CN102553407B - Thermochemical cycle reaction system for decomposing CO2And H2O method and device - Google Patents
Thermochemical cycle reaction system for decomposing CO2And H2O method and device Download PDFInfo
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- CN102553407B CN102553407B CN2012100111772A CN201210011177A CN102553407B CN 102553407 B CN102553407 B CN 102553407B CN 2012100111772 A CN2012100111772 A CN 2012100111772A CN 201210011177 A CN201210011177 A CN 201210011177A CN 102553407 B CN102553407 B CN 102553407B
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Abstract
The invention relates to CO2Emission reduction technology, aiming at providing a thermochemical cycle reactionDecomposition of CO by system2And H2O method and apparatus. The method is that H2O、I2And SO2Sending the mixture into a Bunsen reaction device to perform spontaneous exothermic reaction, and introducing CO2The gas enters a fixed bed or a fluidized bed reactor to perform exothermic reaction with metal Zn or Ni; the products in each reaction process are recycled by each reaction device, and the final product is H2CO and O2. The highest heat source temperature of the invention is lower (less than 900 ℃), and other heat sources in various forms such as solar energy, nuclear energy and the like can be adopted; reduce Zn and CO to a certain extent2Adverse effects due to incomplete reaction; the reaction temperature is proper, and the large-scale industrial application is easy to realize.
Description
Technical field
The present invention relates to the thermochemical cycles reaction system and decompose new method and the technological process of carbon dioxide and water.
Background technology
At present, CO
2Emission problem more and more is subject to everybody attention, how effectively to reduce CO
2Discharging has become the important political economy subject under discussion in countries in the world.The states such as the U.S., Britain and Germany have have all studied and defined CO
2The discharging system, Japan has accelerated CO
2The research of comprehensive utilization aspect is planned to set up with CO with 10 years
2Independent Industrial system for industrial chemicals.CO at present
2Reduction of discharging can Adopts measure be to reduce discharging and controlling increment on the one hand: comprise and readjusting the energy structure, use low-carbon energy, greatly develop the clean energy resourcies such as nuclear energy, Hydrogen Energy, wind energy, improve the utilization ratio of the energy, development power-saving technology and the consumption habit that changes the mankind reduce the use of fossil fuel as far as possible.To strengthen CO on the other hand
2Disposal and utilization, this comprises and capturing and Plugging Technology Applied, carries out oil-gas mining, little algae utilizes and chemical utilization etc.At CO
2Utilize the aspect, although economy and risk assessment show CO
2The organic chemical industry to utilize be an aspect that is worth greatly developing, but due to CO
2Be a torpescence molecule, stable chemical nature needs to adopt high temperature, high pressure or uses catalyst just can make its reaction.Generally, CO
2The conversion ratio of catalytic hydrogenation reaction and yield are all not too high, apply with also being difficult at present economic scale.And thermochemical cycle decomposition and utilize CO
2System had obtained concern and the research of many scientific researchers in the last few years due to its unique superiority being arranged, and wherein, was one of main research direction based on metal-oxide to redox thermochemical cycle decomposition carbon dioxide and water system.
Based on metal-oxide, redox Thermochemical Decomposition carbon dioxide and water circulation are comprised of two steps usually: the first step is that metal oxide at high temperature decomposes and produces oxygen and metal simple-substance or low valent metal oxide; Second step is that metal simple-substance or low valent metal oxide hydrolysis occurs at a lower temperature come hydrogen making or the carbon dioxide decomposition reaction occurs to produce carbon monoxide.Whole process can be expressed as follows:
1/xMO
2→1/x MO
2-x+1/2O
2 (1)
1/xMO
2-x+H
2O→1/xMO
2+H
2 (2)
1/xMO
2-x+CO
2→1/xMO
2+CO (3)
First step decomposition reaction is the process of a high temperature heat absorption, usually needs very high reaction temperature (＞1600 ℃), therefore must adopt the Salar light-gathering high temperature heat source to drive reaction and carry out.Second step hydrolysis and carbon dioxide decomposition reaction are the processes of heat release, and its reaction temperature is relatively low.Can obtain more rational reaction rate when the M in reaction (1) is Fe, Zn or Ce element, the reaction temperature of reaction equation (2) and (3) is between 350～900 ℃.Be easy to find out by formula (1), (2) and (3): the overall reaction of whole process is exactly H
