CN106242946B - A kind of equipment and technique of solar hydrogen making synthesizing methanol - Google Patents
A kind of equipment and technique of solar hydrogen making synthesizing methanol Download PDFInfo
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- CN106242946B CN106242946B CN201610809223.1A CN201610809223A CN106242946B CN 106242946 B CN106242946 B CN 106242946B CN 201610809223 A CN201610809223 A CN 201610809223A CN 106242946 B CN106242946 B CN 106242946B
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses the equipment and technique of a kind of solar hydrogen making synthesizing methanol, which includes solar energy heat build-up system, high-temperature vapor preparation system, solar power system, high-temperature electrolysis hydrogen generating system, carbon dioxide preparation system, gas mixer, system for methanol synthesis, First Heat Exchanger, molecular screen membrane separator, methanol storage drum, water store tank, delivery pump；Wherein, high-temperature vapor preparation system is used to prepare 800 DEG C~900 DEG C of high-temperature vapor using the thermal energy that solar energy heat build-up system provides, and is supplied to high-temperature electrolysis hydrogen generating system；First Heat Exchanger is installed on the conveyance conduit between system for methanol synthesis and molecular screen membrane separator；Molecular screen membrane separator, for separating the water in methanol-water weak solution, the water after separating is delivered to water store tank, is pumped to high-temperature vapor preparation system by delivery pump.Hydrogen feedstock preparation efficiency of the invention is high, solar energy utilization rate is high, and can make full use of by-product water caused by methanol processed.
Description
Technical field
The present invention relates to the equipment and technique of a kind of solar hydrogen making synthesizing methanol.
Background technique
Methanol (CH3OH), be a kind of important Organic Chemicals and high-grade energy, mainly for the manufacture of formaldehyde, acetic acid,
One of a variety of organic products such as chloromethanes, first ammonia, dimethyl sulfate and pesticide, the important source material of medicine.Methanol can also replace
Gasoline as fuel uses, and is used for advanced reforming hydrogen producing process.In the prior art, methanol manufacturing method mainly include with
Under it is several: one, chloromethanes Hydrolyze method: CH3Cl+H2O→CH3OH+HCl；Secondly, methane portion oxidation method, directly oxidizing methane
Generate methanol: 2CH4+O2→2CH3OH；Thirdly, the method for the fossil energies methanol such as coal, coke, oil；Four, hydrogen and an oxidation
The synthesis methanol of carbon, reaction equation: CO+H2→CH3OH, can refer to Chinese invention patent application 97101425.6,
200780005726.2,200610151359.4 etc.；Five, carbon dioxide and hydrogen methanol processed under the action of catalyst: CO2+
3H2→CH3OH+H2O, can refer to Chinese invention patent application 200810046409.1,200910112654.2,
200910163236.6,201310175806.X, 200810046409.1 etc..However, above-mentioned existing methanol manufacturing process is all
It is to directly adopt H2、CH4、CO、CH3Cl or fossil energy make raw material.
In the natural energy of nature, solar energy is very important renewable and clean energy resource.Wherein, the utilization of solar energy
Mode mainly includes three kinds: one, solar energy power generating, and solar energy photovoltaic system can provide illumination and traffic letter for house
Signal lamp and monitoring system, be connected to the grid power supply；Different shape can be made in photovoltaic panel assembly, and component can connect, and generate more
More electric energy；Balcony and the mountable photovoltaic module of building surface, these photovoltaic facilities are commonly known as attached to building
Photovoltaic system.Secondly, solar energy heat build-up, sunlight polymerize by modern sun thermal energy science and technology, and uses its energy production hot water, steam
And electric power.Thirdly, utilize solar battery or lithium battery etc. carry out energy storage.However, above-mentioned solar energy actually utilize during,
Photovoltaic power generation otherwise need it is grid-connected or need and building electricity consumption facility match；Solar energy heat build-up is also needed and is built
Object is matched with hot facility, and the hot water, the steam that generate often cannot be used up；Furthermore energy storage mode is also by the limit of energy-storage battery
System.
With the development of technology, solar hydrogen making technology has gradually formed, and China disclosed in solar hydrogen making aspect is special
Benefit has: a kind of 200810063882.0 high-efficiency self-coupling solar hydrogen-system makings, 200810172947.5 solar energy waters electrolysis system
Hydrogen (oxygen) device, a kind of 201010291005.6 optically focused turn the enhanced solar energy catalytic decomposition water hydrogen generating system of photoreactivation,
201110006999.7 DVD multidisc solar energy heat build-up coupled biological matter supercritical water gasification hydrogen production endothermic reaction device,
200910249943.7 a kind of preparation method of the nano-electrode using decomposing water with solar energy hydrogen manufacturing.However, due to hydrogen boiling point
Very low (- 252.8 DEG C), liquid can just be converted it by needing to apply stronger pressure, and be stored in the pressure vessels such as steel cylinder
In can transport, and have risk of explosion, therefore, the energy storage mode of solar hydrogen making is greatly limited.
