CN108821315B - Thermochemical cycle mineralization of CO2Simultaneous decomposition of H2O system H2Method and apparatus - Google Patents

Thermochemical cycle mineralization of CO2Simultaneous decomposition of H2O system H2Method and apparatus Download PDF

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CN108821315B
CN108821315B CN201810533583.2A CN201810533583A CN108821315B CN 108821315 B CN108821315 B CN 108821315B CN 201810533583 A CN201810533583 A CN 201810533583A CN 108821315 B CN108821315 B CN 108821315B
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CN108821315A (en
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张彦威
王智化
周志军
刘建忠
周俊虎
黄镇宇
杨卫娟
程军
倪明江
岑可法
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Zhejiang University ZJU
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention relates to CO2The field of emission reduction and thermochemistry hydrogen production, and aims to provide thermochemistry cycle mineralization CO2Simultaneous decomposition of H2O system H2Methods and apparatus of (1). The device comprises a Bunsen reaction device, a liquid phase separation device and a HIxConcentration apparatus, H2SO4Concentration device, concentrated H2SO4Catalytic decomposition device, MgI2Production reactor, MgI2Distillation apparatus, MgI2A hydrolysis carbonation reactor and a HI catalytic decomposition reactor. The invention innovatively combines CO2The mineralization technology is organically combined with the thermochemical sulfur-iodine open-loop circulating water decomposition for hydrogen production, and CO is mineralized and fixed under mild reaction conditions2And simultaneously co-producing H with high added value2(ii) a The hydrogen production cycle is organically combined with the mineralization technology, thereby skillfully avoiding HI-I in the traditional hydrogen production cycle2In the rectification separation process, the cycle has higher theoretical thermal efficiency; all parts belong to chemical processes, the reaction temperature is appropriate, and the large-scale industrial application is easy to realize.

Description

Thermochemical cycle mineralization of CO2Simultaneous decomposition of H2O system H2Method and apparatus
Technical Field
The invention belongs to CO2The field of emission reduction and thermochemical hydrogen production, in particular to thermochemical cycle mineralization of CO2Simultaneous decomposition of H2O system H2The method and the process flow of (1).
Background
Artificial greenhouse gases since the industrial revolutionDischarging CO already in the atmosphere2The concentration rises sharply, and CO2The large-scale emission of dominant greenhouse gases is a major cause of global warming. Global warming presents a hazard to humans and the entire global environmental system, CO2The significance of emission reduction work is great.
At present, CO2The capture and sequestration (CCS) technology of (a) is a major terminal emission reduction strategy, and has been widely studied. However, the current CCS technology suffers from economic problems in its commercial application due to its high cost and energy consumption. And, CO2Geological sequestration may also present a series of risks, such as gas leaks, groundwater contamination, even induction of geological disasters, and the like. CO 22Mineralization utilization technology in CO emission reduction2Meanwhile, the method can often produce products with certain additional value, has stable carbon fixation effect and relatively low cost and energy input, and is expected to be developed into CO for future large-scale application2The control utilizes techniques. CO 22The raw materials in the mineralization utilization technology are sources for providing alkaline earth metal cations required by mineralization reaction, and the abundance degree of the raw materials fundamentally determines the upper limit of the mineralization capacity. Alkaline earth metal minerals mainly comprising magnesium silicate minerals in nature, such as serpentine and olivine, have the equivalent ability to mineralize 36,000Gt CO2The ability of the cell to perform. A future that can be implemented on a large scale. CO 22The mineralization must be based on alkaline earth minerals, i.e. calcium magnesium silicates. On the other hand, CO2The main product of the mineralization technology is calcium magnesium carbonate, the economy and the added value of which are low, which is also an important factor restricting the commercial application of the calcium magnesium carbonate. If a term of CO2The mineralization technology has byproducts with high added value and economy, or can be organically combined with other energy technologies with higher economy, and is more active.
Thermochemical iodosulfuration cycle is proposed by GA corporation in the united states as a more ideal hydrogen production cycle, and a great deal of research has been conducted worldwide. In which the Bunsen reaction is exothermic SO2Gas absorption reaction, which is carried out spontaneously in liquid phase at 20-100 ℃ to generate polyhydrated HI and H2SO4. In thatCO2In mineralization techniques, it is often necessary to subject the natural ore to an acid leaching process to extract the alkaline earth metal cations therefrom. Thus, the HI produced in the iodine-sulfur cycle Bunsen reaction can be used for ore processing for mineralization techniques, and the hydrogen production cycle can be combined with CO2The mineralization is organically combined.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and provides thermochemical cycle mineralization CO2Simultaneous decomposition of H2O system H2Methods and apparatus of (1).