2O+CO
2→ H
2+ CO+O
2
Up to the present, Zn/ZnO is one of system of most study in the two-step thermochemical cycles, and this system has obtained research and development energetically.Whole process following steps are carried out:
ZnO(s)→Zn(g)+0.5O
2(g) (1)
Zn+H
2O(g)→ZnO(s)+H
2(g) (2)
Zn+CO
2(g)→ZnO(s)+CO(g) (3)
The pyrolysis of the first step: ZnO is an endothermic process, its Δ G
f 0The temperature of=0 o'clock is 2058 ℃, and its product is zinc fume and oxygen, finally need to separate or quenching to prevent the combination again of product.Second step: CO
2And H
2The decomposition reaction of O, according to kinetics, the reaction of formula (2) and (3) must (419 ℃ be carried out at temperature 1atm) surpassing the zinc fusing point.Yet, when the zinc that melts and water vapour or carbon dioxide reaction, can form layer of ZnO (cr) and float on fused mass, stop the further generation of reaction.Researchers have carried out a large amount of research to some chemical fundamentals of ZnO pyrolytic process.The research discovery, the productivity ratio of Zn depends on largely the dynamic process of decomposition reaction and gaseous products is carried out enough fast quenching to prevent its technical feasibility of combination again.The people such as Steinfeld (document Solar hydrogen progen production via a two-step water-splitting thermochemical cycle based on Zn/ZnO redox reaction.International Journal of Hydrogen Energy, 2002; 27 (6): 611-619) by solar energy Zn/ZnO circulation hydrogen generating system is carried out available energy and economic analysis, declare this system in the situation that do not reclaim any heat, the highest theoretical thermal efficiency can reach 29% (when solar energy system optically focused than 5000, the reactor running temperature is 2027 ℃), its main energy loss comes from hyperthermia radiation loss (account for gross energy 32%) and Zn (g) and the O of solar energy reactor
2Quenching loss (26%).The people such as Venstrom (document Splitting Water and Carbon Dioxide via the Heterogeneous Oxidation of Zinc Vapor:Thermodynamic Considerations.Journal of Solar Energy Engineering, 2011,133 (011017): 1-8) pass through solar energy Zn/ZnO Cycle-decomposition CO
2And H
2The O system carries out thermodynamic analysis, and this system is not in the situation that reclaim heat, and the highest theoretical thermal efficiency is 27%～31%.
The people such as William (document High-Flux Solar-Driven Thermochemical Dissociation of CO
2And H
2Using Nonstoichiometric Ceria.Science, 2010,330 (6012): 1797-1801) by solar energy CeO
2/ Ce
2O
3Cycle-decomposition CO
2And H
2The O system carries out thermodynamic analysis, declares this system in the situation that do not reclaim any heat, and the highest theoretical thermal efficiency can reach 16～19%.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, provides a kind of thermochemical cycles reaction system to decompose CO
2And H
2The method of O and device.
For realizing goal of the invention, the invention provides a kind of thermochemical cycles reaction system and decompose CO
2And H
2The method of O, its total chemical equation is H
2O+CO
2→ H
2+ CO+O
2, specifically comprise the following steps:
(1) with H
2O, I
2And SO
2In amount of substance ratio 14～16: 1.5～9: 1 sends into the Bunsen reaction unit, and at the uniform velocity stirring reaction liquid guarantees that it mixes, and issues 20～120 ℃ and 1～2atm condition and is conigenous the granting thermal response, produces HI phase and the H of many water
2SO
4Phase solution, the chemical equation of this reaction is as follows:
I
2+SO
2+2H
2O→2HI+H
2SO
4
In reaction, excessive iodine has been guaranteed the mixed solution generation liquid-liquid phase separation that the Bunsen reaction generates, HI phase and the H of lower leaf in formation
2SO
4Phase solution;
(2) under 120～260 ℃, 0.08～1.3atm and adiabatic condition, to H
2SO
4Phase solution is implemented multistage sulphuric acid concentration and is processed;
(3) H after concentrating
2SO
4Be warming up to 800～900 ℃, catalytic decomposition generates SO
2, H
2O and end product O
2, the chemical equation of this reaction is as follows:
H
2SO
4→SO
2+H
2O+0.5O
2
SO
2, H
2O and end product O
2Turn back to the recycling of Bunsen reaction unit;
(4) under 350～900 ℃, pass into CO
2Gas generates oxide M O and end product CO to fixed bed or fluidized-bed reactor and metal M generation exothermic reaction, and the chemical equation of this reaction is as follows:
M+CO
2→MO+CO
Described M is metallic element Zn or Ni;
