CN108620093A - A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method - Google Patents
A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method Download PDFInfo
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- CN108620093A CN108620093A CN201810458960.0A CN201810458960A CN108620093A CN 108620093 A CN108620093 A CN 108620093A CN 201810458960 A CN201810458960 A CN 201810458960A CN 108620093 A CN108620093 A CN 108620093A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
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- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The present invention relates to a kind of activation method of methanol steam reintegrating hydrogen manufacturing copper-based catalysts, specific activation process is：Catalyst bed is warming up to activation temperature from room temperature first, and constant temperature is kept, then it is passed through catalyst bed after the preheated device preheating vaporization of activator methanol aqueous solution, activation of catalyst reaction is carried out, after reactor bed outlet tail gas is cooled down by condenser in activation process, carries out gas-liquid separation, and the gas phase composition after separation is analyzed, when gas phase, which forms, to be stablized, activation terminates, and stops methanol aqueous solution charging.The activating process process of the present invention is simple, is easy to control, and reduction efficiency is high, while activating cost is relatively low, can be widely applied to the activation of hydrogen from methyl alcohol copper-based catalysts in methanol fuel-cell system.
Description
Technical field
The present invention relates to fuel cell mobile hydrogen making technical field, more particularly to methanol in a kind of methanol fuel-cell system
The activation method of vapor reforming hydrogen production copper-based catalysts.
Background technology
Hydrogen fuel cell has high efficiency and no pollution Drainage feature, will be led in the energy as a kind of new-generation mode
Domain plays an increasingly important role, and is the important channel realized the energy low-carbon, cleaned.The hydrogen fuel of vehicle fuel battery
There are mainly two types of sources, first, hydrogen is directly used, second is that vehicle-mounted mobile hydrogen producing technology.Vehicle-mounted mobile hydrogen producing technology is mainly with alcohol at present
The substances such as class, ethers and gasoline are raw material, carry out hydrogen manufacturing using catalytic reforming technology, methanol compares other wherein in alcohols feedstock
Hydrogen feedstock has the advantages such as energy density is high, reaction temperature is low, derive from a wealth of sources, convenient transportation, is that electric vehicle is most viable
One of preferred hydrogen supply fuel mode, therefore methanol fuel-cell system is one of the hydrogen fuel cell system for most having development potentiality.
At present preparing hydrogen by reforming methanol technique mainly include hydrogen production from methanol-steam reforming, methanol partial oxidation reforming hydrogen manufacturing,
Three kinds of modes of methanol self-heating reforming hydrogen manufacturing, wherein hydrogen production from methanol-steam reforming technology be study it is the most ripe, most widely used,
The highest technique of hydrogen content is produced, is the most hydrogen producing technology of competitiveness in methanol fuel-cell system.Methanol steam reforming system
The copper-based catalysts that hydrogen reaction is used are required to reduction activation before use, and traditional copper-based catalysts activation method generally uses
The reducibility gas such as hydrogen, carbon monoxide, while selecting nitrogen or the progress of other inert gases dilute according to specific technological requirement
It releases.In terms of using alcohol or containing alcohol liquid to carry out copper-based catalysts activation as reducing agent, patent CN1335201 discloses one kind
The restoring method of Cu-contained catalyst, using C1 ~ C12 primary alconol or secondary alcohol as reducing agent, exist to alcohol dehydrogenase or hydrogenation catalyst
Heating activation is carried out in reactor, since alcohols being used only in reduction process as reducing agent, and in the entire mistake of catalyst reduction
Cheng Zhonghui is related to the decomposition of alcohol, and alcohol generates very complicated gas component in catalyst surface decomposable process, to catalyst
Reduction process have a major impact, be unfavorable for the control of reduction process.A kind of methanol-water steaming is disclosed in patent CN1850332A
The restoring method of gas reformation hydrogen production copper-based catalysts, catalyst water smoking are purged using air, then use hydrogen
Cause the reduction of catalyst with the gas phase mixture of water, finally 0.1 ~ 5% methanol aqueous solution is used to be restored, after activation
Catalyst Conversion reaches 99% or more, but there is some shortcomings, is purged using quantitative gas in reduction process, needs to be equipped with
Special gas distribution channel, and still need to use hydrogen during restoring, the hydrogen being equipped with storage conveying special equipment is needed,
So that entire technical process becomes complicated.Patent CN102416327B discloses a kind of hydrogen production from methanol-steam reforming copper zinc catalysis
The restoring method of agent, catalyst reduction process include that three phases are strengthened in dehydration, reduction and reduction, still need to use water hydrogen in the process
Reduction, operating process are cumbersome.Patent CN106552678 discloses a kind of quick restoring method of Cu-contained catalyst, utilizes early period
Material benzenemethanol aqueous solution is restored after preheating drives catalyst bed entrance to be rapidly heated to 190 DEG C, and catalyst activation temperature is 200
~ 205 DEG C, methanol volume fraction is 1.5 ~ 2.5% in methanol aqueous solution, carries out being restored to end, this restoring method to catalyst
The content of water is too high in reducing solution, and the copper crystal grain for restoring generation continuous redox repeatedly under higher vapour atmosphere is caused to be made
The increase of Viability crystal grain, the final stability in use for influencing catalyst.
