CN105967144B - A kind of heat supply method for preparing hydrogen by reforming methanol reaction - Google Patents
A kind of heat supply method for preparing hydrogen by reforming methanol reaction Download PDFInfo
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- CN105967144B CN105967144B CN201610302025.6A CN201610302025A CN105967144B CN 105967144 B CN105967144 B CN 105967144B CN 201610302025 A CN201610302025 A CN 201610302025A CN 105967144 B CN105967144 B CN 105967144B
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- 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
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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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
Abstract
The present invention relates to a kind of heat supply method for preparing hydrogen by reforming methanol reaction, its heating system includes methanol tank, oxygen tank, combustion chamber, material box, heat exchanger, water tank, vaporizer, reactor, separator, circulating pump；The heating system is using methanol and by the hydrogen containing tail gas that separator obtains as fuel, using compressed oxygen as oxidant, both are burnt in combustion chamber, for water tank heat supply, the mixture of water in water tank and ethylene glycol or glycerine is converted into high temperature and high pressure steam, and flowed by circulating pump in closed cycle, high temperature and high pressure steam successively provides heat for reforming reactor, vaporizer, heat exchanger, methanol-water reaction raw materials are made progressively to heat up, vaporize, reach reforming reaction temperature, carry out reforming reaction hydrogen making in the reactor.A kind of heat supply method for preparing hydrogen by reforming methanol reaction provided by the invention has the advantages such as simple in construction, heat utilization ratio is high, good reliability, easy to maintenance, operation cost is low.
Description
Technical field
The invention belongs to heat supply and transmission technique field, is related to a kind of heat supply method, more particularly to a kind of to be used for first
The heat supply method of alcohol reforming hydrogen production reaction.
Background technology
Environmental pollution, energy crisis it is increasingly serious, make to tap a new source of energy as solving the effective way of the problem.Hydrogen Energy
Efficiently, it is environmentally friendly, it is the generally acknowledged future ideality energy, is just attract increasing researcher and putting into the research of Hydrogen Energy with opening
Among hair.Electrochemistry and heat chemistry are the two ways that hydrogen utilizes, and electrochemistry releases energy at normal temperatures, and product is water, almost
To environment without any pollution.The combustion heat value of hydrogen is high, and calorific value is 14.3 × 107J/kg, the heat after every kilogram of hydrogen burning, about
3 times of gasoline, 3.9 times of alcohol, 4.5 times of coke；In addition to nuclear fuel, the calorific capacity of hydrogen is that all fossil fuels and biology fire
Highest in material.
At present, main hydrogen producing technology includes fossil fuel hydrogen manufacturing, water electrolysis hydrogen producing, solar hydrogen making, biomass hydrogen preparation
Deng.Fuel reforming is the important way of fossil fuel hydrogen manufacturing, and it is in certain catalyst bar by the fossil fuel of high-energy-density
The process of hydrogen-rich gas is converted under part.In numerous raw materials available for fuel reforming, the low-carbon alcohols fuel source such as methanol is extensive,
It can be produced from biomass, cheap, preparation process condition relaxes, and be carbonized less pollution, is the ideal original for onboard hydrogen source
Material selection.