(5) carry out electrodialysis process for step (1) gained HI phase solution, obtain concentrated HI solution at the electrodialytic cell cathode side, the dilution HI solution that anode-side obtains turns back to the recycling of Bunsen reaction unit; HI solution after concentrated carries out rectifying in concentrated rectifier unit, obtain pure HI steam; Spontaneous exothermic reaction generation MI is occured in gained HI steam and metal oxide MO in the aqueous solution of 20～90 ℃
2And H
2O, the chemical equation of this reaction is as follows:
2HI+MO→MI
2+H
2O
(6) obtain MI by distillation
2Solid is placed in fixed bed or fluidized-bed reactor, passes into carrier gas Ar or N
2, carry out thermal decomposition under 600～900 ℃ of conditions, finally obtain simple substance M and I
2The chemical equation of this reaction is as follows:
MI
2→M+I
2
In cooled simple substance M 50% turns back in step (4) as CO
2The recycling of the reducing agent of decomposition reaction, remaining 50% as H in step (7)
2The reducing agent recycling of O decomposition reaction; I
2Recycling as the Bunsen reaction unit that reactant turns back in step (1);
(7) under 390～600 ℃ of conditions, with H
2O steam is passed into H
2In the O decomposition reactor, the simple substance M generation exothermic reaction with on fixed bed or fluid bed obtains MO and end product H
2, the chemical equation of this reaction is as follows:
M+H
2O→H
2+MO
Wherein, MO turns back in step (5) and reuses as reactant.
The present invention further provides a kind of device be used to realizing preceding method, comprised the Bunsen reaction unit, it is characterized in that, also comprised: liquid phase separating device, HI
xConcentrated rectifier unit, H
2O decomposition reactor, H
2SO
4Enrichment facility, dense H
2SO
4Catalytic decomposition device, CO
2Decomposition reactor, MI
2Generate reactor and MI
2The cartalytic decomposition effect device; Described Bunsen reaction unit connecting fluid phase-separating device, liquid phase separating device connects respectively HI
xConcentrated rectifier unit and H
2SO
4Enrichment facility; H
2SO
4C enrichment facility, dense H
2SO
4Catalytic decomposition device, Bunsen reaction unit connect successively; HI
xConcentrated rectifier unit, H
2The O decomposition reactor connects respectively MI
2Generate reactor, MI
2Generate reactor respectively again with CO
2Decomposition reactor, MI
2The cartalytic decomposition effect device connects; MI
2The cartalytic decomposition effect device respectively again with Bunsen reaction unit, H
2O decomposition reactor and CO
2Decomposition reactor connects; Described M refers to metallic element Zn or Ni.
Easily find out from said process, overall reaction is: H
2O+CO
2→ H
2+ CO+O
2
Compared with prior art, the invention has the beneficial effects as follows:
1, the high source temperature of the sorts of systems such as two-step solar heat chemistry Zn/ZnO circulation all higher (＞1600 ℃), the general Salar light-gathering that adopts, and the high source temperature lower (＜900 ℃) of native system can adopt the thermal source of other various ways such as solar energy, nuclear energy;
2, the native system each several part all belongs to chemical-process, and reaction temperature is suitable, is easy to realize the large-scale industrial application.
Description of drawings
Fig. 1 is process chart of the present invention;
Reference numeral in figure is:
1 is that Bunsen reaction unit, 2 is that liquid phase separating device, 3 is H for HIx concentrates rectifier unit, 4
2O decomposition reactor, 5 is H
2SO
4Enrichment facility, 6 is dense H
2SO
4Catalytic decomposition device, 7 is CO
2Decomposition reactor, 8 is ZnI
2Generate reactor, 9 is ZnI
2The cartalytic decomposition effect device.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Be used for realizing that the equipment of the method for the invention comprises: Bunsen reaction unit 1, liquid phase separating device 2, the concentrated rectifier unit 3 of HIx, H
2O decomposition reactor 4, H
2SO
4Enrichment facility 5, dense H
2SO
4Catalytic decomposition device 6, CO
2Decomposition reactor 7, ZnI
2Generate reactor 8, ZnI
2Cartalytic decomposition effect device 9.Bunsen reaction unit 1 connecting fluid phase-separating device 2, liquid phase separating device 2 connect respectively the concentrated rectifier unit 3 of HIx and H
2SO
4Enrichment facility 5, H
2SO
4Enrichment facility 5, dense H
2SO
4Catalytic decomposition device 6, Bunsen reaction unit 1 connect successively, and the concentrated rectifier unit 3 of HIx connects ZnI
2Generate reactor 8, ZnI
2Generate reactor 8 respectively again with CO
2Decomposition reactor 7, H
2O decomposition reactor 4 and ZnI
2Generate reactor 8 is connected, ZnI
2Cartalytic decomposition effect device 9 respectively again with Bunsen reaction unit 1, H
2O decomposition reactor and CO
2Decomposition reactor 7 connects.
