CN109650334A - A kind of method of direct photothermal conversion hydrogen from methyl alcohol - Google Patents
A kind of method of direct photothermal conversion hydrogen from methyl alcohol Download PDFInfo
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- CN109650334A CN109650334A CN201910066060.6A CN201910066060A CN109650334A CN 109650334 A CN109650334 A CN 109650334A CN 201910066060 A CN201910066060 A CN 201910066060A CN 109650334 A CN109650334 A CN 109650334A
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- hydrogen
- methyl alcohol
- reaction solution
- photothermal conversion
- methanol
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1217—Alcohols
- C01B2203/1223—Methanol
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of direct photothermal conversion hydrogen from methyl alcohol, utilize capillary effect, so that nanocatalyst does not stop to transmit reaction solution upwards, form nano-fluid, in conjunction with the strong light absorption characteristic of nano-fluid, under focus irradiation, reaction solution around nanocatalyst gradually evaporates, reaction solution continues to supply to catalyst, at first the temperature of Catalytic Layer does not stop to increase, until temperature keeps stablizing when evaporation rate and liquid feed speed balance, hydrogen is generated at this point, stablizing in gas-liquid intersection catalyst upper surface.Whole Catalysis experiments can be environmentally protective using solar energy as heat source, and the catalytic unit is simple and convenient, can reduce manufacturing cost.
Description
Technical field
The invention belongs to technical field of hydrogen preparation, and in particular to a kind of method of direct photothermal conversion hydrogen from methyl alcohol.
Background technique
Hydrogen has widely as the following indispensable fuel in fields such as fuel cell, chemical treatment and aviations
Using.The generation of hydrogen can come from water, natural gas, coal or biomass.However, there are some defects for some hydrogen production process.Water is logical
It crosses heat absorption Direct Pyrolysis and needs the up to high temperature of 2500K or more, heat source can be provided by solar energy.But it needs a kind of special
Equipment hydrogen and oxygen mixture are separated, place it and generate water or explosive again.Coal Gasification can produce largely
Hydrogen, but coal is rare and non-renewable.Biomass hydrogen preparation technology is also another hydrogen manufacturing approach, but in hydrogen manufacturing
Cheng Zhong still needs to a certain amount of hydrogen as push agent mostly.Currently, methanol steam reforming or Methanol Decomposition are to realize natural gas
The important channel of hydrogen manufacturing.It is well known that methanol is simplest in all alcohol, because of its only one carbon atom.Strong C-
C key can be reformed at 250 DEG C or so, this is lower than other fuel.And methanol decomposition or methanol recapitalization are all that heat absorption is anti-
It answers: CH3OH+H2O——CO2+3H2 ∆H = 50.7kJ mol−1, i.e., using methanol and water mixed vapour under 250 degree of high temperature
It reacts with catalyst.Solar energy can satisfy complete as a kind of renewable energy, inexhaustible, nexhaustible advantage
Ball energy demand.By Solar use in catalyzing manufacturing of hydrogen will be a much progress and breakthrough.Existing expert proposes to utilize parabolic at present
Slot Photospot solar is heated to steel pipe or transparent tube (including catalyst), will be carried out in methanol and water mixed vapour access tube
Catalysis produces hydrogen, but supplementary energy is still utilized in the generation of its methanol and water vapour, and the use of the energy also disappears to a certain extent
Energy is consumed, and single unit system cost is big.In addition to this, conventional methanol hydrogen production process is by focus irradiation steel pipe thus to catalysis
Heat is transmitted in agent, this process heat transmission link is more, causes thermal resistance big, and steel tube surface temperature is high, and radiant heat transfer loss is big, and
And only abutment surface absorbs heat, whole solar energy utilization ratio is low, these can enhance heat loss, reduces solar energy utilization ratio, removes
Except this, also there is expert using photocatalysis hydrogen from methyl alcohol, but its hydrogen generation efficiency is low.
Summary of the invention
Present invention aim to address the above-mentioned prior arts using technical problem present in hydrogen from methyl alcohol, provides a kind of straight
The method for connecing photothermal conversion hydrogen from methyl alcohol makes full use of solar energy, to promote by the photothermal conversion performance using nano-fluid
Into catalytic fluid layer high-efficiency evaporating, reaction solution sustainable supply, so that directly being balanced in Catalytic Layer evaporation with feed flow, and in gas
Liquid layer realizes that catalysis produces hydrogen purpose using photo-thermal coupling and catalyzing.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of method of direct photothermal conversion hydrogen from methyl alcohol forms methanol reaction solution infiltration nanocatalyst using capillarity
Nano-fluid evaporates the methanol reaction solution around nanocatalyst by focus irradiation, while methanol reaction solution sustainable supply,
To generate hydrogen in gas-liquid intersection.