Invention content
Shortcoming present in view of the above technology, the present invention provides a kind of methanol steam reintegrating hydrogen manufacturing is copper-based
The activation method of catalyst, this method is simple, is easy to control, and activation efficiency is high, while cost is relatively low, can be widely applied to methanol
The activation of hydrogen from methyl alcohol catalyst in fuel cell system.
To achieve the above object, the activation process of catalyst for preparing hydrogen by reforming methanol and water vapour is as follows in the present invention：
Catalyst bed is warming up to catalyst activation temperature by a from normal-temperature continuous first, and constant temperature is kept；
B then passes to methanol aqueous solution, enters catalyst bed after preheater preheating vaporization, carries out priming reaction；
After catalyst bed outlet tail gas is cooled down by condenser in c catalyst activation process, gas-liquid separation is carried out, and to dividing
Gas phase composition from after is analyzed, and when forming stable in gas phase, activation terminates, and stops methanol aqueous solution charging.
In the process a, catalyst activation temperature is 190 ~ 250 DEG C.
In the process a, catalyst bed is warming up to activation temperature from normal-temperature continuous, required heating-up time control 60 ~
120min。
In the process b, preheater heats up or heats up simultaneously with catalyst bed in advance, and preheater temperature stablizes 150 ~
200 DEG C, activator methanol aqueous solution enters preheater after reaction bed temperature stabilization and vaporizes.
In the process b, activator methanol aqueous solution group becomes, and the molar ratio of methanol and water is 0.5 ~ 1.
In the process b, the liquid hourly space velocity (LHSV) of methanol aqueous solution charging is 0.015 ~ 0.06h-1。
In the process c, condenser is cooled to liquid phase to water vapour in outlet tail gas, into gas-liquid separation, gas after separation
Phase composition mainly has hydrogen and carbon dioxide, hydrogen content in gas phase is analyzed using hydrogen analytical equipment, when hydrogen contains in gas phase
When amount is stablized, reduction terminates.
In the activation process, the control of catalyst bed operating pressure is 0 ~ 0.2MPa in gauge pressure.
It in the activation process, starts to warm up to activation of catalyst and terminates from catalyst bed, the whole process used time is general
For 8 ~ 20h, process specifically takes to be influenced by factors such as methanol aqueous solution composition, Feed space velocities and activation temperatures.
Activation method provided by the invention is formulated according to methanol steam reintegrating hydrogen manufacturing copper-based catalysts component characteristic,
CuO mass contents valence state of copper generally after the completion of 40 ~ 70%, reduction is mainly zeroth order and monovalence copper wherein in catalyst.This hair
Compared with prior art, for reactor continuous warming to activation temperature, temperature program is simple when activation of catalyst starts, right for bright technology
Heat supply and its control device require low.Terminate to activation since priming reaction, methanol aqueous solution feed constant, while activating
Air, hydrogen or other gases need not be used in journey, are simplified activating process flow, are kept activating process simple and quick.
The raw material composition for activating the methanol aqueous solution composition and the reaction of follow-up methanol steam reforming that use is essentially identical, avoids in addition
It prepares and forms different methanol aqueous solution processes, to improve activating process efficiency, while lower water content avoids in activating solution
Copper crystal grain caused by redox repeatedly of the copper crystal grain of catalyst surface under high concentration vapour atmosphere increases in activation process
Greatly, the stability of catalyst is improved.Entire activation process is easy to operate, and reduction efficiency is high, and the methanol aqueous solution consumed disappears
Consume it is less, convenient for storage and transport.
Specific implementation mode
With reference to specific implementation process, the present invention is described in further detail, to enable those skilled in the art's reference
Specification word can be implemented according to this.
Used raw material is purchased in market unless otherwise specified in the embodiment of the present invention.
