CN107572478A - A kind of preparation method and hydrogen-containing fuel of methanol decomposition hydrogen manufacturing gas - Google Patents
A kind of preparation method and hydrogen-containing fuel of methanol decomposition hydrogen manufacturing gas Download PDFInfo
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- CN107572478A CN107572478A CN201710873067.XA CN201710873067A CN107572478A CN 107572478 A CN107572478 A CN 107572478A CN 201710873067 A CN201710873067 A CN 201710873067A CN 107572478 A CN107572478 A CN 107572478A
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- methanol
- hydrogen
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- catalyst
- methanol decomposition
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Abstract
The invention provides a kind of preparation method and hydrogen-containing fuel of methanol decomposition hydrogen manufacturing gas, belong to auto industry and field of environment protection.The preparation method of methanol decomposition hydrogen manufacturing gas provided by the invention, by the way that methanol is mixed with catalyst, then the heat of automobile engine is utilized, it is the mixed gas containing hydrogen by methanol decomposition, can effectively utilizes the heat of engine, improves the efficiency of fuel, obtained hydrogeneous mixed gas is as hydrogen-containing fuel, automobile use can be supplied, the generation for the thing that reduces environmental pollution, there is important application value.
Description
Technical field
The present invention relates to auto industry and field of environment protection, in particular to a kind of system of methanol decomposition hydrogen manufacturing gas
Preparation Method and hydrogen-containing fuel.
Background technology
Constantly advanced with the economic society in China, socialist cause is constantly pushed ahead；The society in China
Meeting productivity improves constantly, and the material life of the people is greatly enriched；The current principal contradiction in China is still the people and increasingly increased
Contradiction between long material and cultural needs and backwardness of social production power.With the progress that deepens continuously of reform and opening-up, it is a member of a political party
Policy support under lead down, people have gradually taken leave of the worry worn the clothes and had a meal；The life that people start to higher quality has
Yearn for.
Domestic Automotive Industry constantly advances, and China's car ownership increases year by year, and automobile exhaust pollution problem is gradual
Attract people's attention；Vehicle exhaust has automobile engine burning to produce, and heat caused by automobile engine burning, also has very big
A part is fallen with exhaust emissions and causes to waste, and therefore, how recycling this partial heat and being one needs to face and final result
The problem of.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of methanol decomposition hydrogen manufacturing gas, by using car engine
The waste heat of machine, for preparing hydrogen, it can preferably improve the utilization ratio of motor vehicle fuel.
The second object of the present invention is to provide a kind of hydrogen-containing fuel, and the hydrogen-containing fuel passes through automobile engine residual heat system
It is standby, can be standby by fuel storage, for automobile burning, reduce the discharge of pernicious gas.
In order to realize the above-mentioned purpose of the present invention, using following technical scheme：
A kind of preparation method of methanol decomposition hydrogen manufacturing gas, including：
Methanol gaseous mixture and methanol cracking catalyst are subjected to hybrid reaction, obtain mixed gas；
Separation mixed gas obtains hydrogen.
A kind of hydrogen-containing fuel, hydrogen-containing fuel include hydrogen made from the preparation method of above-mentioned methanol decomposition hydrogen manufacturing gas.
Beneficial effects of the present invention are：The preparation method of methanol decomposition hydrogen manufacturing gas provided by the invention, by by methanol with
Catalyst mixes, and is the mixed gas containing hydrogen by methanol decomposition then using the heat of automobile engine, can be effective
Using the heat of engine, the efficiency of fuel is improved, obtained hydrogeneous mixed gas can supply automobile as hydrogen-containing fuel
Use, the generation for the thing that reduces environmental pollution, there is important application value.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
Methanol passes through catalyst, in the presence of catalyst, generation first with vapor under certain temperature, pressure condition
The transformationreation of alcohol cracking reaction and carbon monoxide, hydrogen and carbon dioxide are generated, this is that component more than one, the gas-solid reacted more are urged
Change reaction system.Reactional equation is as follows:
CH3OH→CO2+H2
H2O+CO→CO2+H2
CH3OH+H2O→CO2+3H2
The preparation method to a kind of methanol decomposition hydrogen manufacturing gas of the embodiment of the present invention and hydrogen-containing fuel are carried out specifically below
It is bright.
A kind of preparation method of methanol decomposition hydrogen manufacturing gas, including：
Methanol gaseous mixture and methanol cracking catalyst are subjected to hybrid reaction, obtain mixed gas；
Separation mixed gas obtains hydrogen.
