CN102553407A - 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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- CN102553407A CN102553407A CN2012100111772A CN201210011177A CN102553407A CN 102553407 A CN102553407 A CN 102553407A CN 2012100111772 A CN2012100111772 A CN 2012100111772A CN 201210011177 A CN201210011177 A CN 201210011177A CN 102553407 A CN102553407 A CN 102553407A
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Abstract
The invention relates to CO2Emission reduction technology, aiming at providing a thermochemical cycle reaction system for decomposing CO2And 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 the new method and the technological process of carbon dioxide and water.
Background technology
At present, CO
2Emission problem more and more receives everybody attention, how effectively to reduce CO
2Discharging has become the important political economy subject under discussion in countries in the world.States such as the U.S., Britain and Germany have have all studied and defined CO
2The discharging system, Japan has then 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
2The measure that reduction of discharging can be taked is to reduce discharging and the control increment on the one hand: comprise and readjusting the energy structure; Use the low-carbon (LC) energy; Greatly develop clean energy resourcies such as nuclear energy, Hydrogen Energy, wind energy; Improve utilization efficiency of energy, development power-saving technology and the consumption habit that changes the mankind reduce the use of fossil fuel as far as possible.Then be to strengthen CO on the other hand
2Disposal and utilization, this comprises and captures and seal technology up for safekeeping, carries out oil-gas mining, little algae utilizes and chemical utilization etc.At CO
2Utilize the aspect, though economy and risk assessment show CO
2The organic chemical industry to utilize be an aspect that is worth greatly developing, but because CO
2Be a torpescence molecule, chemical property is stable, needs to adopt high temperature, high pressure or uses catalyst just can make its reaction.Generally speaking, CO
2The conversion ratio of catalytic hydrogenation reaction and yield are all not too high, apply with also being difficult to economic scale at present.And thermochemical cycles is decomposed and utilize CO
2System had obtained many scientific research persons' concern and research in the last few years because its unique advantages is arranged, and wherein, was one of main research direction based on metal-oxide to redox thermochemical cycles decomposition carbon dioxide and water system.
Based on metal-oxide the circulation of redox Thermochemical Decomposition carbon dioxide and water is made up of two steps usually: the first step is that metal oxide at high temperature decomposes and produces oxygen with metal simple-substance or hang down valent metal oxide; Second step be metal simple-substance or low valent metal oxide at a lower temperature hydrolytic reactions produce hydrogen or the carbon dioxide decomposition reaction take place and produce carbon monoxide.Whole process can be represented 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, needs very high reaction temperature (＞1600 ℃) usually, therefore must adopt the Salar light-gathering high temperature heat source to drive reaction and carry out.Reaction of second one-step hydrolysis and carbon dioxide decomposition reaction are the processes of heat release, and its reaction temperature is relatively low.When the M of reaction in (1) is Fe, Zn or Ce element, can obtain relatively more rational reaction rate, 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 the maximum system of studying 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 0=0 o'clock temperature is 2058 ℃, and its product is zinc fume and oxygen, finally need separate perhaps quenching to prevent the combination again of product.Second step: the CO
2And H
2The decomposition reaction of O, according to kinetics, the reaction of formula (2) and (3) must surpass zinc fusing point (419 ℃ are carried out under temperature 1atm).Yet, when the zinc that melts and water vapour or carbon dioxide reaction, can form layer of ZnO (cr) and float on the 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.Discover that the productivity ratio of Zn depends on the dynamic process of decomposition reaction largely and gaseous products is carried out the technical feasibility of enough fast quenching to prevent that it from combining again.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) through solar energy Zn/ZnO circulation hydrogen generating system is carried out available energy and economic analysis; Declare that this system is under the situation that does 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 the Zn (g) and the O of solar energy reactor
2Quenching loss (26%).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) decompose CO through solar energy Zn/ZnO is circulated
2And H
2The O system carries out thermodynamic analysis, and this system is under the situation that does not reclaim heat, and the highest theoretical thermal efficiency is 27%～31%.