For achieving the purpose of the invention, the invention provides a thermochemical cycle mineralization CO2Simultaneous decomposition of H2O system H2The method comprises the following steps:
(1) mixing H with the amount of the substance of 14-16: 1.5-9: 12O、I2And SO2Feeding the mixture into a Bunsen reaction device, stirring the reaction solution at a constant speed to ensure uniform mixing, and carrying out spontaneous exothermic reaction at 20-120 ℃ and 1-2 atm to generate a water-containing HI phase and H2SO4Phase solution; the chemical reaction formula of the reaction is as follows:
I2+SO2+2H2O→2HI+H2SO4
excessive iodine in the reaction ensures that the mixed solution generated by the Bunsen reaction is subjected to liquid-liquid phase separation to form an HI phase (lower layer) and H which are layered up and down2SO4Phase solution (upper layer);
(2) under the conditions of 120-260 ℃, 0.08-1.3 atm and heat insulation, the separated H is treated2SO4Carrying out multi-stage sulfuric acid concentration treatment on the phase solution;
(3) concentrating the concentrated H2SO4Raising the temperature to 800-900 ℃, and generating SO by catalytic decomposition2、H2O and the final product O2The chemical reaction formula of the reaction is as follows:
H2SO4→SO2+H2O+0.5O2
SO2、H2o and O2Returning to the Bunsen reaction apparatus, whichIn SO2And H2Recycling of O, O2Discharged as a final product;
(4) subjecting the HI phase solution obtained in step (1) to electrodialysis treatment to obtain concentrated HI solution at cathode side of electrodialysis cell and I at anode side2And diluting the HI solution and returning the HI solution to the Bunsen reaction device for recycling;
(5) the concentrated HI solution and magnesium silicate natural mineral are subjected to spontaneous exothermic reaction, the reaction temperature is controlled to be 20-90 ℃, and MgI generated by the reaction is generated2、H2O and SiO2With I entrained in the concentrated HI solution of step (4)2The components are mixed to form a mixed solution;
(6) filtering and washing the mixed solution in the step (5) to obtain a by-product SiO2Distilling the filtrate to obtain MgI2·nH2O crystals and isolated I2In which I2Returning to the Bunsen reaction device in the step (1) for recycling;
(7) MgI2·nH2Placing the O crystal in a fixed bed or a fluidized bed reactor, and introducing CO in any proportion2、N2Carrying out hydrolysis and carbonation reaction with water vapor, controlling the reaction temperature at 180-350 ℃, and finally obtaining HI steam and a MgCO product3(ii) a The chemical reaction formula of the reaction is as follows:
MgI2+H2O+CO2→MgCO3+2HI
(8) introducing the generated HI steam into an HI catalytic decomposition reactor for thermal decomposition, controlling the reaction temperature at 300-500 ℃ to finally obtain I2And product H2The chemical reaction formula of the reaction is as follows:
2HI→I2+H2
wherein I2And (4) returning the Bunsen reaction device in the step (1) for recycling.
In the present invention, the magnesium silicate natural mineral is serpentine or olivine.
The invention further provides thermochemical cycle mineralization of CO for implementing the aforementioned process2Simultaneous decomposition of H2O system H2Comprising the Bunsen reactionApparatus, liquid phase separation apparatus, HIxConcentration apparatus, H2SO4Concentration device, concentrated H2SO4Catalytic decomposition device, MgI2Production reactor, MgI2Distillation apparatus, MgI2A hydrolysis carbonation reactor and a HI catalytic decomposition reactor;
the Bunsen reaction device is connected with a liquid phase separation device, and the liquid phase separation device is respectively connected with HIxConcentration device and H2SO4Concentration apparatus, H2SO4Concentration device, concentrated H2SO4The catalytic decomposition device and the Bunsen reaction device are connected in sequence, HIxThe concentration device is respectively connected with the Bunsen reaction device and the MgI2Formation reactor, MgI2Production reactor connection MgI2Distillation apparatus, MgI2The distillation device is respectively connected with the Bunsen reaction device and the MgI2Hydrolysis carbonation reactor, MgI2The hydrolysis carbonating reactor is connected with the HI catalytic decomposition reactor, and the HI catalytic decomposition reactor is connected with the Bunsen reaction device.
