CN116969416A - System and process for oxygen-enriched combustion coupled thermochemical sulfur-iodine cycle - Google Patents
System and process for oxygen-enriched combustion coupled thermochemical sulfur-iodine cycle Download PDFInfo
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- CN116969416A CN116969416A CN202311215689.5A CN202311215689A CN116969416A CN 116969416 A CN116969416 A CN 116969416A CN 202311215689 A CN202311215689 A CN 202311215689A CN 116969416 A CN116969416 A CN 116969416A
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- 238000002485 combustion reaction Methods 0.000 title claims abstract description 127
- 239000001301 oxygen Substances 0.000 title claims abstract description 101
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 101
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 100
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 357
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 135
- 239000007789 gas Substances 0.000 claims abstract description 119
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 108
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 89
- 239000003546 flue gas Substances 0.000 claims abstract description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 229910001868 water Inorganic materials 0.000 claims abstract description 74
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 71
- 239000001257 hydrogen Substances 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 54
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000001307 helium Substances 0.000 claims abstract description 24
- 229910052734 helium Inorganic materials 0.000 claims abstract description 24
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000007132 Bunsen reaction Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims description 85
- 238000003795 desorption Methods 0.000 claims description 76
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims description 59
- 229910052740 iodine Inorganic materials 0.000 claims description 33
- 239000011630 iodine Substances 0.000 claims description 33
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 32
- 239000002918 waste heat Substances 0.000 claims description 25
- 238000000746 purification Methods 0.000 claims description 23
- 238000003860 storage Methods 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 12
- 239000000428 dust Substances 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000005611 electricity Effects 0.000 abstract description 3
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000010248 power generation Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
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- 239000006227 byproduct Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000003345 natural gas Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-N iodic acid Chemical compound OI(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-N 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 238000003303 reheating Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 zinc-sulfur-iodine Chemical compound 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940125532 enzyme inhibitor Drugs 0.000 description 1
- 239000002532 enzyme inhibitor Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/74—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
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- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/106—Peroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The application relates to the technical field of new energy, in particular to a system and a process for realizing zero carbon emission and simultaneously combining heat, electricity, hydrogen and sulfuric acid by oxygen-enriched combustion coupling thermochemical sulfur-iodine circulation, wherein the system comprises an oxygen-enriched combustion furnace and a sulfur-iodine circulating unit which are coupled, a sulfur circulating pipeline is used for decomposing sulfuric acid prepared by the sulfur-iodine circulating unit, a decomposition product is supplied to the oxygen-enriched combustion furnace, and combustion heat is transferred through a helium circulating pipeline for sulfuric acid decomposition and hydroiodic acid decomposition; desulfurization of temperature-changing pressure-changing adsorption-desorption device to produce SO 2 Then feeding Bunsen reaction; the oxygen-enriched combustion flue gas is treated to obtain pure CO 2 And (5) storing. The application couples the sulfur-iodine cycle with the oxygen-enriched combustion, and the oxygen-enriched combustion provides SO for the sulfur-iodine cycle 2 And heat, sulfur-iodine circulation provides circulating gas containing water heat flow carrier and high-purity oxygen for oxygen-enriched combustion, which increases the heat flow density of flue gas, strengthens the heat transfer rate of flue gas, helium and water/steam, and solves the problems of insufficient heat capacity and poor combustion stability of boiler of circulating flue gas of a classical oxygen-enriched combustion system.
Description
Technical Field
The application relates to the technical field of new energy, in particular to a system and a process for realizing zero carbon emission and combining heat, electricity, hydrogen and sulfuric acid by oxygen-enriched combustion coupled with thermochemical sulfur-iodine circulation.
Background
The main reactions of the thermochemical sulfur-iodine cycle process are the Bunsen reaction, the hydrogen iodide decomposition reaction and the sulfuric acid decomposition reaction. The Bunsen reaction is carried out at normal temperature and pressure, and the exothermic amount is 52.626kcal/mol, and is a spontaneous exothermic reaction. The exothermic amount of the hydrogen iodide decomposition reaction was 4.21kcal/mol, but the ΔG of the reaction was 10.818kcal/mol, and it was impossible to spontaneously proceed, and therefore it was necessary to provide a reaction environment higher than 400 ℃. The sulfuric acid decomposition reaction ΔG and ΔH were-16.412 kcal/mol and 44.348kcal/mol, respectively, and it was found that the sulfuric acid decomposition reaction was spontaneous reaction, but a large amount of reaction heat had to be absorbed.
The energy consumption in the thermochemical sulfur-iodine cycle process is mainly used for providing the heat of sulfuric acid decomposition reaction, and Chinese patent publication No.: CN115321479B, name: a method and device for preparing hydrogen and sulfuric acid by circularly decomposing water by thermochemical zinc-sulfur-iodine, which discloses a method for preparing hydrogen by circularly decomposing water by open thermochemical sulfur-iodine, and uses SO in flue gas 2 As raw materials, the sulfuric acid is produced, so that the high energy consumption of sulfuric acid decomposition is avoided, and the hydrogen production cost is obviously reduced. However, this process requires a large amount of pure and stable SO 2 From the source of SO 2 The flow fluctuation will destroy the material balance of the system, resulting in fluctuation or even stop of hydrogen yield, when SO 2 When the catalyst contains impurities, the purification of the sulfuric acid phase and the hydroiodic acid phase can be affected, and finally, the system equipment is scaled, the catalyst is blocked and deactivated. In addition, in the thermochemical sulfur-iodine cycle hydrogen production process, high-purity hydrogen is produced, and high-purity oxygen is produced as a byproduct. Because the high-purity oxygen has lower value and higher storage and transportation cost than selling price, the obtained oxygen is directly discharged in various technologies for preparing hydrogen by cracking water, and the waste of the high-purity oxygen is caused.
The oxygen-enriched combustion is a combustion technology which replaces air with pure oxygen mixed circulating flue gas, and is one of schemes for solving the problem of carbon emission of coal, and the flue gas component of the oxygen-enriched combustion is mainly CO 2 And water vapor, the CO can be directly trapped after the water vapor is cooled down 2 And stored or reused. However, coal typically contains 0.8% to 1.8% nitrogen and typically no more than 9% sulfur in order to obtain higher purity CO 2 Must be specific to CO 2 The purification treatment results in additional carbon capture energy consumption. In addition, oxygen-enriched combustion must provide high-purity oxygen, and air separation oxygen production has high energy consumption, poor economy and difficult popularization.
Technical schemes for coupling multiple systems such as hydrogen production and oxygen-enriched combustion have also been reported, for example, chinese patent publication No.: CN113054750B, name: a clean hydrogen and renewable energy hydrogen combined production system discloses an energy comprehensive utilization system formed by combining a photovoltaic power generation system, a wind power generation system, a hydrogen storage system, an electrolysis water system, an oxygen-enriched combustion system and a CCS system, solves the fluctuation problem of the photovoltaic power generation system and the wind power generation system, realizes power on-grid, simultaneously utilizes electrolysis water to provide oxygen for oxygen-enriched combustion of fuel gas such as natural gas and the like, and realizes steam reforming hydrogen production of the residual natural gas. In the process, although a plurality of energy comprehensive utilization systems are combined, from the system, oxygen which is an electrolytic water byproduct is used for oxygen-enriched combustion of natural gas, and the two systems have no other linkage and mutual promotion; in addition, the scheme of separating hydrogen from reformed gas and then combining the hydrogen into photovoltaic hydrogen production has high energy consumption and difficulty, and the system benefit is greatly reduced by changing green hydrogen into gray hydrogen.