People such as William (document High-Flux Solar-Driven Thermochemical Dissociation of CO
2And H
2Using Nonstoichiometric Ceria.Science, 2010,330 (6012): 1797-1801) through solar energy CeO
2/ Ce
2O
3CO is decomposed in circulation
2And H
2The O system carries out thermodynamic analysis, declares this system under the situation that does not reclaim any heat, and the highest theoretical thermal efficiency can reach 16～19%.
Summary of the invention
The technical problem that the present invention will solve is, overcomes the deficiency of 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 may further comprise the 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, and the HI that produces many water mutually and H
2SO
4Phase solution, the chemical equation of this reaction is following:
I
2+SO
2+2H
2O→2HI+H
2SO
4
Excessive iodine has been guaranteed the mixed solution generation liquid-liquid phase separation that the Bunsen reaction generates in the reaction, the HI of lower leaf phase and H in the 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 handled;
(3) H after will 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 following:
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 ℃, feed CO
2Gas to fixed bed or fluidized-bed reactor and metal M generation exothermic reaction generate oxide M O and end product CO, and the chemical equation of this reaction is following:
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 concentrating carries out rectifying in concentrating rectifier unit, obtain pure HI steam; Spontaneous exothermic reaction generation MI is taken place in gained HI steam and metal oxide MO in 20～90 ℃ the aqueous solution
2And H
2O, the chemical equation of this reaction is following:
2HI+MO→MI
2+H
2O
(6) obtain MI through distillation
2Solid is placed in fixed bed or the fluidized-bed reactor, feeds carrier gas Ar or N
2, under 600～900 ℃ of conditions, carry out thermal decomposition, finally obtain simple substance M and I
2The chemical equation of this reaction is following:
MI
2→M+I
2
Among the cooled simple substance M 50% turns back in the step (4) as CO
2The recycling of the reducing agent of decomposition reaction, remaining 50% as H in the step (7)
2The reducing agent recycling of O decomposition reaction; I
2Turn back to the Bunsen reaction unit recycle in the step (1) as reactant;
(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 the fluid bed obtains MO and end product H
2, the chemical equation of this reaction is following:
M+H
2O→H
2+MO
Wherein, MO turns back in the step (5) and reuses as reactant.
The present invention further provides a kind of device that is used to realize preceding method, comprises the Bunsen reaction unit, it is characterized in that, also comprises: liquid phase separation device, HI
xConcentrate 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; Said Bunsen reaction unit connects the liquid phase separation device, and the liquid phase separation device connects HI respectively
xConcentrate rectifier unit and H
2SO
4Enrichment facility; H
2SO
4C enrichment facility, dense H
2SO
4Catalytic decomposition device, Bunsen reaction unit connect successively; HI
xConcentrate rectifier unit, H
2The O decomposition reactor connects MI respectively
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 is meant metallic element Zn or Ni.
Find out easily that 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 all higher (＞1600 ℃) of sorts of systems such as two-step solar heat chemistry Zn/ZnO circulation; 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 a process chart of the present invention;
Reference numeral among the figure is:
1 is that Bunsen reaction unit, 2 is that liquid phase separation 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 accompanying drawing and specific embodiment the present invention is described in further detail.