Specific embodiment 1:
(1) with 14molH
2O, 1.5molI
2And 1molSO
2Send into Bunsen reaction unit 1, by electric machine stirring reaction liquid at the uniform velocity, guarantee that it mixes, 20 ℃, autonomous exothermic reaction occurs during 1atm, produce the HI phase (HI of many water
x) and H
2SO
4Phase solution, wherein HI mainly comprises hydrogen iodide solution and excess iodine, H mutually
2SO
4Mainly comprise mutually H
2SO
4Solution, the chemical equation of this reaction is as follows:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in Bunsen reaction unit 1 are separated H in liquid phase separating device 2
2SO
4At H
2SO
4Enter dense H after concentrated in enrichment facility 5
2SO
4In catalytic decomposition device 6, first be decomposed into SO in the time of 350 ℃
3And H
2O, the SO of generation
3Carry out catalytic decomposition and generate SO under 800 ℃
2And O
2, end product O
2Follow SO
2And H
2O turns back to 1 separation of Bunsen reaction unit and obtains, and the chemical equation of this reaction is as follows:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn under 350 ℃, produces ZnO and end product CO, and wherein ZnO enters ZnI
2Generate reactor 8, its chemical equation is as follows:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in liquid phase separating device 2
xFurther concentrate, purify and separate in the concentrated rectifier unit 3 of HIx, whole HI steam enter ZnI
2Generate reactor 8 issues at 20 ℃ is conigenous the granting thermal response, the ZnI that wherein generates
2Send into ZnI
2Cartalytic decomposition effect device 9, its chemical equation is as follows respectively:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,600 ℃ of cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return to 1 recycling of Bunsen reaction unit, 50% Zn returns to CO
2Recycling in decomposition reactor 7,50% Zn returns to H
2Recycling in O decomposition reactor 4, its chemical equation is as follows:
ZnI
2→Zn+I
2
(6) in the time of 390 ℃, water vapour is passed into H
2In O decomposition reactor 4 and from H
2In O decomposition reactor 4, exothermic reaction occurs in 50% Zn, obtains ZnO and end product H
2, ZnO sends into ZnI
2Generate reactor 8 is as the reactant utilization, and the chemical equation of this reaction is as follows:
Zn+H
2O→H
2+ZnO。
Specific embodiment 2:
(1) with 15molH
2O, 5molI
2And 1molSO
2Send into Bunsen reaction unit 1, by electric machine stirring reaction liquid at the uniform velocity, guarantee that it mixes, 70 ℃, autonomous exothermic reaction occurs during 1.5atm, produce the HI phase (HI of many water
x) and H
2SO
4Phase solution, wherein HI mainly comprises hydrogen iodide solution and excess iodine, H mutually
2SO
4Mainly comprise mutually H
2SO
4Solution, the chemical equation of this reaction is as follows:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in Bunsen reaction unit 1 are separated H in liquid phase separating device 2
2SO
4At H
2SO
4Enter dense H after concentrated in enrichment facility 5
2SO
4In catalytic decomposition device 6, first be decomposed into SO in the time of 350 ℃
3And H
2O, the SO of generation
3Carry out catalytic decomposition and generate SO under 850 ℃
2And O
2, end product O
2Follow SO
2And H
2O turns back to 1 separation of Bunsen reaction unit and obtains, and the chemical equation of this reaction is as follows:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn under 600 ℃, produces ZnO and end product CO, and wherein ZnO enters ZnI
2Generate reactor 8, its chemical equation is as follows:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in liquid phase separating device 2
xFurther concentrate, purify and separate in the concentrated rectifier unit 3 of HIx, whole HI steam enter ZnI
2Generate reactor 8 issues at 6O ℃ is conigenous the granting thermal response, the ZnI that wherein generates
2Send into ZnI
