 | ????84 | ????99.5 | ????0.10 |
Table 1
Embodiment 6
It is that the stainless steel tubular type reactor of 20mm carries out activity rating that the catalyzer of getting embodiment 2 preparation places internal diameter, estimate and analysis condition with embodiment 5.Evaluation result sees Table 2.
| Temperature of reaction (℃) | Methanol conversion (%) | CO 2Selectivity (%) | CO concentration (%) |
| ????250 | ????99 | ????98.9 | ????0.20 |
| ????225 | ????87 | ????99.5 | ????0.16 |
| ????200 | ????80 | ????99.8 | ????0.09 |
Table 2
Embodiment 7
It is that the stainless steel tubular type reactor of 20mm carries out activity rating that the catalyzer of getting embodiment 3 preparation places internal diameter.Appreciation condition: the vaporization temperature of reaction mass maintains 200 ℃, and temperature of reaction is 200-250 ℃, normal pressure, and with the mixed solution of micro pump feeding first alcohol and water, feeding rate is 0.25ml/min, water alcohol mol ratio is 3: 1.Analysis condition is with embodiment 5.Evaluation result sees Table 3.
| Temperature of reaction (℃) | Methanol conversion (%) | CO 2Selectivity (%) | CO concentration (%) |
| ????250 | ????84 | ????99.4 | ????0.1 |
| ????225 | ????77 | ????99.4 | ????0.1 |
| ????200 | ????69 | ????99.5 | ????0.05 |
Table 3
Embodiment 8
It is that the stainless steel tubular type reactor of 20mm carries out activity rating that the catalyzer of getting embodiment 4 preparation places internal diameter, estimate and analysis condition with embodiment 5.Evaluation result sees Table 4.
| Temperature of reaction (℃) | Methanol conversion (%) | CO 2Selectivity (%) | CO concentration (%) |
| ????250 | ????96 | ????98.7 | ????0.28 |
| ????225 | ????93 | ????99.7 | ????0.16 |
| ????200 | ????70 | ????99.1 | ????0.09 |
Table 4
Comparative example
Take by weighing 59 gram Cu (NO
3)
23H
2O, 31 gram Zn (NO
3)
26H
2O, 13 gram Zr (NO
3) 26H
2O, 45 gram Al (NO
3)
39H
2O after the dissolving, places separating funnel with 4 kinds of solution mixing respectively, gets Na
2CO
3Solution places another separating funnel, prepares catalyzer with coprecipitation method.The control precipitation temperature is about 65 ℃, and under constantly stirring, with both and flow in the there-necked flask, regulate about pH=7.6, stir aging 2h, washing and filtering to filtrate be neutrality, 110 ℃ dry catalyst precursor, roasting, activation condition make the CuZnAlZr composite oxide catalysts with embodiment 1.Powdered catalyst in the moulding of 5-7MPa lower sheeting, is crushed to 0.45-0.9mm again.Measure the 9ml catalyzer, under the condition identical, check and rate catalyzer with embodiment 5.Evaluation result sees Table 5.
| Temperature of reaction (℃) | Methanol conversion (%) | CO 2Selectivity (%) | CO concentration (%) |
| ????250 | ????97 | ????97.0 | ????0.60 |
| ????225 | ????97 | ????99.3 | ????0.10 |
| ????200 | ????95 | ????99.0 | ????0.07 |
Table 5
Claims (7)
1. a preparing hydrogen by reforming methanol integral catalyzer is characterized in that, by cellular structure ceramic carrier, load on the bottom on cellular structure ceramic carrier outside surface and the micropore internal surface, active ingredient and the promoter coatings that loads on the bottom constitutes;
Said bottom is one or more the aluminum oxide that has mixed in lanthanum, cerium, praseodymium, neodymium, zirconium or the titanyl compound;
Said drawing together property component and promoter coatings are the aluminum oxide that contains active ingredient and promotor, wherein:
Said active ingredient is copper and zinc;
Said promotor is one or more in rare-earth oxide or the zirconium white, and its molfraction is:
1.0 parts of zinc 0.1-1.0 of copper part zirconium white 0-0.5 part rare-earth oxide 0-0.5 part, rare earth element is selected from one or more among La, Ce, Pr, Nd, Y, the Sc.
2. catalyzer according to claim 1 is characterized in that, the oxide compound that bottom mixes is the 2-50% of alumina weight.
3. catalyzer according to claim 1 is characterized in that, the charge capacity of active ingredient and promoter coatings is a 50-500 grams per liter catalyzer.
4. catalyzer according to claim 1 is characterized in that, the bottom charge capacity is a 10-200 grams per liter catalyzer.
5. prepare the method for claim 1,2,3 or 4 each described preparing hydrogen by reforming methanol integral catalyzers, it is characterized in that, comprise the steps:
(1) cellular structure ceramic carrier be impregnated in one or more the aluminum oxide slurries in nitrate, acetate, muriate, vitriol or the oxide compound that is mixed with rare-earth elements of lanthanum, cerium, praseodymium, neodymium, zirconium or titanium, wherein the metal oxide incorporation is the 2-50% of alumina weight in the slurry, after the drying, under 300-700 ℃, roasting 2-10 hour, obtain to have the support of the catalyst of bottom;
(2) support of the catalyst that will have a bottom impregnated in the aluminum oxide slurries that are mixed with copper, zinc, zirconium and rare earth element, after the drying, and under 250-600 ℃, roasting 2-10 hour.