In the invention, spontaneous exothermic reaction occurs in the Bunsen reaction device to generate a polyhydrated HI phase and H2SO4A phase solution, wherein the HI phase mainly comprises hydrogen iodide solution and excess iodine, H2SO4The phase comprises predominantly a sulfuric acid solution; concentrated H2SO4Decompose to SO at 350 deg.C3And H2O, SO formed3Further decomposing the mixture at 800-900 ℃ in the presence of a proper catalyst to generate SO2And O2。
With serpentine Mg3Si2O5(OH)4For example, the overall reaction of the whole process is:
Mg3Si2O5(OH)4+3CO2+H2O→3MgCO3+3H2+2SiO2+1.5O2
compared with the prior art, the invention has the beneficial effects that:
1. innovatively CO2Mineralization technology and thermochemical sulfur-iodine open-loop circulation water decomposition hydrogen production organic matterCombined to mineralize and fix CO under mild reaction condition2And simultaneously co-producing H with high added value2；
2. The hydrogen production cycle is organically combined with the mineralization technology, thereby skillfully avoiding HI-I in the traditional hydrogen production cycle2In the rectification separation process, the cycle has higher theoretical thermal efficiency;
3. all parts of the system belong to chemical processes, the reaction temperature is appropriate, and the large-scale industrial application is easy to realize.
Drawings
FIG. 1 is a process flow diagram of the present invention.
The reference numbers in the figures are: 1 is a Bunsen reaction device, 2 is a liquid phase separation device, and 3 is HIxConcentration device, 4 is H2SO4Concentration device, 5 is concentrated H2SO4Catalytic decomposing device, 6 is MgI2The generation reactor 7 is MgI2Distillation device, 8 is MgI2The hydrolysis carbonator and the HI catalytic decomposition reactor 9 are used as the hydrolysis carbonator.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
For thermochemically recycling mineralizing CO2Simultaneous decomposition of H2O system H2The apparatus of the method of (1), comprising: bunsen reaction apparatus 1, liquid phase separation apparatus 2, HIxConcentration apparatus 3, H2SO4Concentration device 4, concentrated H2SO4 Catalytic decomposition device 5, MgI2Production reactor 6, MgI2Distillation plant 7, MgI2 Hydrolysis carbonation reactor 8 and HI catalytic decomposition reactor 9;
these devices are known to those skilled in the art and can be constructed as follows: the Bunsen reaction device 1 is connected with a liquid phase separation device 2, and the liquid phase separation device 2 is respectively connected with HIxConcentration devices 3 and H2SO4Concentration apparatus 4, H2SO4Concentration device 4, concentrated H2SO4The catalytic decomposition device 5 and the Bunsen reaction device 1 are connected in sequence，HIxThe concentration device 3 is respectively connected with the Bunsen reaction device 1 and the MgI2Formation reactor 6, MgI2The generation reactor 6 is connected with MgI2Distillation apparatus 7, MgI2The distillation device 7 is respectively connected with the Bunsen reaction device 1 and the MgI2 Hydrolysis carbonation reactor 8, MgI2The hydrolysis carbonating reactor 8, the HI catalytic decomposition reactor 9 and the Bunsen reaction device 1 are connected in sequence.