2Cartalytic decomposition effect device 9, its chemical equation is as follows respectively:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,750 ℃ of cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return to 1 recycling of Bunsen reaction unit, 50% Zn returns to CO
2Recycling in decomposition reactor 7,50% Zn returns to H
2Recycling in O decomposition reactor 4, its chemical equation is as follows:
ZnI
2→Zn+I
2
(6) in the time of 500 ℃, water vapour is passed into H
2In O decomposition reactor 4 and from H
2In O decomposition reactor 4, exothermic reaction occurs in 50% Zn, obtains ZnO and end product H
2, ZnO sends into ZnI
2Generate reactor 8 is as the reactant utilization, and the chemical equation of this reaction is as follows:
Zn+H
2O→H
2+ZnO。
Specific embodiment 3:
(1) with 16molH
2O, 9molI
2And 1molSO
2Send into Bunsen reaction unit 1, by electric machine stirring reaction liquid at the uniform velocity, guarantee that it mixes, 120 ℃, autonomous exothermic reaction occurs during 2atm, produce the HI phase (HI of many water
x) and H
2SO
4Phase solution, wherein HI mainly comprises hydrogen iodide solution and excess iodine, H mutually
2SO
4Mainly comprise mutually H
2SO
4Solution, the chemical equation of this reaction is as follows:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in Bunsen reaction unit 1 are separated H in liquid phase separating device 2
2SO
4At H
2SO
4Enter dense H after concentrated in enrichment facility 5
2SO
4In catalytic decomposition device 6, first be decomposed into SO in the time of 350 ℃
3And H
2O, the SO of generation
3Carry out catalytic decomposition and generate SO under 900 ℃
2And O
2, end product O
2Follow SO
2And H
2O turns back to 1 separation of Bunsen reaction unit and obtains, and the chemical equation of this reaction is as follows:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn under 900 ℃, produces ZnO and end product CO, and wherein ZnO enters ZnI
2Generate reactor 8, its chemical equation is as follows:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in liquid phase separating device 2
xFurther concentrate, purify and separate in the concentrated rectifier unit 3 of HIx, whole HI steam enter ZnI
2Generate reactor 8 issues at 90 ℃ is conigenous the granting thermal response, the ZnI that wherein generates
2Send into ZnI
2Cartalytic decomposition effect device 9, its chemical equation is as follows respectively:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,900 ℃ of cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return to 1 recycling of Bunsen reaction unit, 50% Zn returns to CO
2Recycling in decomposition reactor 7,50% Zn returns to H
2Recycling in O decomposition reactor 4, its chemical equation is as follows:
ZnI
2→Zn+I
2
(6) in the time of 600 ℃, water vapour is passed into H
2In O decomposition reactor 4 and from H
2In O decomposition reactor 4, exothermic reaction occurs in 50% Zn, obtains ZnO and end product H
2, ZnO sends into ZnI
2Generate reactor 8 is as the reactant utilization, and the chemical equation of this reaction is as follows:
Zn+H
2O→H
2+ZnO。
Specific embodiment 4:
Change the metallic element Zn in specific embodiment 3 into Ni, other all Step By Conditions are all constant.
At last, it is also to be noted that, what more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.The present invention can summarize with other the concrete form without prejudice to spirit of the present invention and principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only be thought can not limit the present invention to explanation of the present invention.Claims have been pointed out scope of the present invention, and scope of the present invention is not pointed out in above-mentioned explanation, therefore, in the implication suitable with claims of the present invention and any change in scope, all should think to be included in the scope of claims.
