CN100420517C - Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen - Google Patents
Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen Download PDFInfo
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- CN100420517C CN100420517C CNB2006100210081A CN200610021008A CN100420517C CN 100420517 C CN100420517 C CN 100420517C CN B2006100210081 A CNB2006100210081 A CN B2006100210081A CN 200610021008 A CN200610021008 A CN 200610021008A CN 100420517 C CN100420517 C CN 100420517C
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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
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- Y02P20/584—Recycling of catalysts
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Abstract
The present invention discloses a reduction method of a catalyst for reforming hydrogen production by using methyl alcohol aqueous vapor, which comprises a dehydration stage of the catalyst, an initiation stage for catalyst reduction and a reduction stage of the catalyst, wherein during the dehydration stage of the catalyst, air or inert gas at the gas air speed of 200 to 1500 h<-1> is led into a reactor while the temperature of the reactor rises, and the air or the inert gas is stopped to be led into the reactor when the temperature reaches 80 to 150 DEG C. During the initiation stage for catalyst reduction, the temperature continues to rise, and hydrogen gas and water at the gas air speed of 800 to 1500 h<-1> are led into the reactor; the hydrogen gas accounts for 0.2 to 5 vol% of the volume of the hydrogen gas and water; when the temperature reaches 160 to 200 DEG C, the hydrogen gas and the water are stopped to be led into the reactor. During the reduction stage of the catalyst, the temperature continues to rise and 0.1 to 5 wt% of methanol aqueous solution is led into the reactor at the liquid air speed of 0.5 to 2 h<1-> and the temperature stops rising when reaching 200 to 260 DEG C; all the temperature rise rate is 5 to 25 DEG C/h in the reaction processes. The reduction method has the advantages of low cost and simple operation.
Description
Technical field
The present invention relates to the method for reducing of a kind of steam reformation of methanol to produce hydrogen, specifically, relate to the method for reducing of copper-based catalysts with catalyst.
Background technology
Hydrogen has very important position in 21 century, and China will be mainly reflected in the following aspects to the demand of Hydrogen Energy: the hydrofinishing of oil plant product oil is to the demand of cheap hydrogen source; The Proton Exchange Membrane Fuel Cells electric motor car is to the demand of hydrogen energy system; The high-power generating of Proton Exchange Membrane Fuel Cells is to the demand of hydrogen energy system; Hydrogenation station or residential quarter are to the demand of the on-the-spot hydrogen manufacturing hydrogen source of decentralized; The demand of industry such as fine chemistry industry, Aero-Space.
Methyl alcohol is easy to deposit and transportation, has higher energy conversion efficiency, and methanol steam reforming reaction product is mainly hydrogen and carbon dioxide, there is not environmental pollution, process realizes easily, therefore becomes the desirable approach of hydrogen source, has become the emphasis of domestic and international research and application.
Steam reformation of methanol to produce hydrogen is in the existing ten years development history of China, and the catalyst that steam reformation of methanol to produce hydrogen uses adopts copper-based catalysts, i.e. CuO/ZnO/Al mostly
2O
3Catalyst for main component.This catalyst needs reduction activation before use, and traditional method is to adopt N
2, CH
4As carrier gas, H
2Activate as reducing gases.Its activation process reaches 50 hours, and the air speed of reducing gases is had certain requirement, generally at 500～1000h
-1Therefore on commercial plant, use roots blower to recycle carrier gas usually, so just strengthened plant investment, and made whole technical process become complicated.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of reducing of copper-radic catalyst for reforming methanol vapour to produce hydrogen, and this method cost is low, simple to operate.
The method of reducing of copper-radic catalyst for reforming methanol vapour to produce hydrogen of the present invention comprises following step:
A. water smoking of catalyst: reactor heats up and feeds gas hourly space velocity simultaneously in reactor is 200～1500h
-1Air or inert gas, stop bubbling air or inert gas during to 80～150 ℃;
B. the initiating stage of catalyst reduction: continuing to heat up also feeds hydrogen and water vapour, and the gas hourly space velocity of hydrogen and water vapour is 800～1500h
-1, the percent by volume that hydrogen accounts for both is 0.2～5%, stops to feed hydrogen and water vapour during to 160～200 ℃;
C. the reduction phase of catalyst: continuing to heat up also feeds methanol aqueous solution 0.1～5% (weight), and liquid hourly space velocity (LHSV) is 0.5～2h
-1, stop during to 200～260 ℃ heating up; The programming rate of above-mentioned reactions steps is 5～25 ℃/h.