6. method according to claim 5, it is characterized in that, the support of the catalyst that will have bottom impregnated in the aluminum oxide slurries that are mixed with copper, zinc, zirconium and rare earth element, the element that mixes is selected from the arbitrary form in nitrate, acetate, muriate, vitriol or the oxide compound, and wherein rare earth element is selected from one or more in lanthanum, cerium, praseodymium, neodymium, yttrium or the scandium.
7. according to claim 5 or 6 described methods, it is characterized in that, adopt conventional method to carry out the carrier pre-treatment.
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| CN1305566C CN1305566C (en) | 2007-03-21 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102872867A (en) * | 2012-10-19 | 2013-01-16 | 厦门大学 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
| CN102897713A (en) * | 2012-09-13 | 2013-01-30 | 上海合既得动氢机器有限公司 | Apparatus and method for hydrogen production through methanol steam reforming |
| CN102897712A (en) * | 2012-09-13 | 2013-01-30 | 上海合既得动氢机器有限公司 | High efficiency methanol-water hydrogen production system and hydrogen production method thereof |
| CN105552414A (en) * | 2016-01-28 | 2016-05-04 | 博源燃料电池(上海)有限公司 | Pure-hydrogen and pure-oxygen high-temperature battery system |
| CN109950589A (en) * | 2019-01-24 | 2019-06-28 | 中氢新能技术有限公司 | Novel carbinol reformer |
| CN111760596A (en) * | 2020-06-13 | 2020-10-13 | 华东理工大学 | Method for preparing structured catalyst carrier by photocuring |
| CN113318722A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
| CN114538374A (en) * | 2022-03-18 | 2022-05-27 | 中国科学院生态环境研究中心 | Device system for reforming and producing hydrogen by vehicle-mounted bioethanol and reforming and hydrogen production method |
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| FR2560531B1 (en) * | 1984-03-02 | 1988-04-08 | Inst Francais Du Petrole | PROCESS FOR THE MANUFACTURE OF CATALYSTS CONTAINING COPPER, ZINC, ALUMINUM AND AT LEAST ONE GROUP METAL FORMED BY RARE EARTHS AND ZIRCONIUM AND USE OF THE CATALYSTS OBTAINED FOR REACTIONS USING SYNTHESIS GAS |
| CN1025158C (en) * | 1989-10-28 | 1994-06-29 | 齐鲁石油化工公司研究院 | Hydrocarbon steam conversion catalyst and its application |
| US6583084B2 (en) * | 2000-07-18 | 2003-06-24 | Mitsui Chemicals, Inc. | Catalyst for steam reforming of methanol and method for producing hydrogen therewith |
| CN1397484A (en) * | 2002-08-13 | 2003-02-19 | 上海燃料电池汽车动力系统有限公司 | Catalyst for preparing hydrogen by reforming methanol vapour |
| CN1239258C (en) * | 2002-11-19 | 2006-02-01 | 南昌大学 | Catalyst for purifying exhausted gas of car and preparation process thereof |
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| CN102897713A (en) * | 2012-09-13 | 2013-01-30 | 上海合既得动氢机器有限公司 | Apparatus and method for hydrogen production through methanol steam reforming |
| CN102897712A (en) * | 2012-09-13 | 2013-01-30 | 上海合既得动氢机器有限公司 | High efficiency methanol-water hydrogen production system and hydrogen production method thereof |
| CN102897712B (en) * | 2012-09-13 | 2014-08-06 | 上海合既得动氢机器有限公司 | Methanol-water hydrogen production system and hydrogen production method thereof |
| CN102897713B (en) * | 2012-09-13 | 2014-12-24 | 上海合既得动氢机器有限公司 | Apparatus and method for hydrogen production through methanol steam reforming |
| CN102872867A (en) * | 2012-10-19 | 2013-01-16 | 厦门大学 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
| CN102872867B (en) * | 2012-10-19 | 2014-05-07 | 厦门大学 | Catalyst used for hydrogen production by methanol steam reforming and preparation method of catalyst |
| CN105552414A (en) * | 2016-01-28 | 2016-05-04 | 博源燃料电池(上海)有限公司 | Pure-hydrogen and pure-oxygen high-temperature battery system |
| CN109950589A (en) * | 2019-01-24 | 2019-06-28 | 中氢新能技术有限公司 | Novel carbinol reformer |
| CN111717890A (en) * | 2019-01-24 | 2020-09-29 | 中氢新能技术有限公司 | Methanol reformer |
| CN111717890B (en) * | 2019-01-24 | 2021-08-10 | 中氢新能技术有限公司 | Methanol reformer |
| CN113318722A (en) * | 2020-02-28 | 2021-08-31 | 广东粤能净环保科技有限公司 | Photocatalyst and preparation method and application thereof |
| CN113318722B (en) * | 2020-02-28 | 2023-08-01 | 中科粤能净(山东)新材料有限公司 | Photocatalyst, and preparation method and application thereof |
| CN111760596A (en) * | 2020-06-13 | 2020-10-13 | 华东理工大学 | Method for preparing structured catalyst carrier by photocuring |
| CN114538374A (en) * | 2022-03-18 | 2022-05-27 | 中国科学院生态环境研究中心 | Device system for reforming and producing hydrogen by vehicle-mounted bioethanol and reforming and hydrogen production method |
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