Disclosure of Invention
In order to reduce the cost of oxygen-enriched combustion and thermochemical sulfur-iodine cycle hydrogen production, the application utilizes resources such as sulfur, nitrogen and the like in fossil fuels such as coal and the like, and couples the oxygen-enriched combustion technology and the thermochemical sulfur-iodine cycle hydrogen production technology, and the oxygen-enriched combustion provides SO for thermochemical sulfur-iodine cycle hydrogen production 2 And heat, thermochemical sulfur-iodine cycle hydrogen production provides a water-containing heat flow carrier and high-purity oxygen for oxygen-enriched combustion, reduces the system operation cost, omits flue gas circulation equipment, improves the stability of a boiler, avoids sulfur loss in a sulfur-iodine circulation system, and increases the hydrogen yield. The application realizes low-cost heat, electricity and hydrogen co-production under the condition of zero carbon emission, and simultaneously produces concentrated sulfuric acid as a byproduct, thereby realizing clean and efficient utilization of coal and full conversion of coal resource value and obtaining maximum system benefit and heat efficiency.
On one hand, the application provides an oxygen-enriched combustion coupled thermochemical sulfur-iodine circulating system, which comprises an oxygen-enriched combustion furnace 1 and a sulfur-iodine circulating unit, wherein a mixed acid outlet 152 of a Bunsen tower 15 of the sulfur-iodine circulating unit is connected with a layering tower 14, the back of the layering tower 14 is divided into two paths, one path is led out from the middle upper part of the layering tower 14 and is sequentially connected with a sulfuric acid purifying tower 12, a sulfuric acid concentrating tower 11 and a sulfuric acid decomposing tower 9, and the other path is led out from the middle lower part of the layering tower 14 and is sequentially connected with a hydroiodic acid purifying tank 17, a hydroiodic acid concentrating tower 16 and a hydrogen iodide decomposing tower 10; a helium gas circulation pipeline 25 for transferring heat is sequentially connected with the oxygen-enriched combustion furnace 1, the sulfuric acid decomposition tower 9 and the hydrogen iodide decomposition tower 10 to form a circulation loop; the oxygen-enriched combustion furnace 1 is provided with a fuel inlet A first inlet 26 for introducing SO-containing gas 2 、O 2 And a third inlet 28 for circulating gas of water, wherein the circulating gas is returned from the sulfuric acid decomposition gas generated by the sulfuric acid decomposition tower 9 to the sulfuric acid concentration tower 11 for heat exchange and cooling, and then is discharged from the Bunsen tower 15 and mainly contains SO 2 Is obtained by mixing the gases of the above steps; the temperature and pressure changing adsorption and desorption device of the flue gas treatment separation unit comprises a plurality of sub-paths which are connected in parallel, at least one adsorption and desorption tower is arranged in each sub-path, porous adsorption materials are filled in the adsorption and desorption towers, and at least one sub-path is used for SO at the same time 2 Adsorption and at least one sub-path for SO 2 Desorption, adsorption and desorption of separated SO 2 Is fed to Bunsen column 15.
In particular, the oxyfuel combustion furnace 1 is provided with a fourth inlet 29 for introducing boiler water, a boiler flue gas outlet 27 for discharging oxyfuel combustion flue gas and a middle-high pressure steam outlet 30 for discharging middle-high pressure steam; the medium-high pressure steam generated by heat exchange between boiler water and high-temperature flue gas is discharged out of the oxygen-enriched combustion furnace 1 to push the high-pressure turbine 31 to generate power and output power, the medium-high pressure steam is cooled and depressurized after acting and is sent back to the oxygen-enriched combustion furnace 1 to reheat, the reheat steam is discharged out of the oxygen-enriched combustion furnace 1 to push the medium-pressure turbine 32 to generate power and output power, and the reheat steam is cooled and depressurized after acting and is sent to the waste heat recoverer 7 and is sent to the Bunsen tower 15 to discharge the waste heat containing main SO 2 Condensed water generated by condensing steam in the waste heat recoverer 7 is returned to the oxygen-enriched combustion furnace 1 through the fourth inlet 29 for continuous heat exchange so as to form steam circulation.
In particular, the temperature and pressure changing adsorption and desorption device comprises two parallel sub-paths, each sub-path is provided with two adsorption and desorption towers which are connected in series, the adsorption and desorption towers are respectively a first adsorption and desorption tower 20 and a third adsorption and desorption tower 22, and a second adsorption and desorption tower 21 and a fourth adsorption and desorption tower 23 of the other sub-path, and the adsorption and desorption operations are alternately carried out on the two sub-paths.
In particular, the adsorption and desorption tower is filled with one or more porous adsorption materials selected from activated carbon, molecular sieve and zeolite.
In particular, the flue gas treatment and separation unit comprises a dust remover 2, a flue gas heat exchanger 3, a flue gas condenser 4 and a variable-temperature and variable-pressure adsorption and desorption unit which are connected in sequenceThe device and the denitration tower 5, dry flue gas obtained by sequentially carrying out dust removal, heat exchange and condensation treatment on oxygen-enriched combustion flue gas enters a variable-temperature and variable-pressure adsorption and desorption device, and the SO separated by adsorption and desorption is adsorbed and desorbed 2 Supplying sulfur-iodine circulation unit to participate in Bunsen reaction, and residual CO 2 And NO X After entering a denitration tower 5 for treatment, pure CO is finally obtained 2 。
In particular, in the denitration tower 5, hydrogen peroxide is used as an oxidation absorbent, and NO X After oxidation, the mixture is dissolved in hydrogen peroxide to generate nitric acid, and finally pure CO is obtained 2 Is pressurized by a first booster fan 6 and then is used for conveying or sealing.
In particular, the sulfuric acid purification column 12 and the hydroiodic acid purification tank 17 are also directly connected to the Bunsen column 15, respectively, the hydrogen iodide decomposition gas outlet 164 of the hydroiodic acid concentration column 16 and the sulfuric acid concentration column 11 are also connected to the gas-liquid separator 19, respectively, and the iodine/hydroiodic acid outlet 192 of the gas-liquid separator 19 is connected to the Bunsen column 15.
In particular, the concentrated sulfuric acid outlet 112 of the sulfuric acid concentration tower 11 is connected with the sulfuric acid decomposition tower 9, the connecting pipeline is further provided with a concentrated sulfuric acid output 115, the sulfuric acid decomposition tower 9 is further provided with a pipeline for discharging sulfuric acid decomposition gas, and is connected with the sulfuric acid decomposition gas inlet 113 of the sulfuric acid concentration tower 11, heat is supplied for sulfuric acid concentration by heat exchange, and the sulfuric acid decomposition gas after heat exchange is led out from the sulfuric acid decomposition gas outlet 114 and is mixed with gas from the Bunsen tower 15 after heat exchange and temperature rise in the waste heat recoverer 7, and then is sent into the oxygen-enriched combustion furnace 1 from the third inlet 28.
Specifically, the concentrated hydroiodic acid outlet 162 of the hydroiodic acid concentrating tower 16 is connected with the hydrogen iodide decomposing tower 10, the hydrogen iodide decomposing tower 10 is further provided with a pipeline for discharging the hydrogen iodide decomposing gas, and is connected with the hydrogen iodide decomposing gas inlet 163 of the hydroiodic acid concentrating tower 16, the heat exchange is performed to concentrate the hydroiodic acid and supply heat, the hydrogen iodide decomposing gas after heat exchange is led out through the hydrogen iodide decomposing gas outlet 164 and then enters the gas-liquid separator 19, the gas is condensed in the gas-liquid separator 19 and then is discharged from the iodine/hydroiodic acid outlet 192, and the residual gas is sent out through the hydrogen outlet 191 to obtain the product hydrogen.