Claims (2)
1. a thermochemical cycles reaction system is decomposed CO
2And H
2The method of O, its total chemical equation is H
2O+CO
2→ H
2+ CO+O
2, it is characterized in that, specifically comprise the following steps:
(1) with H
2O, I
2And SO
2In amount of substance ratio 14～16: 1.5～9: 1 sends into the Bunsen reaction unit, and at the uniform velocity stirring reaction liquid guarantees that it mixes, and issues 20～120 ℃ and 1～2atm condition and is conigenous the granting thermal response, produces HI phase and the H of many water
2SO
4Phase solution, the chemical equation of this reaction is as follows:
I
2+SO
2+2H
2O→2HI+H
2SO
4
In reaction, excessive iodine has been guaranteed the mixed solution generation liquid-liquid phase separation that the Bunsen reaction generates, HI phase and the H of lower leaf in formation
2SO
4Phase solution;
(2) under 120～260 ℃, 0.08～1.3atm and adiabatic condition, to H
2SO
4Phase solution is implemented multistage sulphuric acid concentration and is processed;
(3) H after concentrating
2SO
4Be warming up to 800～900 ℃, catalytic decomposition generates SO
2, H
2O and end product O
2, the chemical equation of this reaction is as follows:
H
2SO
4→SO
2+H
2O+0.5O
2
SO
2, H
2O and end product O
2Turn back to the recycling of Bunsen reaction unit;
(4) under 350～900 ℃, pass into CO
2Gas generates oxide M O and end product CO to fixed bed or fluidized-bed reactor and metal M generation exothermic reaction, and the chemical equation of this reaction is as follows:
M+CO
2→MO+CO
Described M is metallic element Zn or Ni;
(5) carry out electrodialysis process for step (1) gained HI phase solution, obtain concentrated HI solution at the electrodialytic cell cathode side, the dilution HI solution that anode-side obtains turns back to the recycling of Bunsen reaction unit; HI solution after concentrated carries out rectifying in concentrated rectifier unit, obtain pure HI steam; Spontaneous exothermic reaction generation MI is occured in gained HI steam and metal oxide MO in the aqueous solution of 20～90 ℃
2And H
2O, the chemical equation of this reaction is as follows:
2HI+MO→MI
2+H
2O
(6) obtain MI by distillation
2Solid is placed in fixed bed or fluidized-bed reactor, passes into carrier gas Ar or N
2, carry out thermal decomposition under 600～900 ℃ of conditions, finally obtain simple substance M and I
2The chemical equation of this reaction is as follows:
MI
2→M+I
2
In cooled simple substance M 50% turns back in step (4) as CO
2The recycling of the reducing agent of decomposition reaction, remaining 50% as H in step (7)
2The reducing agent recycling of O decomposition reaction; I
2Recycling as the Bunsen reaction unit that reactant turns back in step (1);
(7) under 390～600 ℃ of conditions, with H
2O steam is passed into H
2In the O decomposition reactor, the simple substance M generation exothermic reaction with on fixed bed or fluid bed obtains MO and end product H
2, the chemical equation of this reaction is as follows:
M+H
2O→H
2+MO
Wherein, MO turns back in step (5) and reuses as reactant.
2. a device that is used for realizing the described method of claim 1, comprise the Bunsen reaction unit, it is characterized in that, also comprises: liquid phase separating device, HI
xConcentrated rectifier unit, H
2O decomposition reactor, H
2SO
4Enrichment facility, dense H
2SO
4Catalytic decomposition device, CO
2Decomposition reactor, MI
2Generate reactor and MI
2The cartalytic decomposition effect device; Described Bunsen reaction unit connecting fluid phase-separating device, liquid phase separating device connects respectively HI
xConcentrated rectifier unit and H
2SO
4Enrichment facility; H
2SO
4Enrichment facility, dense H
2SO
4Catalytic decomposition device, Bunsen reaction unit connect successively; HI
xConcentrated rectifier unit, H
2The O decomposition reactor connects respectively MI
2Generate reactor, MI
2Generate reactor respectively again with CO
2Decomposition reactor, MI
2The cartalytic decomposition effect device connects; MI
2The cartalytic decomposition effect device respectively again with Bunsen reaction unit, H
2O decomposition reactor and CO
2Decomposition reactor connects; Described M refers to metallic element Zn or Ni.
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| CN103614119B (en) * | 2013-11-07 | 2016-05-11 | 昆明理工大学 | A kind of preparation method of Zn/ZnO parcel property heat-storing material |
| CN104193584A (en) * | 2014-08-04 | 2014-12-10 | 广东合即得能源科技有限公司 | Manufacturing process of methanol |
| CN106242946B (en) * | 2016-09-08 | 2019-07-05 | 广东合即得能源科技有限公司 | A kind of equipment and technique of solar hydrogen making synthesizing methanol |
| CN108456547A (en) * | 2018-01-26 | 2018-08-28 | 中国科学院上海高等研究院 | Utilize the system and method for solar energy high temperature thermal coupling methane production fuel chemicals |
| CN108715438B (en) * | 2018-05-29 | 2020-05-12 | 浙江大学 | Method and device for thermochemically circulating and mineralizing CO2 and simultaneously decomposing H2O to prepare H2 and coproducing H2SO4 |
| CN114634160B (en) * | 2022-05-18 | 2022-08-23 | 浙江百能科技有限公司 | Full-flow method and device for thermochemical zinc-sulfur-iodine cycle coupling methane hydrogen production |
| CN115321479B (en) * | 2022-10-11 | 2022-12-27 | 浙江百能科技有限公司 | Method and device for producing hydrogen and co-producing sulfuric acid by thermochemical zinc-sulfur-iodine cycle decomposition of water |
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