Hydrogen is a kind of energy substance of cleaning, and combustion of hydrogen produces clean free of contamination water, and quantity of heat production is big, is one
The preferable energy substance of kind；Prepared in the past hydrogen be mostly by be electrolysed produce hydrogen, during can consume substantial amounts of electric energy, do not have
There is the purpose for reaching economy, consume the substantial amounts of energy on the contrary.At present, automobile is more and more, tail gas caused by automobile, and
Heat largely slatterns with tail gas caused by automobile engine, therefore is a feasible method using automotive residual heat,
Hydrogen is produced by automotive residual heat, and the hydrogen produced can supply automobile directly as energy substance and use, combustion of hydrogen production
Raw water is environmentally safe, is a method for preferably utilizing automotive residual heat, simply needs periodically to add methanol.
Further, methanol gaseous mixture is gasified to obtain by methanol solution, and the mol ratio of first alcohol and water is 8- in methanol solution
12:1。
Methanol forms mixed solution with water, is advantageous to the decomposition of methanol, water content can be avoided to absorb heat too much, accelerates
The cracking of methanol.
Further, the temperature of methanol solution gasification is 200-300 DEG C.
By methanol thermalization, the gas of methanol is obtained, is advantageous to methanol gas and is fully contacted with catalyst, is advantageous to accelerate first
The decomposition of alcohol；Because engine is when fuel combustion produces power, the gas of higher temperature can be produced, passes through high-temperature gas
Methanol decomposition reaction is carried out, can both solve the problems, such as methanol Btu utilization, moreover it is possible to reduce the pressure of cooling, be a multiple-effect
Utilization ways.
Further, the pressure 6-8MPa of hybrid reaction.
Pressurizeed after methanol solution is gasified, whole reaction environment can be caused to minimize, reduce the input of equipment, and pressurizeed
Pressure be not it is too big, the requirement to equipment be not also too big, common equipment all can meet demand, so rational pressure model
Enclose be an economical rationality range of choice.
Further, methanol cracking catalyst includes Al2O3、TiO2、Ni2O3, ZnO and CuO.
During methanol decomposition, have some side reactions generation, generations of side reaction can influence the generation of main reaction with
The yield of end-product；In order to suppress the generation of side reaction, it is necessary to generation by selecting appropriate catalyst-initiator side reaction,
Therefore catalyst is the core for improving methanol decomposition hydrogen manufacturing；Simultaneously because using the activation energy that can reduce reaction, can allow anti-
It should be able to be easier to occur；Because in chemical reaction, catalyst can change reactant chemical reaction rate (improve or reduce) and
Do not change chemical balance, and the quality of itself and chemical property all do not change before and after chemical reaction；And it is anti-to reduce this
Required activation energy should occur, be substantially that the reaction of a difficult generation of comparison is become two chemistry for being easy to occur
Reaction.
Further, Al2O3、TiO2、Ni2O3, ZnO and CuO weight ratio be 1.2-1.9:2.2-2.6：0.8-1.4:
1.1-1.5:0.4-0.9。
The composition of catalyst has critically important influence to the catalytic capability of catalyst, therefore by reasonably matching, energy
Improve the catalytic capability of catalyst；By by Al in the present invention2O3、TiO2、Ni2O3, ZnO and CuO reasonably to match, greatly
The catalytic effect of the catalyst of raising, accelerate the progress of reaction.
Further, including by Al2O3、TiO2、Ni2O3, ZnO and CuO be mixed to get catalyst mixture, abrasive catalyst
Mixture, obtains catalyst fines, and sintered catalyst powder obtains methanol cracking catalyst.
Further, the particle diameter of catalyst fines is 400-600 mesh.
Because the particle of catalyst is small, the specific surface area of catalyst is bigger, bigger with the contact area of methanol gas,
More be advantageous to reaction progress, but catalyst in particle after to a certain extent, the lifting to reaction speed is reduced by；So
And more short grained catalyst, it is necessary to accurate instrument could process it is obtained, on the contrary increase production cost and cost increase it is bright
It is aobvious；So the particle diameter of present invention selection 400-600 mesh, is a relatively inexpensive rational selection, that is, can guarantee that reaction efficiency again
Can good control cost.
Further, the temperature of sintering is 760-880 DEG C.
A kind of hydrogen-containing fuel, hydrogen-containing fuel include hydrogen made from the preparation method using above-mentioned methanol decomposition hydrogen manufacturing gas
Gas.
At present, new-energy automobile turns into a trend, and clean energy resource is increasingly valued by people, therefore new energy vapour
The research and development of car and clean energy resource are exactly a trend.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation method of methanol decomposition hydrogen manufacturing gas, includes the preparation of methanol cracking catalyst, has
Body method is as follows：
1.1 by 1.2kg Al2O3, 2.2kg TiO2, 1.4kg Ni2O3, 1.5kg ZnO and 0.4kg CuO mixing,
Obtain catalyst mixture；
1.2 catalyst mixtures that grinding steps 1.1 obtain in ball mill, milling time 3h；
1.3 obtain the catalyst fines that particle diameter is 400 mesh；
Catalyst fines is put into crucible and is sintered by 1.4, and methanol cracking catalyst is made, 760 DEG C of sintering temperature, burns
Tie time 2h.