Preparing hydrogen by reforming methanol mode mainly has three kinds：Thermal reforming, partial oxidative steam reforming and steam reformation are confessed, using which kind of
Mode hydrogen manufacturing depends on use condition and demanded fuel.Methanol cluster hydrogen production reaction be methanol, desalted water mixing after pass through
Enter reforming reactor after heating vaporization, methanol decomposition and an oxidation occur under certain temperature, pressure and catalysts conditions
Carbon water gas shift reaction, produce hydrogen, carbon dioxide and micro carbon monoxide.Preparing hydrogen by reforming methanol have reaction temperature it is low,
Export H2The features such as content height and few CO contents, its net reaction is as follows：
CH3OH+H2O→CO2+3H2-49.5kJ/mol
Preparing hydrogen by reforming methanol reaction temperature is 220~280 DEG C, is the endothermic reaction, it is therefore desirable to which the external world provides heat.Mesh
Before, existing preparing hydrogen by reforming methanol reaction unit is generally used as heating, heat transfer carrier using conduction oil.Conduction oil is mostly high boiling alkane
Base benzene-type, mineral type silicone oil, its heating mainly have two ways, and one kind is to use electrical heating, i.e., using 220V or 380V electricity
Source, conduction oil is heated by heating wire；Another kind is to carry out pot to conduction oil by fossil fuels such as burning diesel oil, coals
Stove formula heats.The advantages of conduction oil is heat transfer carrier is that temperature control is more accurate, is heated evenly inside reforming reactor, safe to use
Property is good, and it is disadvantageous in that：As usage time extends, the reaction such as thermal cracking, thermal polymerization easily occurs for conduction oil, causes
The mobility of deep fat is deteriorated and produces coking, blocks oil pipe or even trigger pipe explosion accident.Therefore, it is necessary to periodic monitoring conduction oil
The parameters such as viscosity, acid number, carbon residue, flash-point, and the dregs of fat in tank are removed in time, regularly replace new conduction oil.So, methanol recapitalization
Device systems need to periodically stop in hydrogen production reaction, and equipment operational reliability will be by extreme influence.In addition, it is limited to liquid not
Compressibility, conduction oil device systems are open heating system, during its long-term work, lower-molecular-weight component in conduction oil
Volatilization will also result in serious pollution to operating environment.
The content of the invention
The purpose of the present invention is for the deficiency in existing hydrogen from methyl alcohol reaction heat supply process, there is provided it is a kind of it is simple in construction,
Heat utilization ratio height, good reliability, the heat supply side for being used for preparing hydrogen by reforming methanol reaction for the advantage such as easy to maintenance, operation cost is low
Method.
The present invention is that technical scheme is used by solving the above problems：
A kind of heat supply method for preparing hydrogen by reforming methanol reaction, its heating system include methanol tank, oxygen tank, burning
Room, material box, heat exchanger, water tank, vaporizer, reactor, separator, circulating pump；The heating system is with methanol and passes through
The hydrogen containing tail gas that separator obtains is fuel, and using compressed oxygen as oxidant, both are burnt in combustion chamber, is supplied for water tank
Heat, the mixture of the water in water tank and ethylene glycol or glycerine is converted into high temperature and high pressure steam, and is in enclosed by circulating pump
Circulate, high temperature and high pressure steam successively provides heat for reforming reactor, vaporizer, heat exchanger, makes methanol-water reaction raw materials
Progressively heat up, vaporize, reach reforming reaction temperature, carry out reforming reaction hydrogen making in the reactor.
Further technical scheme is：
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, the methanol in its methanol tank is both as fuel supply combustion
Room is burnt, also serves as reaction raw materials base feed case, the supply of methanol is controlled by measuring pump and mass flow controller.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, the oxygen in its oxygen tank is compressed gaseous or liquid
Industrial grade oxygen, oxygen its gauge in oxygen tank is 0.1~2.0MPa.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, industrial grade oxygen purity >=99.5%.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, on its water tank installation include temperature transmitter, pressure
Transmitter, liquid level sensor, safety valve component, for monitoring the liquid level of the temperature of high temperature and high pressure steam, pressure and water in water tank
Value, when pressure exceedes setting value in water tank, passes through the timely pressure release of safety valve.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, the HTHP obtained after the water vapor in its water tank
The temperature range of steam is 120~300 DEG C, and pressure limit is 0.5~3.0MPa, and high temperature and high pressure steam is with flowing through heat exchanger, vapour
Change device, the raw material of reactor forms heat convection.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, the raw material of its reactor is methanol water mixed liquid.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, the water in its water tank is deionized water, is added in water
Ethylene glycol or the ratio of glycerine be 1~10wt%.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, its separator are that pressure-swing absorption apparatus or palladium film are pure
Makeup is put.