On the other hand, the application also provides a process of oxygen-enriched combustion coupled with thermochemical sulfur-iodine cycle, which runs as described aboveThe system comprises S1, oxygen-enriched combustion, and delivering recycle gas and fuel into an oxygen-enriched combustion furnace 1 for combustion, wherein the recycle gas is returned to a sulfuric acid concentration tower 11 from sulfuric acid decomposition gas generated by a sulfuric acid decomposition tower 9 for heat exchange and cooling, and then is discharged with a Bunsen tower 15 for SO-containing 2 150-200 ℃ gas obtained by mixing the gases of the fuel, and the products of combustion of the fuel comprise CO 2 Water, SO 2 And NOx, the temperature of the flue gas rises to not lower than 1100 ℃ during combustion; s2, heat exchange is carried out on combustion flue gas, the flue gas generated by combustion exchanges heat with a helium gas circulation pipeline 25 and a water vapor circulation pipeline in the oxygen-enriched combustion furnace 1, helium gas is heated to 850-1000 ℃ from 350-500 ℃, high-pressure circulation steam and low-pressure circulation steam are heated to 350-450 ℃, and the flue gas temperature is reduced to 140-220 ℃ and then is discharged from a flue gas outlet 27 of a boiler; s3, flue gas treatment and separation, namely, flue gas is subjected to dust removal, heat exchange and temperature reduction to 30-50 ℃, separated and dehydrated and then sent to a variable-temperature and variable-pressure adsorption and desorption device, and a plurality of sub-paths alternately perform SO (sulfur dioxide) 2 Adsorption and SO 2 Desorption, adsorption and desorption of separated SO 2 The mixture is supplied to a Bunsen column 15 to participate in Bunsen reaction, and the residual component is high-purity CO 2 The mixture is pressurized and then is used for conveying, sealing or utilizing; s4, sulfur-iodine circulation, SO 2 Water and iodine are subjected to Bunsen reaction in a Bunsen tower 15 to generate a mixed acid solution of sulfuric acid and hydroiodic acid, the mixed acid solution is sent to a layering tower 14 for layering, a lower sulfuric acid phase is sent to a sulfuric acid phase storage tank 13 from a sulfuric acid phase outlet 141, and an upper hydroiodic acid phase is sent to a hydroiodic acid phase storage tank 18 from a hydroiodic acid phase outlet 142; the sulfuric acid is decomposed to generate sulfuric acid decomposed gas at 800-900 ℃ after being purified and concentrated in turn, and the hydroiodic acid is decomposed to hydrogen and iodine vapor at 400-600 ℃ after being purified and concentrated in turn.
On the basis of the common sense in the art, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the application.
The technical scheme has the following advantages or beneficial effects: the application combines the thermochemical sulfur-iodine cycle hydrogen production with the oxygen-enriched combustion, and the oxygen-enriched combustion provides SO for the thermochemical sulfur-iodine cycle hydrogen production 2 And heat, thermochemical sulfur-iodine cycle hydrogen production provides a circulating gas containing water heat flow carrier and high-purity oxygen for oxygen-enriched combustion, thereby replacing the hydrogen produced byThe typical oxyfuel combustion system process uses a main CO-containing gas 2 The circulating gas of the application increases the heat flow density of the flue gas, strengthens the heat transfer rate of the flue gas, helium and water/steam, and solves the problems of insufficient heat capacity and poor combustion stability of the boiler of the circulating flue gas of the classical oxygen-enriched combustion system. SO based 2 、NO x 、CO 2 The physical adsorption and desorption characteristics of the flue gas are selected to separate SO in the flue gas by using a variable-pressure variable-temperature adsorption and desorption process 2 Absorption of NO using an inexpensive and pH neutral hydrogen peroxide X Low cost of implementing CO 2 The purification and the recycling of sulfur and nitrogen obviously reduce the energy consumption of oxygen-enriched combustion air separation and flue gas purification and improve the economy of an oxygen-enriched combustion system. The use of the heat of the oxyfuel furnace provides heat for sulfuric acid decomposition and hydroiodic acid decomposition, and the use of thermal energy to crack water is less costly than the use of prior art electrical energy to crack water. The application also captures the high-purity CO generated by oxygen-enriched combustion 2 Realizes zero carbon emission of the whole system and remarkably reduces CO 2 The trapping cost and the hydrogen production cost achieve the aim of maximizing the technical benefits of two processes. Of course, not all of the advantages described above are necessarily achieved at the same time by any one of the solutions of the application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be obvious to a person skilled in the art that other figures can be obtained from the figures provided without the inventive effort.
FIG. 1 is a schematic illustration of an oxycombustion coupled thermochemical sulfur-iodine recycling system according to one embodiment of the application.
FIG. 2 is a schematic process diagram of an oxycombustion coupled thermochemical sulfur-iodine cycle according to one embodiment of the application.
Wherein, 1-oxygen-enriched combustion furnace; 26-a first inlet; 27-a boiler flue gas outlet; 28-a third inlet; 29-fourth inlet; 30-medium-high pressure steam outlet; 31-high pressure turbine; 32-medium pressure turbine; 33-a power output; 2-a dust remover; 3-a flue gas heat exchanger; 4-a flue gas condenser; 41-excess water outlet; 5-a denitration tower; 6-a first booster fan; 7-a waste heat recoverer; 71-a waste heat steam inlet; 72-a condensate outlet; 8-an axial flow fan; 9-sulfuric acid decomposing tower; a 10-hydrogen iodide decomposition tower; 11-sulfuric acid concentration tower; a 111-sulfuric acid inlet; 112-concentrated sulfuric acid outlet; 113-sulfuric acid decomposition gas inlet; 114-sulfuric acid decomposition gas outlet; 115-concentrated sulfuric acid outlet; a 12-sulfuric acid purification tower; 13-sulfuric acid phase storage tank; 14-layering tower; 141-sulfuric acid phase outlet; 142-hydroiodic acid phase outlet; 15-Bunsen column; 151-purified water inlet; 152-mixed acid outlet; a 16-hydroiodic acid concentration column; 161-hydroiodic acid inlet; 162-concentrated hydroiodic acid outlet; 163-hydrogen iodide decomposition gas inlet; 164-hydrogen iodide decomposition gas outlet; 17-hydroiodic acid purifying tank; 18-hydroiodic acid phase storage tanks; 19-a gas-liquid separator; 191-hydrogen outlet; 192-iodine/hydroiodic acid outlet; 20-a first adsorption and desorption tower; 21-a second adsorption/desorption column; 22-a third adsorption and desorption tower; 23-a fourth adsorption and desorption tower; 24-vacuum pump; 25-helium circulation line.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below with reference to the accompanying drawings. It is obvious that the described embodiments are only some of the embodiments of the present application and are intended to explain the inventive concept. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
The positional or positional relationship indicated by the terms "upper", "lower", etc. used in the description are based on the positional or positional relationship shown in the drawings, and are merely for simplicity of description, and are not intended to indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operate in a particular orientation.
The terms "first," "second," and the like, as used in the description, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. The term "plurality" means two or more, unless specifically defined otherwise.
The terms "coupled," "connected," and the like as used in the description herein are to be construed broadly and may be, for example, fixedly coupled, detachably coupled, or integrally formed, unless otherwise specifically defined and limited; may be a mechanical connection, an electrical connection; can be directly connected and indirectly connected through an intermediate medium; may be a communication between two elements or an interaction between two elements. The specific meaning of the terms in the embodiments can be understood by those of ordinary skill in the art according to the specific circumstances.
Unless expressly stated or limited otherwise, a first feature "above," "below," or "above" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" or "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. A first feature "under", "beneath" or "under" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "under", "beneath" or "under" a second feature may be a first feature being directly under or diagonally under the second feature, or simply indicating that the first feature is less level than the second feature.