Chinese invention application 201410376774.4(applicant: Guangdong is closed up to Energy Science Co., Ltd, is this creation
Person) disclose a kind of methanol manufacturing process；Chinese invention patent 200510045058.9 discloses a kind of using solar energy production
The method of hydrogen or methanol.But during above-mentioned methanol technics processed, the preparation efficiency of hydrogen feedstock is lower, solar energy does not have
Have and preferably utilized, energy dissipation is more serious, and by-product water caused by methanol processed is not also utilized well.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiency of the prior art, provide a kind of solar hydrogen making conjunction
At the equipment of methanol, the hydrogen feedstock preparation efficiency of the equipment is high, solar energy utilization rate is high, and can make full use of methanol institute processed
The by-product water of generation.At the same time, the technique that the present invention also provides a kind of solar hydrogen making synthesizing methanol.
In order to solve the first technical problem mentioned above, the first technical solution of the invention is:
A kind of equipment of solar hydrogen making synthesizing methanol, comprising:
Solar energy heat build-up system is used for optically focused, thermal-arrest, provides thermal energy for high-temperature vapor preparation system；
High-temperature vapor preparation system, the thermal energy for being provided using solar energy heat build-up system prepare 800 DEG C~900 DEG C
High-temperature vapor, the high-temperature vapor are supplied to high-temperature electrolysis hydrogen generating system；
Solar power system is supplied to high-temperature electrolysis hydrogen generating system for issuing direct current using solar energy；
High-temperature electrolysis hydrogen generating system, the direct current supplied using solar power system, is electrolysed high-temperature vapor
Hydrogen manufacturing and oxygen processed, high-temperature hydrogen obtained transfer to gas mixer；
Carbon dioxide preparation system, is used to prepare carbon dioxide, transfers to gas mixer；
Gas mixer, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis；
System for methanol synthesis synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；First
Alcohol synthesis system is equipped with temperature regulating device and pressure control device, wherein temperature regulating device is used for the synthesis temperature tune of system for methanol synthesis
Whole is 220-260 DEG C, and pressure control device is used to the pressure of system for methanol synthesis being adjusted to 5.5-6.2Mpa；
First Heat Exchanger is installed on the conveyance conduit between system for methanol synthesis and molecular screen membrane separator, methanol-water
Mixed gas exchanges heat in First Heat Exchanger with the water to come from water store tank conveying, methanol-water mixed gas temperature drop
It is low, it is liquefied as methanol-water weak solution, the temperature of water increases；
Molecular screen membrane separator makes methanol-water weak solution become methanol-water dense for separating the water in methanol-water weak solution
Solution, the water after separating are delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
Methanol storage drum, for storing methanol-water concentrated solution；
Water store tank for storing water, and receives the water separated from molecular screen membrane separator；
Delivery pump, for sending the water pump in water store tank to high-temperature vapor preparation system.
In order to solve the first technical problem mentioned above, the second technical solution of the invention is:
A kind of equipment of solar hydrogen making synthesizing methanol, comprising:
Solar power system is used for solar power generation, is supplied to high-temperature vapor preparation system and high-temperature electrolysis hydrogen manufacturing
System；
High-temperature vapor preparation system, interior be equipped with utilize solar powered electric heater, high-temperature vapor preparation system
System utilizes the thermal energy of electric heater, and the high-temperature vapor of 800 DEG C~900 DEG C of preparation is supplied to high-temperature electrolysis hydrogen generating system；
High-temperature electrolysis hydrogen generating system, the direct current supplied using solar power system, is electrolysed high-temperature vapor
Hydrogen manufacturing and oxygen processed, high-temperature hydrogen obtained transfer to gas mixer；
Carbon dioxide preparation system, is used to prepare carbon dioxide, transfers to gas mixer；
Gas mixer, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis；
System for methanol synthesis synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；First
Alcohol synthesis system is equipped with temperature regulating device and pressure control device, wherein temperature regulating device is used for the synthesis temperature tune of system for methanol synthesis
Whole is 220-260 DEG C, and pressure control device is used to the pressure of system for methanol synthesis being adjusted to 5.5-6.2Mpa；
First Heat Exchanger is installed on the conveyance conduit between system for methanol synthesis and molecular screen membrane separator, methanol-water
Mixed gas exchanges heat in First Heat Exchanger with the water to come from water store tank conveying, methanol-water mixed gas temperature drop
It is low, it is liquefied as methanol-water weak solution, the temperature of water increases；
Molecular screen membrane separator makes methanol-water weak solution become methanol-water dense for separating the water in methanol-water weak solution
Solution, the water after separating are delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
Methanol storage drum, for storing methanol-water concentrated solution；
Water store tank for storing water, and receives the water separated from molecular screen membrane separator；
Delivery pump, for sending the water pump in water store tank to high-temperature vapor preparation system.