The step of methanol decomposition reacts is as follows：
2.1 by methanol and water according to 8:1 mixed in molar ratio, 50kg methanol solution is made；
2.2 gasify obtained methanol solution under conditions of 200 DEG C；
2.3 the methanol gas of gasification and will be passed through in isothermal reactor, and with step 1.4 made from methanol cracking catalyst
Haptoreaction, reaction pressure 6MPa；
2.4 are made mixed gas, and mixed gas is separated using membrane separator；
2.5, by the separation of membrane separator, are made hydrogen.
Embodiment 2
The present embodiment provides a kind of preparation method of methanol decomposition hydrogen manufacturing gas, includes the preparation of catalyst, specific method is such as
Under：
1.1 by 1.9kg Al2O3, 2.6kg TiO2, 0.8kg Ni2O3, 1.1kg ZnO and 0.9kg CuO mixing,
Obtain catalyst mixture；
1.2 catalyst mixtures that grinding steps 1.1 obtain in ball mill, milling time 4h；
1.3 obtain the catalyst fines that particle diameter is 600 mesh；
Catalyst fines is put into crucible and is sintered by 1.4, and methanol cracking catalyst is made, 880 DEG C of sintering temperature, burns
Tie time 3h.
The step of methanol decomposition reacts is as follows：
2.1 by methanol and water according to 9:1 mixed in molar ratio, 40kg methanol solution is made；
2.2 gasify obtained methanol solution under conditions of 220 DEG C；
2.3 the methanol gas of gasification and will be passed through in isothermal reactor, and with step 1.4 made from methanol cracking catalyst
Haptoreaction, reaction pressure 6.5MPa；
2.4 are made mixed gas, and mixed gas is separated using membrane separator；
2.5, by the separation of membrane separator, are made hydrogen.
Hydrogen made from step 2.5 and CO gas are mixed to prepare hydrogen-containing fuel, obtained hydrogen-containing fuel can be with
Used applied to supply automobile.
Embodiment 3
The present embodiment provides a kind of preparation method of methanol decomposition hydrogen manufacturing gas, includes the preparation of catalyst, specific method is such as
Under：
1.1 by 1.4kg Al2O3, 2.4kg TiO2, 1.1kg Ni2O3, 1.3kg ZnO and 0.6kg CuO mixing,
Obtain catalyst mixture；
1.2 catalyst mixtures that grinding steps 1.1 obtain in ball mill, milling time 3.2h；
1.3 obtain the catalyst fines that particle diameter is 450 mesh；
Catalyst fines is put into crucible and is sintered by 1.4, and methanol cracking catalyst is made, 810 DEG C of sintering temperature, burns
Tie the time.
The step of methanol decomposition reacts is as follows：
2.1 by methanol and water according to 12:1 mixed in molar ratio, 65kg methanol solution is made；
2.2 gasify obtained methanol solution under conditions of 300 DEG C；
2.3 the methanol gas of gasification and will be passed through in isothermal reactor, and with step 1.4 made from methanol cracking catalyst
Haptoreaction, reaction pressure 8MPa；
2.4 are made mixed gas, and mixed gas is separated using membrane separator；
2.5, by the separation of membrane separator, are made hydrogen.
Hydrogen made from step 2.5 and CO gas are mixed to prepare hydrogen-containing fuel, obtained hydrogen-containing fuel can be with
Used applied to supply automobile.
Embodiment 4
The present embodiment provides a kind of preparation method of methanol decomposition hydrogen manufacturing gas, includes the preparation of catalyst, specific method is such as
Under：
1.1 by 1.7kg Al2O3, 2.5kg TiO2, 1.3kg Ni2O3, 1.4kg ZnO and 0.8kg CuO mixing,
Obtain catalyst mixture；
1.2 catalyst mixtures that grinding steps 1.1 obtain in ball mill, milling time 3.2h；
1.3 obtain the catalyst fines that particle diameter is 550 mesh；
Catalyst fines is put into crucible and is sintered by 1.4, and methanol cracking catalyst is made, 780 DEG C of sintering temperature, burns
Tie the time.
The step of methanol decomposition reacts is as follows：
2.1 by methanol and water according to 10:1 mixed in molar ratio, 55kg methanol solution is made；
2.2 gasify obtained methanol solution under conditions of 270 DEG C；
2.3 the methanol gas of gasification and will be passed through in isothermal reactor, and with step 1.4 made from methanol cracking catalyst
Haptoreaction, reaction pressure 7.2MPa；
2.4 are made mixed gas, and mixed gas is separated using membrane separator；
2.5, by the separation of membrane separator, are made hydrogen.