The terms "one particular embodiment" and "one particular embodiment" as used in this description mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Referring to fig. 1, a system for coupling oxyfuel combustion with thermochemical sulfur-iodine cycle is provided in one embodiment of the present application, comprising an oxyfuel combustion furnace 1 and a sulfur-iodine cycle unit, wherein a helium gas circulation pipeline 25 sequentially transfers heat generated by combustion in the oxyfuel combustion furnace 1 to a sulfuric acid decomposition tower 9 and a hydrogen iodide decomposition tower 10 of the sulfur-iodine cycle unit for sulfuric acid decomposition and hydroiodic acid decomposition, respectively; the downstream of the oxygenized combustion furnace 1 is connected with a flue gas treatment and separation unit, the flue gas treatment and separation unit comprises a dust remover 2, a flue gas heat exchanger 3, a flue gas condenser 4, a variable-temperature and variable-pressure adsorption and desorption device, a denitration tower 5 and a first booster fan 6 which are sequentially connected, dry flue gas obtained by the sequential dust removal, heat exchange and condensation treatment of oxygenized combustion flue gas enters the variable-temperature and variable-pressure adsorption and desorption device, and SO separated by adsorption and desorption is adsorbed and desorbed 2 Supplying sulfur-iodine circulation unit to participate in Bunsen reaction, and residual CO 2 And NO X After entering a denitration tower 5 for treatment, pure CO is finally obtained 2 。
The oxygen-enriched combustion furnace 1 is provided with a first inlet 26 for introducing fuel such as coal, coal water slurry, natural gas and the like and a second inlet for introducing fuel mainly containing SO 2 、O 2 And a third inlet 28 for circulating water, a fourth inlet 29 for introducing boiler water, a boiler flue gas outlet 27 for discharging oxyfuel combustion flue gas, and a medium-high pressure steam outlet 30 for discharging medium-high pressure steam. The medium-high pressure steam generated by heat exchange of boiler water and high-temperature flue gas is discharged out of the oxygen-enriched combustion furnace 1 to push the high-pressure turbine 31 to generate power and output power, the medium-high pressure steam is cooled and depressurized after acting and is sent back to the oxygen-enriched combustion furnace 1 to reheat, the reheat steam is discharged out of the oxygen-enriched combustion furnace 1 to push the medium-pressure turbine 32 to generate power and output power, the reheat steam is cooled and depressurized after acting and is sent to the waste heat recoverer 7 to exchange heat with gas to be condensed, and condensed water generated by steam condensation in the waste heat recoverer 7 is sent back to the oxygen-enriched combustion furnace 1 through the fourth inlet 29 to exchange heat continuously to form steam circulation.
The temperature and pressure changing adsorption and desorption device comprises a plurality of sub-paths connected in parallel, wherein each sub-path is provided with at least one adsorption and desorption tower, one or more porous adsorption materials such as active carbon, molecular sieve, zeolite and the like are filled in the adsorption and desorption tower, and at least one sub-path is used for SO at the same time 2 Adsorption with at least one sub-routeRow SO 2 And (5) desorption. Preferably, as illustrated in fig. 1, the temperature and pressure swing adsorption and desorption device includes two parallel sub-paths, each sub-path is provided with two adsorption and desorption towers connected in series, namely a first adsorption and desorption tower 20 and a third adsorption and desorption tower 22, and a second adsorption and desorption tower 21 and a fourth adsorption and desorption tower 23 of the other sub-path, and the two sub-paths alternately perform adsorption and desorption operations. Specifically, in the physical adsorption process at 30-50 ℃, the adsorption priority of the porous adsorption material to each substance in the dry flue gas is SO 2 >NO X >CO 2 I.e. porous adsorption material for SO 2 Is stronger than other components, even for adsorbed CO 2 And NO X Is introduced with SO 2 SO can be used after that 2 To adsorb CO 2 And NO X And replacing. After the dry flue gas enters a variable-temperature and variable-pressure adsorption and desorption device, SO 2 Is absorbed and trapped by porous adsorption material, and the residual CO 2 And NO X Entering a denitration tower 5, taking hydrogen peroxide as an oxidation absorbent in the denitration tower 5, and adding NO X After oxidation, the mixture is dissolved in hydrogen peroxide to react and generate nitric acid, and finally pure CO is obtained 2 Pressurized by the first booster fan 6 for transportation, storage or other means of use.
The sulfur-iodine circulating unit comprises a Bunsen tower 15, wherein the Bunsen tower 15 is provided with a purified water inlet 151 for introducing water and a mixed acid outlet 152, the mixed acid outlet 152 is connected with the layering tower 14, the back of the layering tower 14 is divided into two paths, one path is led out from the middle upper part of the layering tower 14 and is sequentially connected with a sulfuric acid phase storage tank 13, a sulfuric acid purification tower 12, a sulfuric acid concentration tower 11 and a sulfuric acid decomposition tower 9, and the other path is led out from the middle lower part of the layering tower 14 and is sequentially connected with a hydroiodic acid phase storage tank 18, a hydroiodic acid purification tank 17, a hydroiodic acid concentration tower 16 and a hydrogen iodide decomposition tower 10. The reaction occurring in the sulfuric acid decomposition tower 9 is as follows 2H 2 SO 4 →2SO 2 +2H 2 O+O 2 The reaction occurring in the hydrogen iodide decomposition column 10 is as follows 2HI→H 2 +I 2 . The sulfuric acid in the sulfuric acid phase storage tank 13 is conveyed to the sulfuric acid purification tower 12 for purification, and the sulfuric acid purification reaction comprises H 2 SO 4 +2HI→SO 2 +2H 2 O+I 2 Or H 2 SO 4 +8HI=H 2 S+4H 2 O+4I 2 . Purification of sulfuric acid produced SO 2 Or H 2 The S gas is returned to the Bunsen column 15 and the resulting iodine solid is fed to the sulfuric acid concentration column 11 following sulfuric acid. The iodine in the sulfuric acid concentration tower 11 is sublimated and discharged together with the water vapor, and then the sublimated iodine is sent to the gas-liquid separator 19, the separated iodine is sent back to the Bunsen tower 15, the concentrated sulfuric acid is sent out from the concentrated sulfuric acid outlet 112 of the sulfuric acid concentration tower 11, and is sent to the sulfuric acid decomposition tower 9 at a constant flow rate, and the excessive concentrated sulfuric acid is produced from the concentrated sulfuric acid outlet 115. The sulfuric acid pyrolysis gas is returned to the sulfuric acid concentration tower 11 through the sulfuric acid pyrolysis gas inlet 113 to supply heat for sulfuric acid concentration, and the sulfuric acid pyrolysis gas after heat exchange is led out through the sulfuric acid pyrolysis gas outlet 114 and mixed with the gas from the Bunsen tower 15 after heat exchange and temperature rise in the waste heat recoverer 7, and is sent into the oxygen-enriched combustion furnace 1 through the third inlet 28. Hydrogen iodide in the hydrogen iodide decomposition tower 10 is decomposed into hydrogen and iodine steam, hydrogen iodide decomposition gas is returned to the hydrogen iodic acid concentration tower 16 through the hydrogen iodide decomposition gas inlet 163 for heat exchange, then is led out through the hydrogen iodide decomposition gas outlet 164 and is sent into the gas-liquid separator 19, hydrogen iodide decomposition gas is condensed to obtain a hydrogen iodic acid complex solution, and the residual gas is sent out through the hydrogen outlet 191 to obtain the product hydrogen.