Be used to realize that the equipment of the method for the invention comprises: Bunsen reaction unit 1, liquid phase separation device 2, HIx concentrate rectifier unit 3, H
2 O decomposition reactor 4, H
2SO
4Enrichment facility 5, dense H
2SO
4 Catalytic decomposition device 6, CO
2Decomposition reactor 7, ZnI
2 Generate reactor 8, ZnI
2Cartalytic decomposition effect device 9.Bunsen reaction unit 1 connects liquid phase separation device 2, and liquid phase separation device 2 connects HIx respectively and concentrates rectifier unit 3 and H
2SO
4Enrichment facility 5, H
2SO
4Enrichment facility 5, dense H
2SO
4 Catalytic decomposition device 6, Bunsen reaction unit 1 connect successively, and HIx concentrates rectifier unit 3 and connects ZnI
2Generate reactor 8, ZnI
2Generate reactor 8 respectively again with CO
2Decomposition reactor 7, H
2 O decomposition reactor 4 and ZnI
2 Generate 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,, guarantee that it mixes through electric machine stirring reaction liquid at the uniform velocity, 20 ℃, autonomous exothermic reaction takes place 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 H mutually
2SO
4Solution, the chemical equation of this reaction is following:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in the Bunsen reaction unit 1 are separated H in liquid phase separation device 2
2SO
4At H
2SO
4Concentrate the back in the enrichment facility 5 and get into dense H
2SO
4In the catalytic decomposition device 6, in the time of 350 ℃, be decomposed into SO earlier
3And H
2O, the SO of generation
3Under 800 ℃, carry out catalytic decomposition and generate SO
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 following:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn down at 350 ℃, produces ZnO and end product CO, wherein ZnO entering ZnI
2Generate reactor 8, its chemical equation is following:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in the liquid phase separation device 2
xIn the concentrated rectifier unit 3 of HIx, further concentrate, purify and separate, whole HI steam gets into ZnI
2 Generate 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 distinguished as follows:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,600 ℃ of the cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return 1 recycling of Bunsen reaction unit, 50% Zn returns CO
2Recycling in the decomposition reactor 7,50% Zn returns H
2Recycling in the O decomposition reactor 4, its chemical equation is following:
ZnI
2→Zn+I
2
(6) in the time of 390 ℃, water vapour is passed into H
2In the O decomposition reactor 4 and from H
2Exothermic reaction takes place in 50% Zn in the O decomposition reactor 4, obtains ZnO and end product H
2, ZnO sends into ZnI
2 Generate reactor 8 is as the reactant utilization, and the chemical equation of this reaction is following:
Zn+H
2O→H
2+ZnO。
Specific embodiment 2:
(1) with 15molH
2O, 5molI
2And 1molSO
2Send into Bunsen reaction unit 1,, guarantee that it mixes through electric machine stirring reaction liquid at the uniform velocity, 70 ℃, autonomous exothermic reaction takes place 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 H mutually
2SO
4Solution, the chemical equation of this reaction is following:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in the Bunsen reaction unit 1 are separated H in liquid phase separation device 2
2SO
4At H
2SO
4Concentrate the back in the enrichment facility 5 and get into dense H
2SO
4In the catalytic decomposition device 6, in the time of 350 ℃, be decomposed into SO earlier
3And H
2O, the SO of generation
3Under 850 ℃, carry out catalytic decomposition and generate SO
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 following:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn down at 600 ℃, produces ZnO and end product CO, wherein ZnO entering ZnI
2Generate reactor 8, its chemical equation is following:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in the liquid phase separation device 2
xIn the concentrated rectifier unit 3 of HIx, further concentrate, purify and separate, whole HI steam gets into 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 distinguished as follows:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,750 ℃ of the cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return 1 recycling of Bunsen reaction unit, 50% Zn returns CO
2Recycling in the decomposition reactor 7,50% Zn returns H
2Recycling in the O decomposition reactor 4, its chemical equation is following:
ZnI
2→Zn+I
2
(6) in the time of 500 ℃, water vapour is passed into H