The equipment of the solar hydrogen making synthesizing methanol further includes oxygen storage tank and the second heat exchanger, the high-temperature electrolysis
Oxygen made from hydrogen generating system is stored in oxygen storage tank after the second heat exchanger, described that the water to come is conveyed from water store tank
High-temperature vapor preparation system is delivered to after the second heat exchanger again；In the second heat exchanger, oxygen temperature reduces, coolant-temperature gage liter
It is high.
The high-temperature electrolysis hydrogen generating system is equipped with solid oxide electrolyte heap, and the direct current is 36V.
To solve above-mentioned second technical problem, the technical scheme is that
A kind of solar hydrogen making methanol synthetizing technology, comprises the following steps that:
A. solar energy heat build-up or solar power generation are utilized, high-temperature vapor preparation system is made to work, preparation 800 DEG C~900
DEG C high-temperature vapor, and be supplied to high-temperature electrolysis hydrogen generating system；
It b. is that high-temperature electrolysis hydrogen generating system supplies direct current, the electrolysis of high-temperature electrolysis hydrogen generating system using solar power system
Hydrogen and oxygen is made in high-temperature vapor, wherein high-temperature hydrogen transfers to gas mixer；At the same time, carbon dioxide is utilized
Preparation system prepares carbon dioxide, transfers to gas mixer；
C. in gas mixer, high-temperature hydrogen and carbon dioxide mix transfer to system for methanol synthesis at medium temperature gas；
D. in system for methanol synthesis, synthesis temperature is adjusted to 220-260 DEG C, pressure is adjusted to 5.5-6.2Mpa,
Gas space velocity is controlled in 12000-16000h-1, hydrogen, carbon dioxide synthesize methanol-water gaseous mixture under the action of catalyst
Body；
E. methanol water mixed gas is after First Heat Exchanger, and liquefy methanol-water weak solution, into molecular screen membrane separator；
F. methanol-water weak solution isolates a large amount of water after molecular screen membrane separator, becomes methanol-water concentrated solution, separation
Water later is delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
G. the water in water store tank is under the pump action of delivery pump, after First Heat Exchanger heats up, is delivered to high-temperature water
Steam preparation system, to be prepared into high-temperature vapor required for high-temperature electrolysis device for producing hydrogen.
The catalyst that the system for methanol synthesis uses is the bicomponent catalyst that CuO and ZnO is formed, weight percent
For 50:50.
In step g, the water in water store tank is being delivered to high temperature after First Heat Exchanger, then through the second heat exchanger
Vapor preparation system, high-temperature oxygen obtained is stored in oxygen storage tank after the second heat exchanger in the step b.
The high-temperature electrolysis hydrogen generating system is equipped with solid oxide electrolyte heap SOEC, the yin of solid oxide electrolyte heap SOEC
Pole material is Ni, anode material LaMnO3, electrolyte is doping Sc2O3ZrO2, electrolysis temperature is 800 DEG C~900 DEG C, electricity
Decompression force is 5.5-6.2Mpa, and electrolysis direct current voltage is 36V；High-temperature electrolysis hydrogen generating system is additionally provided with for magnetizing high-temperature vapor
Magnetizing assembly.
The beneficial effects of the present invention are: one, the present invention utilize solar energy heat build-up or solar power generation, make high-temperature vapor
Preparation system prepares 800 DEG C~900 DEG C of high-temperature vapor, and is supplied to high-temperature electrolysis device for producing hydrogen, recycles solar energy hair
Electric system is that high-temperature electrolysis device for producing hydrogen supplies direct current, and high-temperature electrolysis device for producing hydrogen is electrolysed high-temperature vapor and hydrogen and oxygen is made
Gas, hydrogen production efficiency is very high, and solar energy is made to be fully used；Secondly, the present invention using gas mixer by high temperature
Hydrogen and carbon dioxide mix transfer to system for methanol synthesis at medium temperature gas, make the mixed gas temperature into system for methanol synthesis
Substantially close to temperature required for synthesizing methanol, to improve heating mixed gas efficiency, heating mixed gas institute has been saved
The energy of demand；Thirdly, in system for methanol synthesis, synthesis temperature is adjusted to 220-260 DEG C, pressure is adjusted to 5.5-
6.2Mpa controls gas space velocity in 12000-16000h-1, the combined coefficient of methanol can be made to reach best；Four, methanol-water is dilute
Solution can isolate pure water after molecular screen membrane separator, reduce methanol waste；Five, the water isolated is stored in water
In holding vessel, and high-temperature vapor preparation system can be delivered under the pump action of delivery pump, after First Heat Exchanger heats up
System, so that by-product water caused by methanol processed be made to be fully used；Six, by utilizing First Heat Exchanger and the second heat exchange
Device increases the temperature of water rapidly, or even gasification, so that the heat demand of high-temperature vapor preparation system is greatly reduced, into one
Step improves the efficiency of solar energy utilization.