Specific example 1:
(1) 14mol of H2O, 1.5mol of I2And 1mol of SO2Feeding into a Bunsen reaction device 1, stirring the reaction solution at constant speed by a motor device to ensure uniform mixing, and generating a water-rich HI phase (HI) by an autonomous exothermic reaction at 20 ℃ and 1atmx) And H2SO4A phase solution, wherein the HI phase mainly comprises hydrogen iodide solution and excess iodine, H2SO4The phases mainly contain H2SO4A solution, the chemical reaction of which is as follows:
I2+SO2+2H2O→2HI+H2SO4
separating the two-phase solution in the Bunsen reaction device 1 in a liquid phase separation device 2;
(2) at 120 deg.C, 0.08atm and adiabatic conditions in H2SO4H separated in the concentration device 42SO4Carrying out multi-stage sulfuric acid concentration treatment on the phase solution;
(3) concentrated H2SO4Phase entry to concentrated H2SO4In the catalytic decomposition device 5, the temperature is raised; decompose to SO at 350 deg.C3And H2O, SO formed3Further decomposing at 800 deg.C in the presence of a suitable catalyst to form SO2And O2Final product O2Associated with SO2And H2O is returned to the Bunsen reaction device 1 and separated, and the chemical reaction formula of the reaction is as follows:
H2SO4→SO2+H2O+0.5O2
SO2、H2o and O2Return toBunsen reaction apparatus 1, in which SO2And H2Recycling of O, O2Discharged as a final product;
(4) HI separated in liquid phase separation apparatus 2xPhase in HIxFurther concentrating and purifying in the concentrating device 3. The method comprises the following steps: subjecting the HI phase solution to electrodialysis to obtain concentrated HI solution at cathode side and concentrated HI solution at anode side of the electrodialysis cell2And diluting the HI solution and returning the HI solution to the Bunsen reaction device 1 for recycling;
(5) feeding the concentrated HI solution into MgI2 A forming reactor 6 which has spontaneous exothermic reaction with serpentine, the reaction temperature is controlled at 20 ℃, and the chemical reaction formula of the reaction is as follows:
6HI+Mg3Si2O5(OH)4→3MgI2+5H2O+2SiO2
MgI produced by the reaction2、H2O and SiO2And (4) concentrating the I entrained in the HI solution2Forming a mixed solution together;
(6) MgI2Filtering and washing the mixed solution in the generation reactor 6 to obtain a byproduct SiO2The filtrate is fed into MgI2The distillation device 7 is used for concentration and crystallization to obtain MgI2·nH2O crystals with simultaneous separation of I2Returning to the Bunsen reaction device 1 for recycling.
(7) MgI2MgI obtained in distillation apparatus 72·nH2Placing O crystal in MgI2In the hydrolysis carbonation reactor 8 (using fixed bed technology) CO is introduced in any proportion2、N2Performing hydrolysis and carbonation reaction with water vapor at 180 deg.C to obtain HI vapor and MgCO product3(ii) a The chemical reaction formula of the reaction is as follows:
MgI2+H2O+CO2→MgCO3+2HI
(8) feeding the generated HI steam into HI catalytic decomposition reactor 9, and reacting at 300 deg.C to obtain I2And the final product H2In which generated I2All return to the Bunsen reactionThe device 1 is reusable.
Specific example 2:
(1) 15mol H2O、5molI2And 1molSO2Sending into Bunsen reaction device 1, stirring reaction solution at uniform speed by motor device to ensure uniform mixing, generating autonomous exothermic reaction at 70 deg.C and 1.5atm to generate polyhydrated HI phase (HI)x) And H2SO4A phase solution, wherein the HI phase mainly comprises hydrogen iodide solution and excess iodine, H2SO4The phases mainly contain H2SO4A solution, the chemical reaction of which is as follows:
I2+SO2+2H2O→2HI+H2SO4
separating the two-phase solution in the Bunsen reaction device 1 in a liquid phase separation device 2;
(2) at 190 deg.C, 0.69atm and adiabatic conditions in H2SO4H separated in the concentration device 42SO4Carrying out multi-stage sulfuric acid concentration treatment on the phase solution;
(3) concentrated H2SO4Phase entry to concentrated H2SO4In the catalytic decomposition device 5, the temperature is raised; decompose to SO at 350 deg.C3And H2O, SO formed3Further decomposing at 850 deg.C in the presence of a suitable catalyst to form SO2And O2Final product O2Associated with SO2And H2O is returned to the Bunsen reaction device 1 and separated, and the chemical reaction formula of the reaction is as follows:
H2SO4→SO2+H2O+0.5O2
SO2、H2o and O2Returning to the Bunsen reaction apparatus 1, wherein SO2And H2Recycling of O, O2Discharged as a final product;
(4) HI separated in liquid phase separation apparatus 2xPhase in HIxFurther concentrating and purifying in the concentrating device 3. The method comprises the following steps: subjecting the HI phase solution to electrodialysis to obtain concentrated HI at the cathode side of the electrodialysis cellSolution, anode side obtained I2And diluting the HI solution and returning the HI solution to the Bunsen reaction device 1 for recycling;
(5) feeding the concentrated HI solution into MgI2 A generation reactor 6 which performs spontaneous exothermic reaction with serpentine, and the reaction temperature is controlled at 60 ℃; the chemical reaction formula of the reaction is as follows:
6HI+Mg3Si2O5(OH)4→3MgI2+5H2O+2SiO2
MgI produced by the reaction2、H2O and SiO2And (4) concentrating the I entrained in the HI solution2Forming a mixed solution together;
(6) MgI2Filtering and washing the mixed solution in the generation reactor 6 to obtain a byproduct SiO2The filtrate is fed into MgI2The distillation device 7 is used for concentration and crystallization to obtain MgI2·nH2O crystals with simultaneous separation of I2Returning to the Bunsen reaction device 1 for recycling.