Referring to fig. 1 and 2, the oxygen-enriched combustion coupled thermochemical sulfur-iodine circulating system of the present application operates as follows: the sulfuric acid decomposition gas discharged from the sulfuric acid decomposition tower 9 and the main SO-containing gas discharged from the Bunsen tower 15 2 Is fed into the oxyfuel combustion furnace 1 through a third inlet 28, fuel such as coal, coal water slurry, natural gas and the like is fed into the oxyfuel combustion furnace 1 through a first inlet 26, and the combustion product of the fuel is mainly CO 2 A small amount of water, SO 2 And NO x . When in combustion, the temperature of the flue gas is increased to not lower than 1100 ℃, the flue gas exchanges heat with a helium gas circulation pipeline 25 and a water vapor circulation pipeline in the oxygen-enriched combustion furnace 1, the temperature of the helium gas is increased from 350 ℃ to 500 ℃ to 850 ℃ to 1000 ℃, high-pressure circulation steam and low-pressure circulation steam are heated to 350 ℃ to 450 ℃, and the temperature of the flue gas is reduced to 140 ℃ to 220 ℃ and then the flue gas is discharged from a flue gas outlet 27 of the boiler.
The flue gas discharged from the flue gas outlet 27 of the boiler is sent to a dust remover 2 for dust removal, and then is sent to a flue gas heat exchanger 3 for heat exchange and temperature reduction to 30-50 ℃, and the flue gas is in the cooled flue gasCondensing water vapor into water, sending the water to a flue gas condenser 4 for separating water, sending the separated water to a Bunsen tower 15, and heating a heat transfer working medium from 30-50 ℃ to 110-130 ℃ by a flue gas heat exchanger 3 to be used for adsorbing and desorbing SO of the tower 2 And (3) a desorption process.
The dehydrated dry flue gas is sent to a variable-temperature and variable-pressure adsorption and desorption device, taking fig. 1 as an example, the dry flue gas firstly enters a first adsorption and desorption tower 20, and SO in the flue gas 2 Is adsorbed by the porous adsorption material in the first adsorption/desorption column 20, and the insufficiently adsorbed SO 2 、CO 2 、NO x The total SO is absorbed by the third absorption and desorption tower 22 from the outlet of the first absorption and desorption tower 20 to the third absorption and desorption tower 22 2 NO in small amounts x After adsorption, the rest CO in the flue gas 2 、NO x Is sent to a denitration tower 5. SO-dependent 2 The adsorption capacity is increased, the adsorption material in the first adsorption and desorption tower 20 is nearly saturated, at the moment, the dry flue gas is introduced into the second adsorption and desorption tower 21 by the switching valve, the heat transfer working medium at 110-130 ℃ is introduced into the first adsorption and desorption tower 20 and the third adsorption and desorption tower 22, the vacuum pump 24 synchronously operates, the absolute operation pressure in the first adsorption and desorption tower 20 and the third adsorption and desorption tower 22 is reduced to 0-0.3 atm, and SO in the adsorbent is realized 2 Is desorbed rapidly, SO desorbed 2 To Bunsen column 15. The heat transfer working medium can circularly flow between the adsorption and desorption tower and the flue gas heat exchanger 3, the heat transfer working medium enters the flue gas heat exchanger 3 to absorb the waste heat of the flue gas, the temperature is increased from 30 ℃ to 50 ℃ to 110 ℃ to 130 ℃, the heat is released after the heat is sent into the adsorption and desorption tower, the temperature is reduced from 110 ℃ to 130 ℃ to 60 ℃ to 90 ℃, and after leaving the desorption tower, the heat transfer working medium naturally exchanges heat with the environment and is conveyed to the flue gas heat exchanger 3, and the temperature is reduced to 30 ℃ to 50 ℃. The other path is similar to the former path, and the two paths are alternately and circularly operated to finally realize SO in the flue gas 2 Is separated and transported continuously. Small amount of NO desorbed x Is poorly soluble in water, with excessive SO 2 The waste heat is discharged from the top of the Bunsen tower 15 and is returned to the oxygen-enriched combustion furnace 1 through the axial flow fan 8, the waste heat recoverer 7 and the third inlet 28 in sequence, and the waste heat is continuously circulated in the system, and the non-adsorbed NO is not adsorbed x Absorbed in the denitrating tower 5. The denitration tower 5 is filled with hydrogen peroxide which is used for adding NO x Oxidation to NO 2 And then absorbed in hydrogen peroxide solution to form nitric acid. After the flue gas is dehydrated, desulfurized and denitrated, the residual component is high-purity CO 2 Is pressurized by a booster fan 6 and then is used for conveying, sealing or utilizing.
SO desorbed by the adsorption and desorption tower 2 Is sent to a Bunsen tower 15 through a vacuum pump 24 to SO 2 The Bunsen reaction takes place in Bunsen column 15 with water and iodine to form a mixed acid solution of sulfuric acid and hydroiodic acid. SO participating in Bunsen reaction 2 From sulfuric acid decomposition and coal combustion, partly from sulfuric acid purification column 12 and hydroiodic acid purification column 17; the water comes from the flue gas condenser 4 and the gas-liquid separator 19, insufficient water is supplemented by the purified water inlet 151, and the water quantity in the Bunsen tower 15 is regulated by opening and closing the purified water inlet 151 and the excessive water outlet 41; iodine is input through iodine/hydroiodic acid outlet 192. The reaction product of Bunsen column 15 is fed to the layering column 14 via mixed acid outlet 152 for layering, and the sulfuric acid phase at the rear lower part is fed from sulfuric acid phase outlet 141 to sulfuric acid phase storage tank 13, and the hydroiodic acid phase at the upper part is fed from hydroiodic acid phase outlet 142 to hydroiodic acid phase storage tank 18.
The sulfuric acid phase sent out by layering tower 14 passes through sulfuric acid phase storage tank 13 and sulfuric acid purifying tower 12 in turn, SO generated is purified 2 Or H 2 The S gas is returned to the Bunsen column 15, the iodine produced by purification is fed to the sulfuric acid concentration column 11 through the sulfuric acid inlet 111, and the iodine sublimates after the sulfuric acid is discharged together with water vapor to be fed to the gas-liquid separator 19 for condensation, and the iodine/hydroiodic acid outlet 192 is returned to the Bunsen column 15. The sulfuric acid concentration tower 11 increases the concentration of sulfuric acid from 30% -60% to 95% -98%, and then sends the sulfuric acid from the concentrated sulfuric acid outlet 112, and sends the concentrated sulfuric acid into the sulfuric acid decomposition tower 9 at a constant flow, and the concentrated sulfuric acid is decomposed into SO at high temperature 2 、O 2 、H 2 O, the excess concentrated sulfuric acid is outputted from the concentrated sulfuric acid output port 115. Concentrated sulfuric acid at the concentrated sulfuric acid outlet 115 is SO generated by combustion of coal 2 Is converted by a thermochemical sulfur-iodine cycle process while producing twice the molar amount of sulfuric acid in hydrogen iodide incorporated into the hydroiodic acid phase and decomposed into hydrogen in the hydrogen iodide decomposition column 10. The sulfuric acid decomposing tower 9 is internally provided with a sulfuric acid decomposing catalyst, and the decomposing temperature is 800-900 ℃. Concentrated sulfuric acid at 180-230 ℃ is heated and decomposed in a sulfuric acid decomposition tower 9 to generate sulfuric acid decomposition gas at 800-900 ℃. Sulfuric acidThe high-temperature decomposed gas of the decomposing column 9 is fed into the sulfuric acid concentration column 11 from the sulfuric acid decomposed gas inlet 113, is discharged from the sulfuric acid concentration column 11 from the sulfuric acid decomposed gas outlet 114, and mainly contains O at a temperature of 200 to 250 DEG C 2 And the sulfuric acid decomposition gas from Bunsen column 15 contains mainly SO 2 Mixing the gases, wherein the temperature is 150-200 ℃ and the mixture mainly contains SO 2 And O 2 Is fed into the oxycombustion furnace 1 from the third inlet 28.