Detailed description of the invention
Fig. 1 is the overall structure block diagram of the embodiment of the present invention one.
Fig. 2 is the overall structure block diagram of the embodiment of the present invention two.
Specific embodiment
Xia Mianjiehefutuduibenfamingjiegouyuanlihegongzuoyuanlizuojinyibuxiangxishuoming.
Embodiment one:
As shown in Figure 1, a kind of equipment of solar hydrogen making synthesizing methanol, comprising:
Solar energy heat build-up system 1 is used for optically focused, thermal-arrest, provides thermal energy for high-temperature vapor preparation system 2；The solar energy
Heat build-up system includes solar concentrating collector, which is groove type solar condenser, disc type solar energy
Condenser, tower type solar condenser, any one in composite parabolic formula condenser；
High-temperature vapor preparation system 2, the thermal energy for being provided using solar energy heat build-up system 1 prepare 800 DEG C~900 DEG C
High-temperature vapor, which is supplied to high-temperature electrolysis hydrogen generating system 3；
Solar power system 4 is supplied to high-temperature electrolysis hydrogen generating system 3 for issuing direct current using solar energy；This is too
Positive energy electricity generation system 4 includes solar battery, which is monocrystaline silicon solar cell or polysilicon solar cell
Or non-crystal silicon solar cell；
High-temperature electrolysis hydrogen generating system 3, the direct current supplied using solar power system 4 carry out electricity to high-temperature vapor
Solution hydrogen manufacturing and oxygen processed, high-temperature hydrogen obtained transfer to gas mixer 5；
Carbon dioxide preparation system 6, is used to prepare carbon dioxide, transfers to gas mixer 5；Carbon dioxide preparation system
6 can directly can also be refined using air using the preparation of the methods of high-temperature calcination lime stone；
Gas mixer 5, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis
7；
System for methanol synthesis 7 synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；First
Alcohol synthesis system is equipped with temperature regulating device and pressure control device (not shown), wherein temperature regulating device is used for system for methanol synthesis 7
Synthesis temperature be adjusted to 220-260 DEG C, pressure control device is used to the pressure of system for methanol synthesis 7 being adjusted to 5.5-6.2Mpa；
First Heat Exchanger 8 is installed on the conveyance conduit between system for methanol synthesis 7 and molecular screen membrane separator 9, methanol
Water mixed gas exchanges heat in First Heat Exchanger 8 with the water to come is conveyed from water store tank 10, methanol water mixed gas temperature
Degree reduces, and is liquefied as methanol-water weak solution, and the temperature of water increases；
Molecular screen membrane separator 9 makes methanol-water weak solution become methanol-water dense for separating the water in methanol-water weak solution
Solution, the water after separating are delivered to water store tank 10, and methanol-water concentrated solution is delivered to methanol storage drum 11；The Molecule Motion of methanol
Aerodynamic diameter is 0.38nm, water 0.29nm, uses 4A molecular screen membrane can be with the water in methanol removal；4A molecular screen membrane aperture is
0.42nm, although bigger than methanol molecules diameter, its hydrophily with super strength, water component Preferential adsorption is in molecular sieve fenestra
In road and pass through, so that methanol crossover channel can also be blocked, can achieve very high separation factor；
Methanol storage drum 11, for storing methanol-water concentrated solution；
Water store tank 10 for storing water, and receives the water separated from molecular screen membrane separator 9, certainly, water storage
Pure water can also be directly added into tank 10；
Delivery pump 12, for sending the water pump in water store tank 10 to high-temperature vapor preparation system 2, the delivery pump 12 by
Solar power system 4 is powered.
In the above-mentioned technical solutions, high-temperature electrolysis hydrogen generating system is equipped with solid oxide electrolyte heap SOEC, soild oxide
The cathode material for being electrolysed heap SOEC is Ni, anode material LaMnO3, electrolyte is doping Sc2O3ZrO2, electrolysis temperature is
800 DEG C~900 DEG C, electrolytic pressure 5.5-6.2Mpa, electrolysis direct current voltage is 36V, and such electrolytic hydrogen production efficiency reaches best；
In addition, high-temperature electrolysis hydrogen generating system is additionally provided with the magnetizing assembly for magnetizing high-temperature vapor, although vapor is obtained in magnetization
The energy obtained is seldom, but magnetic history can trigger steam activation energy, play catalyzed aqueous vapour activation.