The embodiment of the present invention carries out in the fixed bed reactor system of laboratory, the system include methanol-water feeding part,
Several parts such as methanol aqueous solution preheater, reactor, tail gas condenser, gas-liquid separator.It first will reaction in entire implementation process
Then the reforming catalyst heating reduction loaded in advance in device adjusts temperature and carries out preparing hydrogen by reforming methanol reaction.
Embodiment 1
The present embodiment activates and reaction pressure is normal pressure.
50g reforming catalysts are added in fixed bed reactors, the weight percent of copper oxide is 55% in catalyst, so
Rear feeding preheater and reactor heating, wherein reactor bed are warming up to 230 DEG C from room temperature 60min, constant temperature, feed preheater
It synchronizes and is warming up to 170 DEG C, then pass to methanol aqueous solution activated catalyst, the molar ratio of methanol and water is 1, methanol aqueous solution
Charging liquid hourly space velocity (LHSV) is 0.02h-1, while gas-liquid separator exit gas composition is analyzed, analytical sampling was every 1 hour one
It is secondary, after hydrogen content in gas maintains to stablize, close methanol solution charging, entire activation process used time 14h.Adjust reactor
For temperature to 280 DEG C, preheater temperature then passes to 54% to 240 DEG C（Weight）Methanol solution, charging liquid hourly space velocity (LHSV) are respectively
1.2h-1、1.6h-1、1.8h-1, tested by liquid phase to reaction end gas and gas phase, calculate methanol under corresponding Feed space velocities
Conversion ratio is 99.8%, 99.2%, 97.5% respectively, and CO contents are respectively 0.86%, 0.75%, 0.64% in reaction end gas.
Embodiment 2
The present embodiment activates and reaction pressure is 0.1MPa (gauge pressure).
100g reforming catalysts are added in fixed bed reactors, the weight percent of copper oxide is 60% in catalyst, so
Rear feeding preheater and reactor heating, wherein reactor bed are warming up to 240 DEG C from room temperature 90min, constant temperature, feed preheater
It synchronizes and is warming up to 150 DEG C, then pass to methanol aqueous solution activated catalyst, the molar ratio of methanol and water is 0.5, methanol aqueous solution
Charging liquid hourly space velocity (LHSV) be 0.03h-1, while gas-liquid separator exit gas composition is analyzed, analytical sampling was every 1 hour
Once, after hydrogen content in gas maintains to stablize, methanol solution charging is closed, it is entire to activate used time 16h.Adjust reactor temperature
For degree to 280 DEG C, preheater temperature then passes to 54% to 240 DEG C（Weight）Methanol solution, charging liquid hourly space velocity (LHSV) is respectively 1.2h-1、1.6h-1、1.8h-1, by gas-liquid separator liquid phase and gas phase test, calculate methanol under corresponding Feed space velocities
Conversion ratio is 100%, 99.1%, 98.0% respectively, and CO contents are respectively 1.06%, 0.84%, 0.79% in reaction end gas.
Embodiment 3
50g reforming catalysts are added in fixed bed reactors, the weight percent of copper oxide is 55% in catalyst, then into
Expect that preheater and reactor heating, wherein reactor bed are warming up to 230 DEG C from room temperature 60min, constant temperature, feed preheater synchronizes
Be warming up to 150 DEG C, then pass to methanol aqueous solution activated catalyst, the molar ratio of methanol and water is 0.1, methanol aqueous solution into
Material liquid hourly space velocity (LHSV) is 0.10h-1, while gas-liquid separator exit gas composition is analyzed, analytical sampling was every 1 hour one
It is secondary, after hydrogen content in gas maintains to stablize, methanol solution charging is closed, it is entire to activate used time 16h.Adjust temperature of reactor
To 280 DEG C, preheater temperature then passes to 54% to 240 DEG C（Weight）Methanol solution, charging liquid hourly space velocity (LHSV) is respectively 1.2h-1、
1.6h-1、1.8h-1, by gas-liquid separator liquid phase and gas phase test, calculate turning for methanol under corresponding Feed space velocities
Rate is 100%, 99.0%, 97.1% respectively, and CO contents are respectively 0.82%, 0.74%, 0.71% in reaction end gas.
Embodiment 4
Activated catalyst carries out 72h reformation tests to the present embodiment in embodiment 1 and embodiment 3, has lived in two embodiments
Change catalyst and be respectively designated as C-1 and C-3, is tested under the same reaction conditions, specific reaction condition：Temperature of reactor
280 DEG C, preheater temperature is passed through 54% to 240 DEG C（Weight）Methanol solution, charging liquid hourly space velocity (LHSV) are 1.8h-1, analyzed every 4h
Primary to reform tail gas composition, the results are shown in table below.