2In the O decomposition reactor 4 and from H
2Exothermic reaction takes place in 50% Zn in the O decomposition reactor 4, 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 following:
Zn+H
2O→H
2+ZnO。
Specific embodiment 3:
(1) with 16molH
2O, 9molI
2And 1molSO
2Send into Bunsen reaction unit 1,, guarantee that it mixes through electric machine stirring reaction liquid at the uniform velocity, 120 ℃, autonomous exothermic reaction takes place 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 H mutually
2SO
4Solution, the chemical equation of this reaction is following:
I
2+SO
2+2H
2O→2HI+H
2SO
4
(2) two solution in the Bunsen reaction unit 1 are separated H in liquid phase separation device 2
2SO
4At H
2SO
4Concentrate the back in the enrichment facility 5 and get into dense H
2SO
4In the catalytic decomposition device 6, in the time of 350 ℃, be decomposed into SO earlier
3And H
2O, the SO of generation
3Under 900 ℃, carry out catalytic decomposition and generate SO
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 following:
H
2SO
4→SO
2+H
2O+0.5O
2
(3) simultaneously, with CO
2Send into CO
2Decomposition reactor 7 reacts with Zn down at 900 ℃, produces ZnO and end product CO, wherein ZnO entering ZnI
2Generate reactor 8, its chemical equation is following:
Zn+CO
2→ZnO+CO
(4) separating obtained HI in the liquid phase separation device 2
xIn the concentrated rectifier unit 3 of HIx, further concentrate, purify and separate, whole HI steam gets into 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 distinguished as follows:
2HI+ZnO→ZnI
2+H
2O
(5) ZnI that generates
2Send into ZnI
2Carry out cartalytic decomposition effect under 9,900 ℃ of the cartalytic decomposition effect devices, wherein the I of the generation of reaction
2All return 1 recycling of Bunsen reaction unit, 50% Zn returns CO
2Recycling in the decomposition reactor 7,50% Zn returns H
2Recycling in the O decomposition reactor 4, its chemical equation is following:
ZnI
2→Zn+I
2
(6) in the time of 600 ℃, water vapour is passed into H
2In the O decomposition reactor 4 and from H
2Exothermic reaction takes place in 50% Zn in the O decomposition reactor 4, 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 following:
Zn+H
2O→H
2+ZnO。
Specific embodiment 4:
Change the metallic element Zn in the 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 only is specific embodiment of the present 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 implication suitable with claims of the present invention and any change in the 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 may further comprise the 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, and the HI that produces many water mutually and H
2SO
4Phase solution, the chemical equation of this reaction is following:
I
2+SO
2+2H
2O→2HI+H
2SO
4
Excessive iodine has been guaranteed the mixed solution generation liquid-liquid phase separation that the Bunsen reaction generates in the reaction, the HI of lower leaf phase and H in the 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 handled;
(3) H after will 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 following:
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 ℃, feed CO
2Gas to fixed bed or fluidized-bed reactor and metal M generation exothermic reaction generate oxide M O and end product CO, and the chemical equation of this reaction is following:
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 concentrating carries out rectifying in concentrating rectifier unit, obtain pure HI steam; Spontaneous exothermic reaction generation MI is taken place in gained HI steam and metal oxide MO in 20～90 ℃ the aqueous solution
2And H
2O, the chemical equation of this reaction is following:
2HI+MO→MI
2+H
2O
(6) obtain MI through distillation
2Solid is placed in fixed bed or the fluidized-bed reactor, feeds carrier gas Ar or N
2, under 600～900 ℃ of conditions, carry out thermal decomposition, finally obtain simple substance M and I
2The chemical equation of this reaction is following:
MI
2→M+I
2
Among the cooled simple substance M 50% turns back in the step (4) as CO
2The recycling of the reducing agent of decomposition reaction, remaining 50% as H in the step (7)
2The reducing agent recycling of O decomposition reaction; I
2Turn back to the Bunsen reaction unit recycle in the step (1) as reactant;
(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 the fluid bed obtains MO and end product H
2, the chemical equation of this reaction is following:
M+H
2O→H
2+MO
Wherein, MO turns back in the step (5) and reuses as reactant.