In the above-mentioned technical solutions, the internal pressure of high-temperature electrolysis hydrogen generating system is by vapor self-assembling formation, methanol-fueled CLC
The internal pressure of system is by mixed gas self-assembling formation；In addition, system for methanol synthesis is preferably duct type system for methanol synthesis.
As shown in Figure 1, the equipment of the solar hydrogen making synthesizing methanol further includes oxygen storage tank 14 and the second heat exchanger
13, oxygen made from the high-temperature electrolysis hydrogen generating system 3 is stored in oxygen storage tank 14 after the second heat exchanger 13, it is described from
Water store tank 10 conveys the water to come and is delivered to high-temperature vapor preparation system 2 after the second heat exchanger 13；In the second heat exchanger
In 14, oxygen temperature is reduced, and coolant-temperature gage increases, or even gasification.
Embodiment two:
As shown in Fig. 2, a kind of equipment of solar hydrogen making synthesizing methanol, comprising:
Solar power system 4 is used for solar power generation, is supplied to high-temperature vapor preparation system 2 and high-temperature electrolysis system
Hydrogen system 3；The solar power system 4 includes solar battery, which is monocrystaline silicon solar cell or polycrystalline
Silicon solar cell or non-crystal silicon solar cell；
High-temperature vapor preparation system 2, interior be equipped with utilize solar powered electric heater (not shown), high temperature
Vapor preparation system 2 prepares 800 DEG C~900 DEG C of high-temperature vapor, is supplied to high-temperature electrolysis using the thermal energy of electric heater
Hydrogen generating system 3；
High-temperature electrolysis hydrogen generating system 3, the direct current supplied using solar power system 4 carry out electricity to high-temperature vapor
Solution hydrogen manufacturing and oxygen processed, high-temperature hydrogen obtained transfer to gas mixer 5；
Carbon dioxide preparation system 6, is used to prepare carbon dioxide, transfers to gas mixer 5；Carbon dioxide preparation system
6 can directly can also be refined using air using the preparation of the methods of high-temperature calcination lime stone；
Gas mixer 5, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis
7；
System for methanol synthesis 7 synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；First
Alcohol synthesis system is equipped with temperature regulating device and pressure control device (not shown), wherein temperature regulating device is used for system for methanol synthesis 7
Synthesis temperature be adjusted to 220-260 DEG C, pressure control device is used to the pressure of system for methanol synthesis 7 being adjusted to 5.5-6.2Mpa；
First Heat Exchanger 8 is installed on the conveyance conduit between system for methanol synthesis 7 and molecular screen membrane separator 9, methanol
Water mixed gas exchanges heat in First Heat Exchanger 8 with the water to come is conveyed from water store tank 10, methanol water mixed gas temperature
Degree reduces, and is liquefied as methanol-water weak solution, and the temperature of water increases；
Molecular screen membrane separator 9 makes methanol-water weak solution become methanol-water dense for separating the water in methanol-water weak solution
Solution, the water after separating are delivered to water store tank 10, and methanol-water concentrated solution is delivered to methanol storage drum 11；The Molecule Motion of methanol
Aerodynamic diameter is 0.38nm, water 0.29nm, uses 4A molecular screen membrane can be with the water in methanol removal；4A molecular screen membrane aperture is
0.42nm, although bigger than methanol molecules diameter, its hydrophily with super strength, water component Preferential adsorption is in molecular sieve fenestra
In road and pass through, so that methanol crossover channel can also be blocked, can achieve very high separation factor；
Methanol storage drum 11, for storing methanol-water concentrated solution；
Water store tank 10 for storing water, and receives the water separated from molecular screen membrane separator 9, certainly, water storage
Pure water can also be directly added into tank 10；
Delivery pump 12, for sending the water pump in water store tank 10 to high-temperature vapor preparation system 2, the delivery pump 12 by
Solar power system 4 is powered.
In the above-mentioned technical solutions, high-temperature electrolysis hydrogen generating system is equipped with solid oxide electrolyte heap SOEC, soild oxide
The cathode material for being electrolysed heap SOEC is Ni, anode material LaMnO3, electrolyte is doping Sc2O3ZrO2, electrolysis temperature is
800 DEG C~900 DEG C, electrolytic pressure 5.5-6.2Mpa, electrolysis direct current voltage is 36V, and such electrolytic hydrogen production efficiency reaches best；
In addition, high-temperature electrolysis hydrogen generating system is additionally provided with the magnetizing assembly for magnetizing high-temperature vapor, although vapor is obtained in magnetization
The energy obtained is seldom, but magnetic history can trigger steam activation energy, play catalyzed aqueous vapour activation.