Although the embodiments of the present invention have been disclosed as above, but it is not limited in listed utilization in embodiment, is not carrying on the back
From under universal defined by claim and equivalency range, the technology of the present invention be not limited to specific details with it is depicted herein
Go out embodiment.
Claims (9)
1. a kind of activation method for hydrogen production from methanol-steam reforming copper-based catalysts in methanol fuel-cell system, feature
It is, this activation method comprises the following processes：Catalyst bed is warming up to activation temperature, and constant temperature by a from normal-temperature continuous first
It keeps；B then passes to methanol aqueous solution, enters catalyst bed after preheater preheating vaporization, carries out priming reaction；C lives
After reactor bed outlet tail gas is cooled down by condenser during change, gas-liquid separation is carried out, then to the gas phase group after separation
At being analyzed, when hydrogen composition is stablized in gas phase, activation terminates.
2. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that described copper-based to urge
The mass percent of agent copper oxide is 40 ~ 70%.
3. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the process a
Middle activation temperature is 190 ~ 250 DEG C.
4. methanol steam reforming copper-based catalysts activation process as claimed in claim 2, which is characterized in that the process a
Middle activation temperature is preferably 210 ~ 240 DEG C.
5. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the process a
Middle catalyst bed is warming up to activation temperature from normal-temperature continuous, and required heating-up time control is in 60 ~ 120min.
6. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the process b
Middle preheater preheating vapourizing temperature control is at 150 ~ 200 DEG C, and preheater heats up in advance or heating synchronous with catalyst bed.
7. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the process b
Middle activator methanol aqueous solution, consisting of the molar ratio of methanol and water is 0.5 ~ 1.
8. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the process b
In be passed through methanol aqueous solution liquid hourly space velocity (LHSV) be 0.015 ~ 0.06h-1。
9. methanol steam reforming copper-based catalysts activation process as described in claim 1, which is characterized in that the activation side
Method, the control of catalyst bed operating pressure are 0 ~ 0.2MPa in gauge pressure.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111086973A (en) * | 2019-12-30 | 2020-05-01 | 北京蓝玖新能源科技有限公司 | Hydrogen production process and application thereof |
| CN112023923A (en) * | 2020-08-18 | 2020-12-04 | 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 cracking |
| 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 |
| CN112495383A (en) * | 2020-11-13 | 2021-03-16 | 华东理工大学 | Activation method of copper-based catalyst for hydrogen production by methanol steam reforming |
| CN112916017A (en) * | 2021-01-29 | 2021-06-08 | 华东理工大学 | Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming |
| CN114225971A (en) * | 2021-12-27 | 2022-03-25 | 广东蓝玖新能源科技有限公司 | Automatic activation system and activation process of methanol hydrogen production catalyst |
| CN114477086A (en) * | 2022-01-27 | 2022-05-13 | 北京联力源科技有限公司 | Methanol steam reforming hydrogen production device and starting method thereof |
| CN116159602A (en) * | 2023-03-01 | 2023-05-26 | 江苏京盈化工新材料有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
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| CN101927200A (en) * | 2010-08-26 | 2010-12-29 | 河南煤业化工集团有限责任公司 | Method for activating and reducing catalyst for hydrogenation of dimethyl oxalate to prepare glycol |
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| 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 |
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| CN1335201A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Reduction process of copper-containing catalyst |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111086973A (en) * | 2019-12-30 | 2020-05-01 | 北京蓝玖新能源科技有限公司 | Hydrogen production process and application thereof |
| CN112023923A (en) * | 2020-08-18 | 2020-12-04 | 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 cracking |
| 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 |
| CN112495383A (en) * | 2020-11-13 | 2021-03-16 | 华东理工大学 | Activation method of copper-based catalyst for hydrogen production by methanol steam reforming |
| CN112916017A (en) * | 2021-01-29 | 2021-06-08 | 华东理工大学 | Raw material gas activation method for 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 |
| CN114225971A (en) * | 2021-12-27 | 2022-03-25 | 广东蓝玖新能源科技有限公司 | Automatic activation system and activation process of methanol hydrogen production catalyst |
| CN114477086A (en) * | 2022-01-27 | 2022-05-13 | 北京联力源科技有限公司 | Methanol steam reforming hydrogen production device and starting method thereof |
| 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 |
| CN116159602A (en) * | 2023-03-01 | 2023-05-26 | 江苏京盈化工新材料有限公司 | Reduction process of copper catalyst for N-methylaniline synthesis |
| 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 |
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Application publication date: 20181009 |