The hydroiodic acid phase is transferred from the hydroiodic acid phase storage tank 18 to the hydroiodic acid purification tank 17, and the product SO is purified 2 Returned to Bunsen column 15. Pure hydroiodic acid and dissolved iodine are fed from a hydroiodic acid inlet 161 to a hydroiodic acid concentration column 16, the concentration of the hydroiodic acid is concentrated from 10% to 30% to 55% to 57%, and the concentrated hydroiodic acid is output from a concentrated hydroiodic acid outlet 162. The concentrated hydroiodic acid is fed to the hydrogen iodide decomposition column 10. The hydrogen iodide decomposition tower 10 is internally provided with a hydrogen iodide decomposition catalyst, and hydrogen iodide is decomposed into hydrogen and iodine vapor at 400-600 ℃. The hydrogen iodide decomposition gas at 400-600 ℃ is delivered from the hydrogen iodide decomposition gas inlet 163 to the hydrogen iodide concentration tower 16 to supply heat to the hydrogen iodide concentration tower 16, and is delivered from the hydrogen iodide decomposition gas outlet 164 to the hydrogen iodide concentration tower 16, and the temperature is reduced to 80-90 ℃. And then into a gas-liquid separator 19. Hydrogen iodide, water and iodine in the hydrogen iodide decomposition gas are condensed into a hydroiodic acid complex solution, which is sent to the Bunsen column 15 from an iodine/hydroiodic acid outlet 192, and hydrogen in the hydrogen iodide decomposition gas is sent from a hydrogen outlet 191.
The heat of the oxygen-enriched combustion furnace 1 is respectively used for the heat supply and power generation processes of the thermochemical sulfur-iodine cycle hydrogen production process through helium circulation and steam circulation. The helium gas circulation process is as follows: helium gas is heated to 850-1000 ℃ in the oxygen-enriched combustion furnace 1, firstly enters the sulfuric acid decomposition tower 9 to provide a reaction environment and reaction heat at 800-900 ℃ for sulfuric acid decomposition, and then enters the hydrogen iodide decomposition tower 10 to provide a reaction environment at 400-600 ℃ for hydrogen iodide decomposition after the helium gas temperature is reduced to 500-600 ℃, and the helium gas temperature is further reduced to 350-500 ℃. Thereafter, helium is circulated back to the oxycombustion furnace 1 and the temperature is raised to 850-1000 ℃. The steam cycle comprises the following steps: the boiler water is sent into the oxygen-enriched combustion furnace 1 from the boiler water inlet 29, and the boiler water absorbs heat and is vaporized and superheated into superheated steam with the temperature of 400-600 ℃ to be heatedThe volume expansion in the process of stove water vaporization and temperature rising, the pressure of the steam absorbing heat at high temperature is increased from 0.1MPa to 3-30 MPa, medium-high pressure steam is discharged from a medium-high pressure steam outlet 30 to an oxycombustion boiler 1 and pushes a high-pressure turbine 31 to generate power, power is output from a power output end 33, the pressure and the temperature of the medium-high pressure steam are respectively reduced to 2-5 MPa and 300-500 ℃, the steam is returned to the oxycombustion boiler 1 to reheat, the pressure and the temperature after reheating are respectively reduced to 2-5 MPa and 400-600 ℃, the reheat steam enters a medium-pressure turbine 32 to generate power, the pressure and the temperature after reheating are respectively reduced to 0.1-1 MPa and 120-150 ℃, then the waste heat is recycled from a waste heat steam inlet 71 to a waste heat recoverer 7, and part of the heat is used for recovering 8 excessive SO 2 The temperature is increased from 60 ℃ to 80 ℃ to 110 ℃ to 140 ℃, and then the mixture is mixed with sulfuric acid decomposed gas at 200 ℃ to 250 ℃ to become mixed gas at 150 ℃ to 200 ℃, and the rest heat is used for providing hot water for a park. The reheat steam is condensed into 80-90 ℃ boiler water after heat release, then flows out from a condensate water outlet 72, and returns to the oxyfuel combustion furnace 1 through a boiler water inlet 29, thereby completing a steam cycle.
In order to control the flame temperature and the combustion time of fuel combustion, the existing oxygen-enriched combustion technology usually adopts circulating flue gas to dilute O 2 Is to CO 2 The heat capacity and emissivity of (c) are greatly different from those of air, resulting in a reduction in the circulating heat flow of the boiler. The application sends the sulfuric acid decomposition gas generated by sulfuric acid decomposition into the oxygen-enriched combustion furnace 1, and the components and the mole ratio of the sulfuric acid decomposition gas are about SO 2 ：H 2 O：O 2 The oxygen content of the oxygen-enriched combustion furnace is equivalent to that of air, the molar ratio of water vapor is up to 40%, and the heat flow density and the incineration capacity of the oxygen-enriched combustion furnace 1 are greatly improved. The coal and sulfuric acid decomposition gas are equal to the mixed combustion in the oxygen-enriched combustion furnace 1, and mainly produce CO 2 At the same time produce water, SO 2 And NO x The flue gas temperature is raised to not lower than 1100 ℃. SO is generated by the coal combustion process 2 SO entering Bunsen column 15 2 Always in excess of the molar amount required for the Bunsen reaction, excess SO 2 More sulfuric acid and hydroiodic acid are produced after absorption, wherein the additionally produced sulfuric acid is produced as concentrated sulfuric acid, and more hydroiodic acid is produced after decompositionIs a hydrogen gas of (a). Unabsorbed SO in Bunsen column 15 2 、CO 2 And NO X Is withdrawn from the top of Bunsen column 15.
Water and SO are used in Bunsen tower 15 2 And iodine is used as raw material, and mixed acid solution of sulfuric acid and hydroiodic acid is produced by reaction. Iodine is cyclic iodine generated by decomposition of hydriodic acid. The water mainly comes from the oxygen-enriched combustion flue gas, water generated by decomposition of sulfuric acid and water generated by combustion of coal, is condensed in a flue gas condenser and returned to the Bunsen tower 15, insufficient water is replenished through a pure water inlet 151 of the Bunsen tower 15, and if the water quantity is excessive, the water is discharged from an excessive water outlet 41. SO (SO) 2 The gas comes from sulfuric acid decomposition and coal combustion. SO (SO) 2 The gas is absorbed by the Bunsen tower 15, the unabsorbed gas is pumped out from the top of the tower by an axial flow fan, the latent heat of the waste heat steam is absorbed in a waste heat recoverer, the temperature is increased from 60 ℃ to 80 ℃ to 110 ℃ to 140 ℃, and then the gas is mixed with the sulfuric acid decomposition gas with heat recovered in the sulfuric acid concentration tower to enter the oxygen-enriched combustion furnace 1, and the temperature of the oxygen-containing gas entering the oxygen-enriched combustion furnace 1 is 150 ℃ to 200 ℃. The temperature of the waste heat steam in the waste heat recoverer is reduced from 120-150 ℃ to 80-90 ℃, condensed into water, and then sent into a boiler to be heated and boosted again. The heat of the waste heat steam is far higher than SO 2 The heat required by gas heating is used for providing hot water at 70-90 ℃ by redundant waste heat steam, and can be used for heat supply, cold supply and living use in a park.