The described heat supply method for being used for preparing hydrogen by reforming methanol reaction, its circulating pump is high-pressure circulation pump.
The beneficial effects of the present invention are：
1st, a kind of heat supply method for preparing hydrogen by reforming methanol reaction provided by the invention, its heating system have structure simple
Singly, the features such as reliability is high, easy to operate.
2nd, the present invention will not occur fouling, block phenomena such as pipeline, and pass through height using high temperature and high pressure steam as heat transfer carrier
Circulating pump is pressed to be flowed in closed cycle, not only heat utilization ratio is high, working service is convenient, also improves the life of hydrogen production units by carbinol
Efficiency is produced, significantly reduces operation cost, and to environment without any pollution.
Brief description of the drawings
Fig. 1 is a kind of heat supply method Xi System annexations for preparing hydrogen by reforming methanol reaction provided by the invention and stream
Journey schematic diagram.
Device name corresponding to mark is in figure：1- methanol tanks, 2- oxygen tanks, 3- combustion chambers, 4- material boxes, 5-
Heat exchanger, 6- water tanks, 6.1- temperature transmitters, 6.2- pressure transmitters, 6.3- fluid level transmitters, 6.4- safety valves,
7- vaporizers, 8- reactors, 9- separators, 10- circulating pumps.
Embodiment
It is as follows that the invention will be further described in conjunction with the accompanying drawings and embodiments：
Embodiment 1：As shown in figure 1, it is a basic embodiment.A kind of heat supply side for preparing hydrogen by reforming methanol reaction
Method, its heating system include methanol tank 1, oxygen tank 2, combustion chamber 3, material box 4, heat exchanger 5, water tank 6, vaporizer 7, reactor
8th, separator 9, circulating pump 10；The heating system is with the methanol in methanol tank 1 and the hydrogeneous tail obtained by separator 9
Gas is fuel, and using the compressed oxygen in oxygen tank 2 as oxidant, both are burnt in combustion chamber 3, is the heat supply of water tank 6, by water
The mixture of water and ethylene glycol or glycerine in case 6 is converted into high temperature and high pressure steam, and is in closed cycle by circulating pump 10
Flowing, high temperature and high pressure steam successively for reforming reactor 8, vaporizer 7, heat exchanger 5 provide heat, make methanol-water reaction raw materials by
Step heating, vaporization, reach reforming reaction temperature, and reforming reaction hydrogen making is carried out in reactor 8.
The one outlet of the methanol tank 1 and the outlet of oxygen tank 2 respectively with the import UNICOM of combustion chamber 3；Methanol tank 1
Another outlet and the import UNICOM of material box 4；Material box 4, heat exchanger 5, vaporizer 7, reactor 8, separator 9 sequentially join
It is logical；Combustion chamber 3 and the UNICOM of water tank 6, at the same combustion chamber 3 also with the UNICOM of separator 9；From water tank 6 to circulating pump 10, reactor 8,
Vaporizer 7, heat exchanger 5, then form closed cycle flow circuits to the UNICOM of water tank 6.
Embodiment 2：It is the further embodiment on the basis of embodiment 1.The described preparing hydrogen by reforming methanol that is used for reacts
Heat supply method, the methanol in its methanol tank 1 also serves as reaction raw materials base feed case 4 both as fuel supply combustion chamber 3,
The supply of methanol is controlled by measuring pump and mass flow controller.Oxygen in described oxygen tank 2 is compressed gaseous
Or the industrial grade oxygen of liquid, oxygen its gauge in oxygen tank 2 is 0.1~2.0MPa.Described industrial grade oxygen is pure
Degree >=99.5%.Installation includes temperature transmitter 6.1, pressure transmitter 6.2, liquid level sensor 6.3, peace on described water tank 6
The part of full valve 6.4, for monitoring the level value of the temperature of high temperature and high pressure steam, pressure and water in water tank 6, when pressure in water tank 6
During more than setting value, pass through 6.4 timely pressure release of safety valve.The high temperature and high pressure steam obtained after water vapor in described water tank 6
Temperature range be 120~300 DEG C, pressure limit be 0.5~3.0MPa, and high temperature and high pressure steam is with flowing through heat exchanger 5, vaporizer
7th, the raw material of reactor 8 forms heat convection, to improve the heat exchange efficiency of two media.The raw material of described reactor 8 is first
Alcohol-water mixture.Water in described water tank 6 is deionized water, the ethylene glycol or the ratio of glycerine added in water be 1~
10wt%, both it is used for the flow resistance for reducing steam, can be also used as antifreezing agent.Described separator 9 is pressure-swing absorption apparatus or palladium
Film purification devices.Described circulating pump 10 is high-pressure circulation pump.