In the above-mentioned technical solutions, the internal pressure of high-temperature electrolysis hydrogen generating system is by vapor self-assembling formation, methanol-fueled CLC
The internal pressure of system is by mixed gas self-assembling formation；In addition, system for methanol synthesis is preferably duct type system for methanol synthesis.
As shown in Fig. 2, the equipment of the solar hydrogen making synthesizing methanol further includes oxygen storage tank 14 and the second heat exchanger
13, oxygen made from the high-temperature electrolysis hydrogen generating system 3 is stored in oxygen storage tank 14 after the second heat exchanger 13, it is described from
Water store tank 10 conveys the water to come and is delivered to high-temperature vapor preparation system 2 after the second heat exchanger 13；In the second heat exchanger
In 14, oxygen temperature is reduced, and coolant-temperature gage increases, or even gasification.
As shown in Fig. 2, the high-temperature electrolysis hydrogen generating system 3 is equipped with solid oxide electrolyte heap (not shown), it is described
Direct current is 36V, and the structure of solid oxide electrolyte heap can refer to Chinese invention application 201510126438.9.
Embodiment three:
A kind of solar hydrogen making methanol synthetizing technology, comprises the following steps that:
A. solar energy heat build-up or solar power generation are utilized, high-temperature vapor preparation system is made to work, preparation 800 DEG C~900
DEG C high-temperature vapor, and be supplied to high-temperature electrolysis device for producing hydrogen；
It b. is that high-temperature electrolysis device for producing hydrogen supplies direct current, the electrolysis of high-temperature electrolysis device for producing hydrogen using solar power system
Hydrogen and oxygen is made in high-temperature vapor, wherein high-temperature hydrogen transfers to gas mixer；At the same time, carbon dioxide is utilized
Preparation system prepares carbon dioxide, transfers to gas mixer；
C. in gas mixer, high-temperature hydrogen and carbon dioxide mix transfer to system for methanol synthesis at medium temperature gas；
D. in system for methanol synthesis, synthesis temperature is adjusted to 220-260 DEG C, pressure is adjusted to 5.5-6.2Mpa,
Gas space velocity is controlled in 12000-16000h-1, hydrogen, carbon dioxide synthesize methanol-water gaseous mixture under the action of catalyst
Body.
E. methanol water mixed gas is after First Heat Exchanger, and liquefy methanol-water weak solution, into molecular screen membrane separator；
F. methanol-water weak solution isolates a large amount of water after molecular screen membrane separator, becomes methanol-water concentrated solution, separation
Water later is delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
G. the water in water store tank is under the pump action of delivery pump, after First Heat Exchanger heats up, is delivered to high-temperature water
Steam preparation system, to be prepared into high-temperature vapor required for high-temperature electrolysis device for producing hydrogen.
Preferably, the high-temperature electrolysis hydrogen generating system is equipped with solid oxide electrolyte heap SOEC, solid oxide electrolyte heap
The cathode material of SOEC is Ni, anode material LaMnO3, electrolyte is doping Sc2O3ZrO2, electrolysis temperature be 800 DEG C~
900 DEG C, electrolytic pressure 5.5-6.2Mpa, electrolysis direct current voltage is 36V, and such electrolytic hydrogen production efficiency reaches best；In addition, high
Warm electrolytic hydrogen production system is additionally provided with the magnetizing assembly for magnetizing high-temperature vapor, although the energy that vapor is obtained in magnetization
Seldom, but magnetic history can trigger steam activation energy, play catalyzed aqueous vapour activation.
Preferably, the catalyst that the system for methanol synthesis uses is the bicomponent catalyst that CuO and ZnO is formed, heavy
Amount percentage is 50:50.
In step g, the water in water store tank is being delivered to high temperature after First Heat Exchanger, then through the second heat exchanger
Vapor preparation system, high-temperature oxygen obtained is stored in oxygen storage tank after the second heat exchanger in the step b.
The above is only better embodiment of the present invention, and all technical solutions according to the present invention are to above implementation
Any subtle modifications, equivalent variations and modifications, belong in the range of technical solution of the present invention made by mode.