The mixed acid solution produced in the Bunsen tower 15 enters a layering tower, layering occurs due to the density difference of sulfuric acid and hydriodic acid, the sulfuric acid phase containing hydriodic acid impurities at the upper layer is input into a sulfuric acid phase storage tank, and the hydriodic acid phase containing sulfuric acid impurities at the lower layer is input into a hydriodic acid phase storage tank. The sulfuric acid in the sulfuric acid phase storage tank is sent into a sulfuric acid purification tower to generate Bunsen reverse reaction or side reaction, and the hydroiodic acid and sulfuric acid are consumed to generate SO 2 Or H 2 The S gas is returned to Bunsen column 15. The purified sulfuric acid phase is input into a sulfuric acid concentration tower, the concentration of the sulfuric acid is increased from 30% -60% to 95% -98%, and the distilled water vapor is sent to a liquid separator. The heat of the sulfuric acid decomposition gas is recovered by the sulfuric acid concentration tower, the temperature of the sulfuric acid decomposition gas is reduced from 800 ℃ to 900 ℃ to 200 ℃ to 250 ℃, and the temperature of the concentrated sulfuric acid discharged by the sulfuric acid concentration tower is 180 ℃ to 230 ℃. Concentrate sent to sulfuric acid decomposing towerThe flow rate of sulfuric acid is constant, and the amount of oxygen generated by decomposition of the sulfuric acid is required to be matched with the fuel combustion amount of the oxygen-enriched combustion furnace 1. SO generated by fuel combustion process 2 The gas is supplemented into thermochemical sulfur-iodine circulation, the flow of the concentrated sulfuric acid discharged from the sulfuric acid concentration tower exceeds the required decomposition amount, and the excessive concentrated sulfuric acid is output from a concentrated sulfuric acid output port as a byproduct, so that the purity is higher, and the concentrated sulfuric acid does not contain impurities. At the same time, 2mol HI is produced more per 1mol sulfuric acid produced, and further converted into 1mol H 2 The actual yield of hydrogen is improved without increasing the cost.
The sulfuric acid decomposing catalyst is arranged in the sulfuric acid decomposing tower, circulating helium from the oxygen-enriched combustion furnace 1 is used as a heat source, concentrated sulfuric acid is introduced from the bottom, and is heated and gasified first and decomposed into steam and SO 3 ，SO 3 Decomposition to SO at the catalyst surface 2 And O 2 . After the circulating helium releases heat in the sulfuric acid decomposition tower, the temperature is reduced from 850 ℃ to 1000 ℃ to 500 ℃ to 600 ℃, then the circulating helium enters the hydrogen iodide decomposition tower to provide a reaction environment of 400 ℃ to 600 ℃ for hydrogen iodide decomposition, the temperature of the circulating helium is further reduced to 350 ℃ to 500 ℃ and the circulating helium is returned to the oxygen-enriched combustion furnace 1 for heating and heating.
The hydriodic acid phase contains excessive iodine and sulfuric acid impurity, and is transferred from the hydriodic acid phase storage tank to the hydriodic acid purifying tank, and the hydriodic acid is purified through Bunsen reverse reaction to convert sulfuric acid impurity into SO 2 Gas or other material and separated from the hydroiodic acid. SO generated during purification 2 Or H 2 The S gas and sulfuric acid purified product is returned to Bunsen column 15. The purified hydroiodic acid is stripped and concentrated in a hydroiodic acid concentration tower and finally is delivered to a hydrogen iodide decomposition tower to be decomposed into hydrogen and iodine. The hydrogen iodide decomposition product contains hydrogen, iodine, water and unretracted hydrogen iodide gas, the hydrogen iodide decomposition mixed gas is sent into a hydriodic acid concentration tower to recover heat, the temperature of the hydrogen iodide decomposition mixed gas is reduced from 400 ℃ to 600 ℃ to 80 ℃ to 90 ℃, the iodine, the water and the unretracted hydrogen iodide gas in the hydrogen iodide decomposition mixed gas are condensed into a hydriodic acid solution, wherein the iodine simple substance and the hydrogen iodide form HI x A complex. Delivering cooled hydrogen iodide decomposition product into gas-liquid separator, outputting hydrogen from hydrogen outlet, and obtaining hydriodic acid solutionCarry iodine back to Bunsen column 15.
The system of the application converts sulfur in coal into high-purity concentrated sulfuric acid to be produced and extra hydrogen to be produced, iodine circulation realizes the hydrogen production purpose of thermochemical sulfur-iodine circulation process, carbon dioxide trapping system realizes zero carbon emission of oxygen-enriched combustion, and finally converts water and coal into hydrogen, electric energy, heat energy and high-purity CO 2 And by-producing high-purity concentrated sulfuric acid.
Example 1
The oxygen-enriched combustion fuel is selected from coal mine coking coal in black pond in six-branch mining area of Guizhou, the coal is high sulfur coal, after coal dust is produced, a small amount of defoamer, pH regulator, enzyme inhibitor, surface modifier and accelerator are added, after water is mixed, the mixture is stirred to produce coal-containing water slurry with about 65% of coal, about 34% of water and 1% of additive as oxygen-enriched combustion fuel, and the total sulfur content of the water slurry is about 2.6%. By adopting the process scheme shown in FIG. 1, iodine solid particles 11.5t, water 10t and SO are slowly added into a Bunsen tower 2 500m of gas 3 Realize the start-up operation of the sulfur-iodine circulating system. The oxygen-enriched combustion furnace is an air staged combustion furnace with a front hearth, and after sulfuric acid decomposition gas is sent into the oxygen-enriched combustion furnace, the feeding amount of the coal water slurry is gradually increased and stabilized at 0.6 t/h, so that the stable operation of the system is finally achieved. Under rated working condition, the hydrogen yield of the system is about 1000m 3 The power generation power is about 2.5kW, the Bunsen tower is supplemented with purified water at about 600kg/h, and CO is trapped 2 About 1t/h, and about 48kg/h of byproduct concentrated sulfuric acid.
While embodiments of the present application have been illustrated and described above, it will be appreciated that the above described embodiments are illustrative and should not be construed as limiting the application. The present application is subject to various changes and modifications without departing from the spirit and scope thereof, and such changes and modifications fall within the scope of the application as hereinafter claimed.
Claims (10)
1. The oxygen-enriched combustion coupled thermochemical sulfur-iodine circulating system comprises an oxygen-enriched combustion furnace (1) and a sulfur-iodine circulating unit, wherein a mixed acid outlet (152) of a Bunsen tower (15) of the sulfur-iodine circulating unit is connected with a layering tower (14), the back of the layering tower (14) is divided into two paths, and one path is led out from the middle upper part of the layering tower (14)The device is sequentially connected with a sulfuric acid purification tower (12), a sulfuric acid concentration tower (11) and a sulfuric acid decomposition tower (9), and the other device is communicated with the middle lower part of a routing layering tower (14) and is sequentially connected with a hydroiodic acid purification tank (17), a hydroiodic acid concentration tower (16) and a hydrogen iodide decomposition tower (10); the method is characterized in that: a helium circulation pipeline (25) for transferring heat is sequentially connected with the oxygen-enriched combustion furnace (1), the sulfuric acid decomposition tower (9) and the hydrogen iodide decomposition tower (10) to form a circulation loop; the oxygen-enriched combustion furnace (1) is provided with a first inlet (26) for introducing fuel and a second inlet for introducing SO-containing gas 2 、O 2 And a third inlet (28) of the circulating gas of water, the circulating gas is returned to the sulfuric acid concentration tower (11) from the sulfuric acid decomposition gas generated by the sulfuric acid decomposition tower (9), and then is discharged from the Bunsen tower (15) to contain SO after heat exchange and temperature reduction 2 Is obtained by mixing the gases of the above steps; the oxygen-enriched combustion furnace (1) is connected with a flue gas treatment separation unit, the temperature and pressure changing adsorption and desorption device of the flue gas treatment separation unit comprises a plurality of sub-paths which are connected in parallel, at least one adsorption and desorption tower is arranged in each sub-path, porous adsorption materials are filled in the adsorption and desorption towers, and at least one sub-path is used for SO at the same time 2 Adsorption and at least one sub-path for SO 2 Desorption, adsorption and desorption of separated SO 2 Is fed to Bunsen column (15).
2. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the oxygen-enriched combustion furnace (1) is provided with a fourth inlet (29) for introducing boiler water, a boiler flue gas outlet (27) for discharging oxygen-enriched combustion flue gas and a medium-high pressure steam outlet (30) for discharging medium-high pressure steam; the medium-high pressure steam generated by heat exchange between boiler water and high-temperature flue gas is discharged out of the oxygen-enriched combustion furnace (1) and then pushes a high-pressure turbine (31) to generate power and output power, the medium-high pressure steam is cooled and depressurized after acting and is sent back to the oxygen-enriched combustion furnace (1) to reheat, the reheat steam is discharged out of the oxygen-enriched combustion furnace (1) and then pushes a medium-pressure turbine (32) to generate power and output power, and the reheat steam is cooled and depressurized after acting and is sent to a waste heat recoverer (7) and is communicated with main SO-containing discharged by a Bunsen tower (15) 2 Condensed water generated by condensing steam in the waste heat recoverer (7) passes through a fourth inlet (29)And returning the oxygen-enriched combustion furnace (1) to continuously exchange heat so as to form a steam cycle.
3. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the temperature and pressure changing adsorption and desorption device comprises two sub-paths connected in parallel, wherein two adsorption and desorption towers connected in series are arranged in each sub-path, the adsorption and desorption towers are respectively a first adsorption and desorption tower (20) and a third adsorption and desorption tower (22), and a second adsorption and desorption tower (21) and a fourth adsorption and desorption tower (23) of the other sub-path, and the adsorption and desorption operations are alternately carried out on the two sub-paths.
4. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the adsorption and desorption tower is filled with one or more porous adsorption materials selected from activated carbon, molecular sieve and zeolite.
5. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the flue gas treatment separation unit comprises a dust remover (2), a flue gas heat exchanger (3), a flue gas condenser (4), a variable-temperature and variable-pressure adsorption and desorption device and a denitration tower (5) which are sequentially connected, wherein dry flue gas obtained by sequentially carrying out dust removal, heat exchange and condensation treatment on oxygen-enriched combustion flue gas enters the variable-temperature and variable-pressure adsorption and desorption device, and SO (sulfur dioxide) separated by adsorption and desorption is adsorbed and desorbed 2 Supplying sulfur-iodine circulation unit to participate in Bunsen reaction, and residual CO 2 And NO X After entering a denitration tower (5) for treatment, the pure CO is finally obtained 2 。
6. The oxycombustion coupled thermochemical sulfur-iodine recycle system according to claim 5, wherein: in the denitration tower (5), hydrogen peroxide is used as an oxidation absorbent, and NO X After oxidation, the mixture is dissolved in hydrogen peroxide to generate nitric acid, and finally pure CO is obtained 2 Is pressurized by a first booster fan (6) and then is used for conveying or sealing.
7. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein:
the sulfuric acid purification tower (12) and the hydroiodic acid purification tank (17) are also respectively and directly connected with the Bunsen tower (15), a hydrogen iodide decomposition gas outlet (164) of the hydroiodic acid concentration tower (16) and the sulfuric acid concentration tower (11) are also respectively connected with a gas-liquid separator (19), and an iodine/hydroiodic acid outlet (192) of the gas-liquid separator (19) is connected with the Bunsen tower (15).
8. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the concentrated sulfuric acid outlet (112) of the sulfuric acid concentration tower (11) is connected with the sulfuric acid decomposition tower (9), the connecting pipeline is further provided with a concentrated sulfuric acid production outlet (115), the sulfuric acid decomposition tower (9) is further provided with a pipeline for discharging sulfuric acid decomposition gas, the sulfuric acid concentration tower is connected with the sulfuric acid decomposition gas inlet (113) of the sulfuric acid concentration tower (11), heat is supplied for sulfuric acid concentration by heat exchange, the sulfuric acid decomposition gas after heat exchange is led out from the sulfuric acid decomposition gas outlet (114) and is mixed with gas from the Bunsen tower (15) after heat exchange and temperature rise in the waste heat recoverer (7), and then the mixed gas is sent into the oxygen-enriched combustion furnace (1) from the third inlet (28).
9. The oxycombustion coupled thermochemical sulfur-iodine cycle system of claim 1, wherein: the concentrated hydroiodic acid outlet (162) of the hydroiodic acid concentration tower (16) is connected with the hydrogen iodide decomposition tower (10), the hydrogen iodide decomposition tower (10) is also provided with a pipeline for discharging hydrogen iodide decomposition gas and is connected with the hydrogen iodide decomposition gas inlet (163) of the hydroiodic acid concentration tower (16), heat exchange is carried out for concentrating the hydroiodic acid to supply heat, the hydrogen iodide decomposition gas after heat exchange is led out by the hydrogen iodide decomposition gas outlet (164), then enters the gas-liquid separator (19), the gas is condensed in the gas-liquid separator (19) and then is discharged from the iodine/hydroiodic acid outlet (192), and the residual gas is sent out from the hydrogen outlet (191) to obtain the product hydrogen.
10. Process for the oxyfuel combustion coupled with the thermochemical sulfur-iodine cycle, operating a system according to any one of claims 1 to 9, characterized in that: s1, the method comprises the steps of (1),the method comprises the steps of (1) burning circulating gas and fuel in an oxygen-enriched combustion furnace, returning sulfuric acid decomposition gas generated by a sulfuric acid decomposition tower (9) to a sulfuric acid concentration tower (11), exchanging heat and cooling, and then discharging the circulating gas and the fuel with a Bunsen tower (15) to contain SO 2 150-200 ℃ gas obtained by mixing the gases of the fuel, and the products of combustion of the fuel comprise CO 2 Water, SO 2 And NOx, the temperature of the flue gas rises to not lower than 1100 ℃ during combustion;
s2, exchanging heat of combustion flue gas, namely exchanging heat of the flue gas generated by combustion with a helium gas circulation pipeline (25) and a steam circulation pipeline in the oxygen-enriched combustion furnace (1), heating helium gas from 350-500 ℃ to 850-1000 ℃, heating high-pressure circulation steam and low-pressure circulation steam to 350-450 ℃, and discharging the flue gas from a flue gas outlet (27) of the boiler after the temperature of the flue gas is reduced to 140-220 ℃;
s3, flue gas treatment and separation, namely, flue gas is subjected to dust removal, heat exchange and temperature reduction to 30-50 ℃, separated and dehydrated and then sent to a variable-temperature and variable-pressure adsorption and desorption device, and a plurality of sub-paths alternately perform SO (sulfur dioxide) 2 Adsorption and SO 2 Desorption, adsorption and desorption of separated SO 2 Feeding Bunsen column (15) to participate in Bunsen reaction, and collecting high-purity CO as the rest component 2 The mixture is pressurized and then is used for conveying, sealing or utilizing;
s4, sulfur-iodine circulation, SO 2 Water and iodine are subjected to Bunsen reaction in a Bunsen tower (15) to generate a mixed acid solution of sulfuric acid and hydroiodic acid, the mixed acid solution is sent to a layering tower (14) for layering, a lower sulfuric acid phase is sent to a sulfuric acid phase storage tank (13) from a sulfuric acid phase outlet (141), and an upper hydroiodic acid phase is sent to a hydroiodic acid phase storage tank (18) from a hydroiodic acid phase outlet (142); the sulfuric acid is decomposed to generate sulfuric acid decomposed gas at 800-900 ℃ after being purified and concentrated in turn, and the hydroiodic acid is decomposed to hydrogen and iodine vapor at 400-600 ℃ after being purified and concentrated in turn.
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