Further, the methanol reaction solution is the mixed liquor of water and methanol.
Further, the molar ratio of water and methanol is 1:1-1:2 in the water and methyl alcohol mixed liquor.
Further, the nanocatalyst has strong light absorption characteristic and catalysis characteristics simultaneously.
Further, the intensity of illumination of the focus irradiation is 10-20kW/m2。
Capillary effect is utilized in the present invention, so that nanocatalyst does not stop to transmit reaction solution upwards, forms nano-fluid, knot
The strong light absorption characteristic of nano-fluid is closed, under the focus irradiation of sunlight, reaction solution gradually evaporates, and reaction solution continues to catalysis
Agent supply, at first the temperature of Catalytic Layer does not stop to increase, until temperature keeps steady when evaporation rate and liquid feed speed balance
It is fixed, hydrogen is generated at this point, stablizing in gas-liquid intersection catalyst upper surface.Using solar energy as heat source for reaction, not only provide
It is fast that methanol and water evaporation institute calorific requirement, reaction heat needed for also providing catalysis, and its catalysis produce hydrogen.Whole Catalysis experiments are available
Solar energy is environmentally protective as heat source, and the catalytic unit is simple and convenient, can reduce manufacturing cost.
Detailed description of the invention
Fig. 1 is direct photothermal conversion hydrogen from methyl alcohol Method And Principle of the invention；
Fig. 2 is catalytic reactor constructed in embodiment 1；
Fig. 3 is catalyst carrier device constructed in embodiment 1；
Wherein: 1 be catalyst, 2 be porous flat plate, 3 be reaction solution, 4 be gas-liquid have a common boundary, 5 be generate gas, 6 be sponge.
Specific embodiment
Technical solution of the present invention is described further in the following with reference to the drawings and specific embodiments.
The present invention provides a kind of methods of direct photothermal conversion hydrogen from methyl alcohol to pass through nanometer using biological evaporating principle
Fluid local heating realizes evaporation and catalysis in multifunctional nano catalyst surface, to generate hydrogen simultaneously.
Specifically, as shown in Figure 1, using multifunctional material as catalyst 1, under capillary action, nanocatalyst by
It is gradually infiltrated by methanol reaction solution 3, forms nano-fluid, under focus irradiation, nano-fluid is because of its strong light absorption characteristic, by the sun
It can be converted into thermal energy, so that reaction solution rapid evaporation, simultaneous reactions liquid sustainable supply is even in 4 catalyst surface of gas-liquid intersection
Speed generates hydrogen 5.
Multifunctional material as catalyst need to have strong light absorption characteristic and catalysis characteristics economic benefits and social benefits characteristic.
Under focus irradiation, at first catalyst layer temperature is constantly increased, until when evaporation rate and liquid feed speed balance,
Temperature keeps stablizing, at the uniform velocity generate hydrogen.Catalyst infiltrating time is adjusted, infiltrating time is shorter, and temperature is lower；When infiltration
Between it is longer, temperature is high, and it is fast to produce gas.Water/methanol molar ratio is adjusted, molar ratio is bigger, and liquid level is high, and temperature is low；Molar ratio is smaller, liquid
Position is lower, and temperature is higher, and it is faster to produce gas.Optically focused intensity is smaller, and temperature is lower；Optically focused intensity is higher, and temperature is high, and it is fast to produce gas.
CuO/ZnO/Al of following embodiments to buy2O3Commercial catalysts as hydrogen catalyst is produced, using the above method and
Easy device is illustrated by three change catalyst infiltrating time, water/methanol molar ratio and intensity of illumination aspects respectively
Illustrate to produce hydrogen situation, to prove the feasibility and its advantage of the direct photothermal conversion hydrogen from methyl alcohol method.
Embodiment 1
In the lab, the present embodiment is to realize above scheme by Fig. 2 and easy device shown in Fig. 3.Catalyst 1 is flat
It is laid on porous flat plate 2, under capillary action, 6 absorbing reaction liquid 3 of sponge is supplied to catalyst 1, and catalyst 1 is gradually filled instead
Liquid 3 is answered, nano-fluid is formed, under focus irradiation, surface layer fast liquid evaporation, meanwhile, bottom liquid sustainable supply is evaporating
When with balance between supply and demand, in 4 catalyst surface catalyst generation of hydrogen 5 of gas-liquid intersection.