Hydrogen made from step 2.5 and CO gas are mixed to prepare hydrogen-containing fuel, obtained hydrogen-containing fuel can be with
Used applied to supply automobile.
Embodiment 5
The present embodiment provides a kind of preparation method of methanol decomposition hydrogen manufacturing gas, includes the preparation of catalyst, specific method is such as
Under：
1.1 by 1.6kg Al2O3, 2.3kg TiO2, 0.9kg Ni2O3, 1.2kg ZnO and 0.6kg CuO mixing,
Obtain catalyst mixture；
1.2 catalyst mixtures that grinding steps 1.1 obtain in ball mill, milling time 4.5h；
1.3 obtain the catalyst fines that particle diameter is 530 mesh；
Catalyst fines is put into crucible and is sintered by 1.4, and methanol cracking catalyst is made, 720 DEG C of sintering temperature, burns
Tie the time.
The step of methanol decomposition reacts is as follows：
2.1 by methanol and water according to 11:1 mixed in molar ratio, 60kg methanol solution is made；
2.2 gasify obtained methanol solution under conditions of 255 DEG C；
2.3 the methanol gas of gasification and will be passed through in isothermal reactor, and with step 1.4 made from methanol cracking catalyst
Haptoreaction, reaction pressure 6.8MPa；
2.4 are made mixed gas, and mixed gas is separated using membrane separator；
2.5, by the separation of membrane separator, are made hydrogen.
Hydrogen made from step 2.5 and CO gas are mixed to prepare hydrogen-containing fuel, obtained hydrogen-containing fuel can be with
Used applied to supply automobile.
In summary, the present invention prepares hydrogen by components utilising automotive residual heat for dissociated methanol, improves automobile hair
To the utilization rate of fuel by simple technique, dissociated methanol, above-mentioned hydrogen, and hydrogen-containing fuel is made in hydrogen by motivation；Both may be used
To improve the utilization rate of fuel, obtained hydrogen can be used with supply engine, and engine uses hydrogen fuel, it is possible to reduce
Environmental pollution, improve automobile environment-protection performance.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made
Every other embodiment, belongs to the scope of protection of the invention.
Claims (10)
- A kind of 1. preparation method of methanol decomposition hydrogen manufacturing gas, it is characterised in that including：Methanol gaseous mixture and methanol cracking catalyst are subjected to hybrid reaction, obtain mixed gas；Separate the mixed gas and obtain the hydrogen.
- 2. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 1, it is characterised in that the methanol gaseous mixture by Methanol solution gasifies to obtain, and the mol ratio of first alcohol and water is 8-12 in the methanol solution:1.
- 3. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 2, it is characterised in that the methanol solution gasification Temperature be 200-300 DEG C.
- 4. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 2, it is characterised in that the pressure of the hybrid reaction Power 6-8MPa.
- 5. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 1, it is characterised in that the methanol decomposition catalysis Agent includes Al2O3、TiO2、Ni2O3, ZnO and CuO.
- 6. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 5, it is characterised in that the Al2O3, it is described TiO2, the Ni2O3, the ZnO and the CuO weight ratio be 1.2-1.9:2.2-2.6:0.8-1.4:1.1-1.5:0.4- 0.9。
- 7. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 6, it is characterised in that including by the Al2O3、 The TiO2, the Ni2O3, the ZnO and the CuO be mixed to get catalyst mixture, grind the catalyst mixture, Catalyst fines is obtained, the catalyst fines is sintered and obtains the methanol cracking catalyst.
- 8. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 7, it is characterised in that the catalyst fines Particle diameter is 400-600 mesh.
- 9. the preparation method of methanol decomposition hydrogen manufacturing gas according to claim 7, it is characterised in that the temperature of the sintering is 760-880℃。
- 10. a kind of hydrogen-containing fuel, it is characterised in that the hydrogen-containing fuel is included using as described in claim any one of 1-9 The hydrogen made from the preparation method of methanol decomposition hydrogen manufacturing gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108745363A (en) * | 2018-05-14 | 2018-11-06 | 中国科学院山西煤炭化学研究所 | It is a kind of for the copper-based catalysts and preparation method of hydrogen from methyl alcohol and application |
| CN115893315A (en) * | 2022-11-29 | 2023-04-04 | 本源精化环保科技有限公司 | Preparation method of high-purity hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108745363A (en) * | 2018-05-14 | 2018-11-06 | 中国科学院山西煤炭化学研究所 | It is a kind of for the copper-based catalysts and preparation method of hydrogen from methyl alcohol and application |
| CN115893315A (en) * | 2022-11-29 | 2023-04-04 | 本源精化环保科技有限公司 | Preparation method of high-purity hydrogen |
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