Embodiment 3：From implementing unlike 2, the oxygen in the oxygen tank 2 is the industrial grade oxygen of compressed gaseous, pure
Spend and be：99.5%, its gauge is 0.5MPa.The water tank 6 can pass through peace when pressure exceedes setting value 1.5MPa in case
6.4 timely pressure release of full valve.The temperature of high temperature and high pressure steam is 220 ± 10 DEG C, 1.2 ± 0.1MPa of pressure limit in the water tank 6,
High temperature and high pressure steam and the material benzenemethanol water mixed liquid formation convective heat transfer for flowing through heat exchanger 5, vaporizer 7, reactor 8, with
Improve the heat exchange efficiency of two media.
Embodiment 4：From implementing unlike 2, the water in the water tank 6 is deionized water, and 5wt% second is added with water
Glycol, both it is used for the flow resistance for reducing steam, can be also used as antifreezing agent.The separator 9 of the reforming reaction products therefrom gas is
Pressure-swing absorption apparatus.
Embodiment 5：Oxygen in the oxygen tank 2 is that the industrial grade oxygen purity of compressed gaseous is：99.9%, its gauge pressure
Pressure is 2.0MPa.The water tank 6 can pass through 6.4 timely pressure release of safety valve when pressure exceedes setting value 3.0MPa in case.Institute
The temperature for stating high temperature and high pressure steam in water tank 6 is 280 ± 10 DEG C, and 2.5 ± 0.1MPa of pressure limit, high temperature and high pressure steam is with flowing through
Heat exchanger 5, vaporizer 7, the raw material of reactor 8 form convective heat transfer for methanol water mixed liquid, to improve changing for two media
The thermal efficiency.
Embodiment 6：Water in the water tank 6 is deionized water, and 10wt% glycerine is added with water, is both used to reduce
The flow resistance of steam, it can also be used as antifreezing agent.The separator 9 of the reforming reaction products therefrom gas is palladium film purification devices.
The claims of the present invention are not limited to above-described embodiment.
Claims (7)
1. a kind of heat supply method for preparing hydrogen by reforming methanol reaction, it is characterised in that heating system includes methanol tank（1）, oxygen
Gas tank（2）, combustion chamber（3）, material box（4）, heat exchanger（5）, water tank（6）, vaporizer（7）, reactor（8）, separator
（9）, circulating pump（10）；The heating system is with methanol and passes through separator（9）Obtained hydrogen containing tail gas is fuel, with compression
Oxygen is oxidant, and both are in combustion chamber（3）Burnt, be water tank（6）Heat supply, by water tank（6）In water and ethylene glycol or
The mixture of glycerine is converted into high temperature and high pressure steam, and passes through circulating pump（10）Flowed in closed cycle, high temperature and high pressure steam
It is successively reforming reactor（8）, vaporizer（7）, heat exchanger（5）Heat is provided, methanol-water reaction raw materials is progressively heated up, vapour
Change, reach reforming reaction temperature, in reactor（8）Middle progress reforming reaction hydrogen making；Oxygen tank（2）In oxygen for compression
The industrial grade oxygen of gaseous state or liquid, oxygen tank（2）In oxygen its gauge be 0.1 ~ 2.0MPa；The industrial grade oxygen
Purity >=99.5%；The water tank（6）In water be deionized water, the ethylene glycol or the ratio of glycerine added in water be 1 ~
10wt%。
2. the heat supply method according to claim 1 for preparing hydrogen by reforming methanol reaction, it is characterised in that the methanol tank
（1）In methanol both as fuel supply combustion chamber（3）, also serve as reaction raw materials base feed case（4）, the supply of methanol passes through
Measuring pump and mass flow controller are controlled.