2. a device that is used to realize the said method of claim 1 comprises the Bunsen reaction unit, it is characterized in that, also comprises: liquid phase separation device, HI
xConcentrate 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; Said Bunsen reaction unit connects the liquid phase separation device, and the liquid phase separation device connects HI respectively
xConcentrate rectifier unit and H
2SO
4Enrichment facility; H
2SO
4Enrichment facility, dense H
2SO
4Catalytic decomposition device, Bunsen reaction unit connect successively; HI
xConcentrate rectifier unit, H
2The O decomposition reactor connects MI respectively
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 is meant metallic element Zn or Ni.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100111772A CN102553407B (en) | 2012-01-15 | 2012-01-15 | Thermochemical cycle reaction system for decomposing CO2And H2O method and device |
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|---|---|---|---|
| CN2012100111772A CN102553407B (en) | 2012-01-15 | 2012-01-15 | Thermochemical cycle reaction system for decomposing CO2And H2O method and device |
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| Publication Number | Publication Date |
|---|---|
| CN102553407A true CN102553407A (en) | 2012-07-11 |
| CN102553407B CN102553407B (en) | 2013-11-06 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614119A (en) * | 2013-11-07 | 2014-03-05 | 昆明理工大学 | Preparation method of Zn/ZnO encapsulated heat storage 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 |
| CN105531222A (en) * | 2013-08-02 | 2016-04-27 | 米兰理工大学 | Syngas production by CO2 reduction process |
| CN106242946A (en) * | 2016-09-08 | 2016-12-21 | 广东合即得能源科技有限公司 | The equipment of a kind of solar hydrogen making synthesizing methanol and technique |
| 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 |
| CN108715438A (en) * | 2018-05-29 | 2018-10-30 | 浙江大学 | The method and device of thermochemical cycles mineralising CO2 while decomposing H 2O H2 coproduction H2SO4 |
| CN114634160A (en) * | 2022-05-18 | 2022-06-17 | 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 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020064494A1 (en) * | 1999-05-13 | 2002-05-30 | Yongxian Zeng | Production of hydrogen and carbon monoxide |
| US20050000825A1 (en) * | 2003-07-04 | 2005-01-06 | Japan Atomic Energy Research Institute | Process for efficient hydrogen production by thermochemical water splitting using iodine and sulfur dioxide |
| CN1785796A (en) * | 2005-10-14 | 2006-06-14 | 浙江大学 | Technical method of sulfur iodine open circuit circulation hydrogen manufacture and its equipment |
| CN101857204A (en) * | 2010-06-18 | 2010-10-13 | 清华大学 | Process and device for purifying sulfuric acid phase in iodine and sulfur cycle under low pressure |
-
2012
- 2012-01-15 CN CN2012100111772A patent/CN102553407B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020064494A1 (en) * | 1999-05-13 | 2002-05-30 | Yongxian Zeng | Production of hydrogen and carbon monoxide |
| US20050000825A1 (en) * | 2003-07-04 | 2005-01-06 | Japan Atomic Energy Research Institute | Process for efficient hydrogen production by thermochemical water splitting using iodine and sulfur dioxide |
| CN1785796A (en) * | 2005-10-14 | 2006-06-14 | 浙江大学 | Technical method of sulfur iodine open circuit circulation hydrogen manufacture and its equipment |
| CN101857204A (en) * | 2010-06-18 | 2010-10-13 | 清华大学 | Process and device for purifying sulfuric acid phase in iodine and sulfur cycle under low pressure |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105531222A (en) * | 2013-08-02 | 2016-04-27 | 米兰理工大学 | Syngas production by CO2 reduction process |
| CN105531222B (en) * | 2013-08-02 | 2018-11-06 | 米兰理工大学 | Pass through CO2The synthesis gas of reduction method produces |
| CN103614119A (en) * | 2013-11-07 | 2014-03-05 | 昆明理工大学 | Preparation method of Zn/ZnO encapsulated heat storage material |
| 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 |
| CN106242946A (en) * | 2016-09-08 | 2016-12-21 | 广东合即得能源科技有限公司 | The equipment of a kind of solar hydrogen making synthesizing methanol and technique |
| 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 |
| CN108715438A (en) * | 2018-05-29 | 2018-10-30 | 浙江大学 | The method and device of thermochemical cycles mineralising CO2 while decomposing H 2O H2 coproduction H2SO4 |
| 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 |
| CN114634160A (en) * | 2022-05-18 | 2022-06-17 | 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 |
| CN115321479A (en) * | 2022-10-11 | 2022-11-11 | 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 |
| 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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