The percentage by weight of cupric oxide is 45～90% in the described copper-based catalysts, is preferably 50～70%.
Preferred 110～120 ℃ of the dehydration temperaturre of described step a; Preferred 800～the 1200h of feeding air speed of its gas
-1
Preferred 150～180 ℃ of the reduction initiation temperature of described step b; The hydrogen volume percentage preferred 0.5～2% of its feeding.
Preferred 200～230 ℃ of the reduction temperature of described step c; Preferred 0.5～the 1h of the liquid hourly space velocity (LHSV) of the methanol aqueous solution of its feeding
-1
Programming rate among described step a, b, the c preferably is respectively 20 ℃/h, 10 ℃/h and 10 ℃/h.
The method of reducing of catalyst for steam reformation of methanol to produce hydrogen provided by the invention is according to CuO/ZnO/Al
2O
3The characteristic of catalyst is carried out different method of reducing to the different phase of catalyst reduction process.Adopt cheap air in the low temperature dewatering stage, adopt water vapour as carrier gas at the initiating stage of catalyst reduction, the hydrogen that adopts the methyl alcohol reaction to generate at the reduction phase of catalyst comes reducing catalyst.In methanol steam is reformed the system industrialized unit instrument air source of the gas is arranged all generally, methyl alcohol is the raw material of this technology, and whole reduction process only needs a spot of hydrogen of outsourcing just can realize, has therefore really saved investment in industrialized technology.Adopt the catalyst performance of this patented method reduction to compare with traditional method, this method also has temperature control easy, and catalyst reduction is advantage of uniform relatively, and catalyst activity is compared with traditional method does not have evident difference substantially.
Below the present invention is further detailed explanation for the embodiment by the specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made include within the scope of the invention.
The specific embodiment
Reaction is all carried out in the industrial Gas-phase reactor of simulation in following examples, and reactor adopts electric heater unit.With feed vaporization, heat temperature raising is passed in the catalyst earlier, with the variation of gas chromatographic detection reactant.
Embodiment 1
Add the 60ml catalyst for steam reformation of methanol to produce hydrogen in Gas-phase reactor, the percentage by weight of cupric oxide is 65% in the catalyst, and to device vaporization part, reactive moieties heats up simultaneously, and programming rate is 20 ℃/h, simultaneously with gas hourly space velocity 1000h
-1Bubbling air when being warming up to 110 ℃, stops bubbling air.Use measuring pump with gas hourly space velocity 1200h then
-1Feed the deionized water of steam-like, and feed that to account for both percents by volume be 0.5% H
2(being 0.37L/h), programming rate are 10 ℃/h.Stop to feed H when being warming up to 200 ℃
2And water vapour, and with measuring pump with liquid hourly space velocity (LHSV) 1h
-1The methanol aqueous solution of feeding 0.5% continues to heat up, and programming rate is 10 ℃/h, stops when being warming up to 230 ℃ heating up, and continues with liquid hourly space velocity (LHSV) 1h
-1The methanol aqueous solution of feeding 1%, beginning analyzing and testing reformed gas component.
GC conditions: chromatographic column TDX-01, GDX-105,120 ℃ of column temperatures, 120 ℃ of sensing chamber's temperature, 120 ℃ of temperature of vaporization chamber, flow velocity 40～60ml/min H
2, bridge stream 150mA.
By chemical equation: CH
3OH+H
2O=3H
2+ CO
2As can be known, CO
2Theoretical content show that near 25% o'clock catalyst no longer consumes H
2, this moment, catalyst reduced thoroughly.Experimental result is because of the CO that exists of water vapour and CO
2Content can be more on the low side.Therefore test CO in the reformed gas
2Content (percent by volume) near 24～24.5% o'clock the explanation catalyst reduced thoroughly.