3. the heat supply method according to claim 1 for preparing hydrogen by reforming methanol reaction, it is characterised in that the water tank
（6）Upper installation includes temperature transmitter（6.1）, pressure transmitter（6.2）, liquid level sensor（6.3）, safety valve（6.4）Part,
For monitoring water tank（6）The level value of the temperature of interior high temperature and high pressure steam, pressure and water, works as water tank（6）Interior pressure exceedes setting
During value, pass through safety valve（6.4）Timely pressure release.
4. the heat supply method according to claim 1 for preparing hydrogen by reforming methanol reaction, it is characterised in that the water tank
（6）The temperature range of the high temperature and high pressure steam obtained after interior water vapor is 120 ~ 300 DEG C, and pressure limit is 0.5 ~ 3.0MPa,
High temperature and high pressure steam is with flowing through heat exchanger（5）, vaporizer（7）, reactor（8）Raw material formed heat convection.
5. the heat supply method according to claim 4 for preparing hydrogen by reforming methanol reaction, it is characterised in that the reactor
（8）Raw material be methanol water mixed liquid.
6. the heat supply method according to claim 1 for preparing hydrogen by reforming methanol reaction, it is characterised in that the separation dress
Put（9）For pressure-swing absorption apparatus or palladium film purification devices.
7. the heat supply method according to claim 1 for preparing hydrogen by reforming methanol reaction, it is characterised in that the circulating pump
（10）For high-pressure circulation pump.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109081307A (en) * | 2018-10-26 | 2018-12-25 | 浙江氢谷新能源汽车有限公司 | Solar powered auxiliary hydrogen production units by carbinol |
| CN111336038A (en) * | 2018-12-18 | 2020-06-26 | 杭州醇电科技有限公司 | Low-temperature cold start method for methanol engine |
| CN109775660B (en) * | 2019-03-25 | 2024-02-13 | 樊品良 | Alcohol water high-efficiency hydrogen production equipment |
| CN110606467B (en) * | 2019-10-11 | 2022-12-09 | 上海齐耀动力技术有限公司 | Methanol reforming hydrogen production process and system |
| CN110655057B (en) * | 2019-10-16 | 2022-05-03 | 天津大学 | Method for preparing biochar and hydrogen by using anaerobic fermentation byproducts |
| CN110550604A (en) * | 2019-10-17 | 2019-12-10 | 华润智慧能源有限公司 | novel thermodynamic system for thermal power coupling methanol hydrogen production |
| CN112678770B (en) * | 2020-12-28 | 2022-11-29 | 四川天采科技有限责任公司 | Methanol and water hydrogen production device adopting PSA tail gas catalytic combustion for heat supply |
| CN115594147A (en) * | 2021-07-09 | 2023-01-13 | 中国石化工程建设有限公司（Cn） | Method for preparing hydrogen from methanol and system for preparing hydrogen from methanol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033059A (en) * | 2007-02-08 | 2007-09-12 | 西南化工研究设计院 | Method of preparing hydrogen by reforming methanol-water steam |
| CN201343445Y (en) * | 2008-12-31 | 2009-11-11 | 四川亚连科技有限责任公司 | Methanol-vapor reforming installation with circulated fume as heat carrier |
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2016
- 2016-05-09 CN CN201610302025.6A patent/CN105967144B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033059A (en) * | 2007-02-08 | 2007-09-12 | 西南化工研究设计院 | Method of preparing hydrogen by reforming methanol-water steam |
| CN201343445Y (en) * | 2008-12-31 | 2009-11-11 | 四川亚连科技有限责任公司 | Methanol-vapor reforming installation with circulated fume as heat carrier |
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