(7) MgI2MgI obtained in distillation apparatus 72·nH2Placing O crystal in MgI2In the hydrolysis carbonation reactor 8 (using the fluidized bed technique) CO is introduced in any proportion2、N2Performing hydrolysis and carbonation reaction with water vapor at 260 deg.C to obtain HI vapor and MgCO product3(ii) a The chemical reaction formula of the reaction is as follows:
MgI2+H2O+CO2→MgCO3+2HI
(8) feeding the generated HI steam into HI catalytic decomposition reactor 9, and reacting at 400 deg.C to obtain I2And the final product H2In which generated I2All return to the Bunsen reaction device 1 for recycling.
Specific example 3:
(1) mixing 16molH2O、9molI2And 1molSO2Sending into Bunsen reaction device 1, stirring reaction solution at uniform speed by motor device to ensure uniform mixing, generating autonomous exothermic reaction at 120 deg.C and 2atm to generate polyhydrated HI phase (HI)x) And H2SO4A phase solution, wherein the HI phase mainly comprises hydrogen iodide solution and excess iodine, H2SO4The phases mainly contain H2SO4A solution, the chemical reaction of which is as follows:
I2+SO2+2H2O→2HI+H2SO4
separating the two-phase solution in the Bunsen reaction device 1 in a liquid phase separation device 2;
(2) at 260 deg.C, 1.3atm and adiabatic conditions in H2SO4H separated in the concentration device 42SO4Carrying out multi-stage sulfuric acid concentration treatment on the phase solution;
(3) concentrated H2SO4Phase entry to concentrated H2SO4In the catalytic decomposition device 5, the temperature is raised; h2SO4Phase at H2SO4Enters concentrated H after being concentrated in the concentration device 42SO4In the catalytic decomposition device 5, SO is decomposed at 350 DEG C3And H2O, SO formed3Further decomposing at 900 deg.C in the presence of a suitable catalyst to form SO2And O2Final product O2Associated with SO2And H2O is returned to the Bunsen reaction device 1 and separated, and the chemical reaction formula of the reaction is as follows:
H2SO4→SO2+H2O+0.5O2
SO2、H2o and O2Returning to the Bunsen reaction apparatus 1, wherein SO2And H2Recycling of O, O2Discharged as a final product;
(4) HI separated in liquid phase separation apparatus 2xPhase in HIxFurther concentrating and purifying in the concentrating device 3. The method comprises the following steps: subjecting the HI phase solution to electrodialysis to obtain concentrated HI solution at cathode side and concentrated HI solution at anode side of the electrodialysis cell2And diluting the HI solution and returning the HI solution to the Bunsen reaction device 1 for recycling;
(5) feeding the concentrated HI solution into MgI2Formation reactor 6, with serpentineSpontaneous exothermic reaction occurs, and the reaction temperature is controlled at 90 ℃; the chemical reaction formula of the reaction is as follows:
6HI+Mg3Si2O5(OH)4→3MgI2+5H2O+2SiO2
MgI produced by the reaction2、H2O and SiO2And (4) concentrating the I entrained in the HI solution2Forming a mixed solution together;
(6) MgI2Filtering and washing the mixed solution in the generation reactor 6 to obtain a byproduct SiO2The filtrate is fed into MgI2The distillation device 7 is used for concentration and crystallization to obtain MgI2·nH2O crystals with simultaneous separation of I2Returning to the Bunsen reaction device 1 for recycling.
(7) MgI2MgI obtained in distillation apparatus 72·nH2Placing O crystal in MgI2In the hydrolysis carbonation reactor 8 (using fixed bed technology) CO is introduced in any proportion2、N2Performing hydrolysis and carbonation reaction with water vapor at 350 deg.C to obtain HI vapor and MgCO product3(ii) a The chemical reaction formula of the reaction is as follows:
MgI2+H2O+CO2→MgCO3+2HI
(8) feeding the generated HI steam into HI catalytic decomposition reactor 9, and reacting at 500 deg.C to obtain I2And the final product H2In which generated I2All return to the Bunsen reaction device 1 for recycling.
Specific example 4:
serpentine (Mg) from example 33Si2O5(OH)4) By changing to forsterite (Mg)2SiO4) The chemical reaction formula of the corresponding steps is as follows, and all other steps and conditions are not changed.