Use measuring pump with liquid hourly space velocity (LHSV) 1h then
-1Feed the methanol aqueous solution of 50% (wt), reformed gas records H with above-mentioned chromatographic condition
2: 74.7%, CO
2: 24.4%, CO:0.8%, CH
40.1%, it is 0.2% that the condensate liquid of reaction measures methanol content, and calculating conversion of methanol thus is 99.5%, and the selectivity of hydrogen is 99.9%.
Embodiment 2
Add the 60ml catalyst for steam reformation of methanol to produce hydrogen in Gas-phase reactor, the percentage by weight of cupric oxide is 55% in the catalyst, and to device vaporization part, reactive moieties heats up simultaneously, and programming rate is 20 ℃/h, simultaneously gas hourly space velocity 1500h
-1Bubbling air when being warming up to 120 ℃, stops bubbling air.Use measuring pump with gas hourly space velocity 1500h then
-1Feed the deionized water of steam-like, and feed that to account for both percents by volume be 1% H
2, programming rate is 10 ℃/h.Stop to feed H when being warming up to 160 ℃
2And water vapour, and with measuring pump with liquid hourly space velocity (LHSV) 1.2h
-1The methanol aqueous solution of feeding 1% continues to heat up, and programming rate is 10 ℃/h, stops when being warming up to 220 ℃ heating up, and continues with liquid hourly space velocity (LHSV) 1.2h
-1The methanol aqueous solution of feeding 2%.Detection method and computational methods are with embodiment 1.CO in detecting reformed gas
2Content (percent by volume) near 24～24.5% o'clock the explanation catalyst reduced thoroughly.
Use measuring pump with liquid hourly space velocity (LHSV) 1.3h then
-1Feed the methanol aqueous solution of 50% (weight), by gas chromatographic detection, the selectivity that calculates hydrogen then is 99.5%, and conversion of methanol is 95.4%.
Embodiment 3
Add the 60ml catalyst for steam reformation of methanol to produce hydrogen in Gas-phase reactor, the percentage by weight of cupric oxide is 60% in the catalyst, and to device vaporization part, reactive moieties heats up simultaneously, and programming rate is 20 ℃/h, simultaneously with gas hourly space velocity 1000h
-1Bubbling air when being warming up to 120 ℃, stops bubbling air; This step also can feed inert gas, as helium, neon or argon gas etc.Use measuring pump with gas hourly space velocity 1000h then
-1Feed the deionized water of steam-like, and feed that to account for both percents by volume be 0.5% H
2, programming rate is 10 ℃/h.Stop to feed H when being warming up to 180 ℃
2And water vapour, and with measuring pump with liquid hourly space velocity (LHSV) 0.8h
-1The methanol aqueous solution of feeding 0.5% continues to heat up, and programming rate is 10 ℃/h, stops when being warming up to 230 ℃ heating up, and continues with liquid hourly space velocity (LHSV) 0.8h
-1The methanol aqueous solution of feeding 1%.
Up to detecting reformed gas CO
2Content (percent by volume) near 24～24.5% o'clock the explanation catalyst reduced thoroughly.
Use measuring pump with liquid air speed 0.5h then
-1Feed the methanol aqueous solution of 50% (weight), by gas chromatographic detection, the selectivity that calculates hydrogen then is 99.6%, and conversion of methanol is 99.8%.
Above-mentioned detection method and computational methods are with embodiment 1.
Claims (10)
1. the method for reducing of a copper-radic catalyst for reforming methanol vapour to produce hydrogen is characterized in that, this method comprises following step:
A. water smoking of catalyst: reactor heats up and feeds gas hourly space velocity simultaneously in reactor is 200～1500h
-1Air or inert gas, stop bubbling air or inert gas during to 80～150 ℃;
B. the initiating stage of catalyst reduction: continuing to heat up also feeds hydrogen and water vapour, and the gas hourly space velocity of hydrogen and water vapour is 800～1500h
-1, the percent by volume that hydrogen accounts for both is 0.2～5%, stops to feed hydrogen and water vapour during to 160～200 ℃;
C. the reduction phase of catalyst: continuing to heat up also feeds methanol aqueous solution 0.1～5% (weight), and liquid hourly space velocity (LHSV) is 0.5～2h
-1, stop during to 200～260 ℃ heating up;
The programming rate of above-mentioned reactions steps is 5～25 ℃/h.
2. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the percentage by weight of cupric oxide is 45～90% in the described copper-based catalysts.
3. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 2 is characterized in that, the percentage by weight of described cupric oxide is 50～70%.
4. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the dehydration temperaturre of described step a is 110～120 ℃.
5. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the feeding gas hourly space velocity of gas is 800～1200h among the described step a
-1
6. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the reduction initiation temperature of described step b is 150～180 ℃.
7. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the percent by volume of hydrogen is 0.5～2% among the described step b.
8. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the reduction temperature of described step c is 200～230 ℃.
9. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the liquid hourly space velocity (LHSV) that feeds methanol aqueous solution among the described step c is 0.5～1h
-1
10. the method for reducing of a kind of copper-radic catalyst for reforming methanol vapour to produce hydrogen according to claim 1 is characterized in that, the programming rate among described step a, b, the c is respectively 20 ℃/h, 10 ℃/h and 10 ℃/h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100210081A CN100420517C (en) | 2006-05-26 | 2006-05-26 | Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen |
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| CNB2006100210081A CN100420517C (en) | 2006-05-26 | 2006-05-26 | Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen |
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| CN100420517C true CN100420517C (en) | 2008-09-24 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416327B (en) * | 2011-10-25 | 2013-12-25 | 江苏诺盟化工有限公司 | Reduction method of copper zinc catalyst for hydrogen production by methanol steam reforming |
| CN103977843B (en) * | 2014-05-27 | 2016-01-20 | 山西兰花科技创业股份有限公司 | A kind of method of methyl alcohol catalyst heating reduction |
| CN106552678A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | The quick method of reducing of Cu-contained catalyst |
| CN106552679A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | The method of reducing of cuprio desulphurization catalyst |
| CN108993615B (en) * | 2018-08-11 | 2021-11-26 | 四川蜀泰化工科技有限公司 | Reduction and passivation method of copper-based catalyst for hydrogen production by methanol reforming |
| CN112138728A (en) * | 2020-08-18 | 2020-12-29 | 广东醇氢新能源研究院有限公司 | Activation method of copper-based catalyst for hydrogen production by methanol-water reforming reaction |
| CN112023923B (en) * | 2020-08-18 | 2024-01-30 | 广东醇氢新能源研究院有限公司 | Copper-based catalyst activation method for hydrogen production by methanol pyrolysis |
| CN112495383B (en) * | 2020-11-13 | 2022-05-06 | 华东理工大学 | Activation method of copper-based catalyst for hydrogen production by methanol steam reforming |
| CN112916017B (en) * | 2021-01-29 | 2022-05-06 | 华东理工大学 | Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming |
| CN114477086B (en) * | 2022-01-27 | 2024-04-16 | 北京联力源科技有限公司 | Methanol steam reforming hydrogen production device and starting method thereof |
| CN115041174B (en) * | 2022-06-20 | 2023-09-29 | 西南化工研究设计院有限公司 | Preparation method of copper-based catalyst of large-scale methanol hydrogen production device |
| CN116159602B (en) * | 2023-03-01 | 2023-09-15 | 西南化工研究设计院有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5756302A (en) * | 1980-08-11 | 1982-04-03 | Kiyatarisutsu Ando Chem Yuurop | Metal reforming method and device |
| JPS60209255A (en) * | 1984-03-02 | 1985-10-21 | アンステイテユ・フランセ・デユ・ペトロール | Preparation of catalyst |
| CN1662306A (en) * | 2002-06-27 | 2005-08-31 | 益达科技责任有限公司 | Methanol steam reforming catalysts, steam reformers, and fuel cell systems incorporating the same |
-
2006
- 2006-05-26 CN CNB2006100210081A patent/CN100420517C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5756302A (en) * | 1980-08-11 | 1982-04-03 | Kiyatarisutsu Ando Chem Yuurop | Metal reforming method and device |
| JPS60209255A (en) * | 1984-03-02 | 1985-10-21 | アンステイテユ・フランセ・デユ・ペトロール | Preparation of catalyst |
| CN1662306A (en) * | 2002-06-27 | 2005-08-31 | 益达科技责任有限公司 | Methanol steam reforming catalysts, steam reformers, and fuel cell systems incorporating the same |
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| CN1850332A (en) | 2006-10-25 |
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