Instrument connection will configure 159.5mL water/methyl alcohol mixed liquor that molar ratio is 1.5 and entered instead by feed liquor bottle suck-back
It answers in bottle, then waits for the profit of self inhaling of catalyst, setting intensity of illumination is 17kW/m2.Equal catalyst are beaten after being filled mixed liquor
Source switch of turning on light starts to react under focus irradiation, in the steady timed collection gas of its temperature.
The discovery of this case, in 159.5mL liquid inlet volume, and when water/methyl alcohol mixed liquor molar ratio is 1.5, the leaching of catalyst
The profit time is 23min, and catalyst layer temperature is 168 DEG C when balancing at this time, and catalysis hydrogen-producing speed at this time is 2.0mL/s.
Embodiment 2
Experimental provision is same as Example 1.
Instrument connection will configure 159.5mL water/methyl alcohol mixed liquor that molar ratio is 1.25 and entered instead by feed liquor bottle suck-back
It answers in bottle, then waits for the profit of self inhaling of catalyst, setting intensity of illumination is 17kW/m2.Equal catalyst are beaten after being filled mixed liquor
Source switch of turning on light starts to react under focus irradiation, in the steady timed collection gas of its temperature.
The discovery of this case balances at this time in 159.5mL liquid inlet volume, and when water/methyl alcohol mixed liquor molar ratio is 1.25
When catalyst layer temperature be 198 DEG C, catalysis hydrogen-producing speed at this time is 2.3mL/s.
Embodiment 3
Experimental provision is same as Example 1.
Instrument connection will configure 159.5mL water/methyl alcohol mixed liquor that molar ratio is 1.5 and entered instead by feed liquor bottle suck-back
It answers in bottle, then waits for the profit of self inhaling of catalyst, setting intensity of illumination is 12kW/m2.Equal catalyst are beaten after being filled mixed liquor
Source switch of turning on light starts to react under focus irradiation, in the steady timed collection gas of its temperature.
The discovery of this case, in 159.5mL liquid inlet volume, and when water/methyl alcohol mixed liquor molar ratio is 1.5, catalyst
Infiltrating time is 23min, changes concentrating power to 12kW/m2, and catalyst layer temperature is 136 DEG C when balancing at this time, urging at this time
Change hydrogen-producing speed is 0.8mL/s.
Claims (5)
1. a kind of method of direct photothermal conversion hydrogen from methyl alcohol, it is characterised in that: infiltrate methanol reaction solution using capillarity
Nanocatalyst forms nano-fluid, evaporates the methanol reaction solution around nanocatalyst by focus irradiation, while methanol
Reaction solution sustainable supply, to generate hydrogen in gas-liquid intersection.
2. the method for direct photothermal conversion hydrogen from methyl alcohol according to claim 1, it is characterised in that: the methanol reaction solution
It is the mixed liquor of water and methanol, nanocatalyst has both catalysis characteristics and strong light absorption characteristic.
3. the method for direct photothermal conversion hydrogen from methyl alcohol according to claim 2, it is characterised in that: the water and methanol are mixed
Closing the molar ratio of water and methanol in liquid is 1:1-1:2.
4. the method for direct photothermal conversion hydrogen from methyl alcohol according to claim 1, it is characterised in that: the nanocatalyst
There are strong light absorption characteristic and catalysis characteristics simultaneously.
5. the method for direct photothermal conversion hydrogen from methyl alcohol according to claim 1, it is characterised in that: the focus irradiation is
Focus irradiation is carried out using sunlight, the intensity of illumination of sunlight is 10-20kW/m2。
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Cited By (6)
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| CN110240119A (en) * | 2019-07-14 | 2019-09-17 | 中国科学院山西煤炭化学研究所 | A kind of bimetallic photochemical catalyst and bio-alcohol aqueous-phase reforming hydrogen production process |
| CN112079332A (en) * | 2020-09-18 | 2020-12-15 | 北京大学 | Method for preparing hydrogen by directly inducing solid ammonia borane through photo-thermal method |
| CN112439420A (en) * | 2020-12-03 | 2021-03-05 | 南京航空航天大学 | Preparation method of photo-thermal coupling methanol steam reforming hydrogen production composite catalyst |
| CN112791670A (en) * | 2020-12-23 | 2021-05-14 | 南京大学 | Interfacial thermocatalytic system |
| CN112833569A (en) * | 2021-01-08 | 2021-05-25 | 西安交通大学 | Integrated light-gathering solar photo-thermal synergetic catalytic reaction device |
| CN112973703A (en) * | 2021-01-26 | 2021-06-18 | 南京航空航天大学 | Method for producing hydrogen by direct photo-thermal concerted catalysis of methanol |
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Application publication date: 20190419 |