Claims (7)
1. a kind of equipment of solar hydrogen making synthesizing methanol characterized by comprising
Solar energy heat build-up system is used for optically focused, thermal-arrest, provides thermal energy for high-temperature vapor preparation system；
High-temperature vapor preparation system, the thermal energy for being provided using solar energy heat build-up system prepare 800 DEG C~900 DEG C of high temperature
Vapor, the high-temperature vapor are supplied to high-temperature electrolysis hydrogen generating system；
Solar power system is supplied to high-temperature electrolysis hydrogen generating system for issuing direct current using solar energy；
High-temperature electrolysis hydrogen generating system, the direct current supplied using solar power system carry out electrolytic hydrogen production to high-temperature vapor
And oxygen processed, high-temperature hydrogen obtained transfer to gas mixer；
Carbon dioxide preparation system, is used to prepare carbon dioxide, transfers to gas mixer；
Gas mixer, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis；
System for methanol synthesis synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；Methanol closes
Temperature regulating device and pressure control device are equipped at system, wherein temperature regulating device is for the synthesis temperature of system for methanol synthesis to be adjusted to
220-260 DEG C, pressure control device is used to the pressure of system for methanol synthesis being adjusted to 5.5-6.2Mpa；
First Heat Exchanger is installed on the conveyance conduit between system for methanol synthesis and molecular screen membrane separator, methanol-water mixing
Gas exchanges heat, methanol-water mixed gas temperature reduces, liquid in First Heat Exchanger with the water to come from water store tank conveying
It is melted into methanol-water weak solution, the temperature of water increases；
Molecular screen membrane separator makes methanol-water weak solution become methanol-water concentrated solution for separating the water in methanol-water weak solution,
Water after separation is delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
Methanol storage drum, for storing methanol-water concentrated solution；
Water store tank for storing water, and receives the water separated from molecular screen membrane separator；
Delivery pump, for sending the water pump in water store tank to high-temperature vapor preparation system；
It further include oxygen storage tank and the second heat exchanger, oxygen made from the high-temperature electrolysis hydrogen generating system is after the second heat exchanger
It is stored in oxygen storage tank, the water to come from water store tank conveying is delivered to high-temperature vapor system after the second heat exchanger
Standby system；In the second heat exchanger, oxygen temperature reduces, and coolant-temperature gage increases.
2. the equipment of solar hydrogen making synthesizing methanol according to claim 1, it is characterised in that: the high-temperature electrolysis hydrogen manufacturing
System is equipped with solid oxide electrolyte heap, and the direct current is 36V.
3. a kind of equipment of solar hydrogen making synthesizing methanol characterized by comprising
Solar power system is used for solar power generation, is supplied to high-temperature vapor preparation system and high-temperature electrolysis hydrogen generating system；
High-temperature vapor preparation system, interior be equipped with utilize solar powered electric heater, high-temperature vapor preparation system benefit
With the thermal energy of electric heater, the high-temperature vapor of 800 DEG C~900 DEG C of preparation is supplied to high-temperature electrolysis hydrogen generating system；
High-temperature electrolysis hydrogen generating system, the direct current supplied using solar power system carry out electrolytic hydrogen production to high-temperature vapor
And oxygen processed, high-temperature hydrogen obtained transfer to gas mixer；
Carbon dioxide preparation system, is used to prepare carbon dioxide, transfers to gas mixer；
Gas mixer, for high-temperature hydrogen and carbon dioxide mix at medium temperature gas, to be transferred to system for methanol synthesis；
System for methanol synthesis synthesizes methanol water mixed gas for hydrogen and carbon dioxide under the action of catalyst；Methanol closes
Temperature regulating device and pressure control device are equipped at system, wherein temperature regulating device is for the synthesis temperature of system for methanol synthesis to be adjusted to
220-260 DEG C, pressure control device is used to the pressure of system for methanol synthesis being adjusted to 5.5-6.2Mpa；
First Heat Exchanger is installed on the conveyance conduit between system for methanol synthesis and molecular screen membrane separator, methanol-water mixing
Gas exchanges heat, methanol-water mixed gas temperature reduces, liquid in First Heat Exchanger with the water to come from water store tank conveying
It is melted into methanol-water weak solution, the temperature of water increases；
Molecular screen membrane separator makes methanol-water weak solution become methanol-water concentrated solution for separating the water in methanol-water weak solution,
Water after separation is delivered to water store tank, and methanol-water concentrated solution is delivered to methanol storage drum；
Methanol storage drum, for storing methanol-water concentrated solution；
Water store tank for storing water, and receives the water separated from molecular screen membrane separator；
Delivery pump, for sending the water pump in water store tank to high-temperature vapor preparation system；
It further include oxygen storage tank and the second heat exchanger, oxygen made from the high-temperature electrolysis hydrogen generating system is after the second heat exchanger
It is stored in oxygen storage tank, the water to come from water store tank conveying is delivered to high-temperature vapor after the second heat exchanger again
Preparation system；In the second heat exchanger, oxygen temperature reduces, and coolant-temperature gage increases.
4. the equipment of solar hydrogen making synthesizing methanol according to claim 3, it is characterised in that: the high-temperature electrolysis hydrogen manufacturing
System is equipped with solid oxide electrolyte heap, and the direct current is 36V.