4HI+Mg2SiO4→2MgI2+2H2O+SiO2
Finally, it should also be noted that the above-mentioned list is only a specific embodiment of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive. The scope of the invention is indicated by the appended claims, and the foregoing description is not intended to indicate the scope of the invention, and therefore, all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (2)

1. Thermochemical cycle mineralization CO2Simultaneous decomposition of H2O system H2The method is characterized by comprising the following steps:
(1) mixing H with the amount of the substance of 14-16: 1.5-9: 12O、I2And SO2Sending the mixture into a Bunsen reaction device, stirring the reaction solution at a constant speed to ensure that the reaction solution is uniformly mixed, and carrying out spontaneous exothermic reaction at the temperature of 20-120 ℃ and the pressure of 1-2 atm to generate a water-containing HI phase and H2SO4Phase solution; the chemical reaction formula of the reaction is as follows:
I2+ SO2+ 2H2O → 2HI + H2SO4
excessive iodine in the reaction ensures that the mixed solution generated by the Bunsen reaction is subjected to liquid-liquid phase separation to form an HI phase and H phase which are layered up and down2SO4Phase solution;
(2) under the conditions of 120-260 ℃, 0.08-1.3 atm and heat insulation, the separated H is treated2SO4Carrying out multi-stage sulfuric acid concentration treatment on the phase solution;
(3) concentrating the concentrated H2SO4Raising the temperature to 800-900 ℃, and generating SO by catalytic decomposition2、H2O and the final product O2The chemical reaction formula of the reaction is as follows:
H2SO4→ SO2+ H2O + 0.5 O2
SO2、H2o and O2Returning to the Bunsen reaction apparatus, wherein SO2And H2Recycling of O, O2Discharged as a final product;
(4) subjecting the HI phase solution obtained in step (1) to electrodialysis treatment to obtain concentrated HI solution at cathode side of electrodialysis cell and I at anode side2And diluting the HI solution and returning the HI solution to the Bunsen reaction device for recycling;
(5) the concentrated HI solution and magnesium silicate natural mineral are subjected to spontaneous exothermic reaction, the reaction temperature is controlled to be 20-90 ℃, and MgI is generated through the reaction2、H2O and SiO2And (4) concentrating the I entrained in the HI solution2The components are mixed to form a mixed solution; the magnesium silicate natural mineral is serpentine or olivine;
(6) filtering and washing the mixed solution in the step (5) to obtain a by-product SiO2Distilling the filtrate to obtain MgI2·nH2O crystals and isolated I2In which I2Returning to the Bunsen reaction device in the step (1) for recycling;
(7) MgI2·nH2Placing the O crystal in a fixed bed or a fluidized bed reactor, and introducing CO in any proportion2、N2Carrying out hydrolysis and carbonation reaction with water vapor, controlling the reaction temperature at 180-350 ℃, and finally obtaining HI steam and a MgCO product3(ii) a The chemical reaction formula of the reaction is as follows:
MgI2+ H2O + CO2→ MgCO3+ 2HI
(8) introducing the generated HI steam into an HI catalytic decomposition reactor for thermal decomposition, controlling the reaction temperature at 300-500 ℃ to finally obtain I2And product H2The chemical reaction formula of the reaction is as follows:
2HI → I2+ H2
wherein I2And (4) returning the Bunsen reaction device in the step (1) for recycling.
2. Thermochemical cycle mineralization of CO for carrying out the method of claim 12Simultaneous decomposition of H2O system H2The device comprises a Bunsen reaction device, and is characterized by also comprising: liquid phase separation device, HIxConcentration apparatus, H2SO4Concentration device, concentrated H2SO4Catalytic decomposition device, MgI2Production reactor, MgI2Distillation apparatus, MgI2A hydrolysis carbonation reactor and a HI catalytic decomposition reactor;
the Bunsen reaction device is connected with a liquid phase separation device, and the liquid phase separation device is respectively connected with HIxConcentration device and H2SO4Concentration apparatus, H2SO4Concentration device, concentrated H2SO4The catalytic decomposition device and the Bunsen reaction device are connected in sequence, HIxThe concentration device is respectively connected with the Bunsen reaction device and the MgI2Formation reactor, MgI2Production reactor connection MgI2Distillation apparatus, MgI2The distillation device is respectively connected with the Bunsen reaction device and the MgI2Hydrolysis carbonation reactor, MgI2The hydrolysis carbonating reactor is connected with the HI catalytic decomposition reactor, and the HI catalytic decomposition reactor is connected with the Bunsen reaction device.
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