5. a kind of solar hydrogen making methanol synthetizing technology, which is characterized in that comprise the following steps that:
A. solar energy heat build-up or solar power generation are utilized, high-temperature vapor preparation system is made to work, 800 DEG C~900 DEG C of preparation
High-temperature vapor, and it is supplied to high-temperature electrolysis hydrogen generating system；
It b. is that high-temperature electrolysis hydrogen generating system supplies direct current using solar power system, high-temperature electrolysis hydrogen generating system is electrolysed high temperature
Hydrogen and oxygen is made in vapor, wherein high-temperature hydrogen transfers to gas mixer；At the same time, it is prepared using carbon dioxide
System prepares carbon dioxide, transfers to gas mixer；
C. in gas mixer, high-temperature hydrogen and carbon dioxide mix transfer to system for methanol synthesis at medium temperature gas；
D. in system for methanol synthesis, synthesis temperature is adjusted to 220-260 DEG C, pressure is adjusted to 5.5-6.2Mpa, by gas
Body air speed is controlled in 12000-16000h-1, hydrogen, carbon dioxide synthesize methanol water mixed gas under the action of catalyst；
E. methanol water mixed gas is after First Heat Exchanger, and liquefy methanol-water weak solution, into molecular screen membrane separator；
F. methanol-water weak solution isolates a large amount of water after molecular screen membrane separator, becomes methanol-water concentrated solution, after separation
Water be delivered to water store tank, methanol-water concentrated solution is delivered to methanol storage drum；
G. the water in water store tank is under the pump action of delivery pump, after First Heat Exchanger heats up, is delivered to high-temperature vapor
Preparation system, to be prepared into high-temperature vapor required for high-temperature electrolysis device for producing hydrogen；
In step g, the water in water store tank is being delivered to high-temperature water steaming after First Heat Exchanger, then through the second heat exchanger
Gas preparation system, high-temperature oxygen obtained is stored in oxygen storage tank after the second heat exchanger in the step b.
6. solar hydrogen making methanol synthetizing technology according to claim 5, it is characterised in that: high-temperature electrolysis hydrogen manufacturing system
System is equipped with solid oxide electrolyte heap SOEC, and the cathode material of solid oxide electrolyte heap SOEC is Ni, and anode material is
LaMnO3, electrolyte is doping Sc2O3ZrO2, electrolysis temperature is 800 DEG C~900 DEG C, electrolytic pressure 5.5-6.2Mpa, electricity
Solution DC voltage is 36V；High-temperature electrolysis hydrogen generating system is additionally provided with the magnetizing assembly for magnetizing high-temperature vapor.
7. solar hydrogen making methanol synthetizing technology according to claim 5, it is characterised in that: the system for methanol synthesis makes
Catalyst is CuO and the bicomponent catalyst of ZnO composition, weight percent 50:50.
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| KR102599470B1 (en) * | 2017-07-25 | 2023-11-08 | 토프쉐 에이/에스 | Process for simultaneous production of methanol and ammonia |
| EP3850124A1 (en) * | 2018-09-13 | 2021-07-21 | Haldor Topsøe A/S | Process for the preparation of methanol |
| CN110358594A (en) * | 2019-06-21 | 2019-10-22 | 清华四川能源互联网研究院 | Water electrolysis hydrogen production and CO2The device and method of methanation synthetic natural gas |
| CN110904464A (en) * | 2019-11-14 | 2020-03-24 | 深圳大学 | Seawater electrolysis hydrogen production system based on offshore wind power |
| CN111139493B (en) * | 2019-12-23 | 2021-04-20 | 西安交通大学 | Solar photovoltaic photo-thermal high-temperature water electrolysis hydrogen production system and hydrogen production method |
| CN111621799B (en) * | 2020-06-08 | 2021-09-03 | 阳光电源股份有限公司 | Renewable energy hydrogen production and storage system and control method thereof |
| CN113511955A (en) * | 2021-06-03 | 2021-10-19 | 中国华能集团清洁能源技术研究院有限公司 | Device and method for synthesizing methanol by using carbon dioxide and water |
| CN113388425A (en) * | 2021-06-04 | 2021-09-14 | 南京航空航天大学 | Device and method for preparing carbon dioxide hydrocarbon fuel by utilizing solar energy through full spectrum |
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| CN114262262A (en) * | 2021-12-27 | 2022-04-01 | 西安热工研究院有限公司 | Energy storage system and method for preparing methanol by using synthetic methanol waste gas |
| CN114249297B (en) * | 2021-12-30 | 2023-01-31 | 江苏科技大学 | Methanol reforming hydrogen production system utilizing solar energy |
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