CN116099342A - System and method for boiler flue gas desulfurization and carbon dioxide resource utilization - Google Patents
System and method for boiler flue gas desulfurization and carbon dioxide resource utilization Download PDFInfo
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- CN116099342A CN116099342A CN202310112535.7A CN202310112535A CN116099342A CN 116099342 A CN116099342 A CN 116099342A CN 202310112535 A CN202310112535 A CN 202310112535A CN 116099342 A CN116099342 A CN 116099342A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 162
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 239000003546 flue gas Substances 0.000 title claims abstract description 147
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 81
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 81
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 26
- 230000023556 desulfurization Effects 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 71
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 68
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000001502 supplementing effect Effects 0.000 claims abstract description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013049 sediment Substances 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000004064 recycling Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 13
- 238000007599 discharging Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
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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
- B01D53/34—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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- 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
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur 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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/03—Acyclic or carbocyclic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention discloses a system and a method for boiler flue gas desulfurization and carbon dioxide resource utilization, wherein the system comprises a boiler flue, a flue gas booster fan, a flue gas washing device, a carbon dioxide absorbing device, a water supplementing device, a sediment treatment device and a sulfurous acid pump; the boiler flue is a flue after boiler denitration and dust removal, the outlet of the boiler flue is connected to the inlet of a flue gas booster fan, the outlet of the flue gas booster fan is connected to the first inlet of a flue gas washing device, the outlet of a water supplementing device is connected to the second inlet of the flue gas washing device, the first outlet of the flue gas washing device is connected to the first inlet of a carbon dioxide absorbing device, the second outlet of the flue gas washing device is connected to the inlet of a thionic acid pump, and the third outlet of the flue gas washing device is connected to the inlet of a sediment treatment device. The method utilizes the pollution waste gas sulfur dioxide in the boiler flue gas as a resource, generates industrial product sulfuric acid and generates clean energy hydrogen; no additional carbon emissions etc. are generated during the sulfur dioxide removal process.
Description
Technical Field
The invention belongs to the technical fields of hydrogen preparation, carbon dioxide electrochemical reduction and boiler environmental protection, and particularly relates to a system and a method for boiler flue gas desulfurization and carbon dioxide resource utilization.
Background
The boiler burns sulfur-containing coal to produce sulfur dioxide and carbon dioxide. The emission of sulfur dioxide to the atmosphere causes atmospheric pollution, and carbon dioxide emission increases carbon emission.
The boiler flue gas adopts desulfurization measures to eliminate sulfur dioxide in the flue gas, at present, a main flue gas desulfurization device needs to utilize calcium hydroxide, the calcium hydroxide is obtained by pyrolysis of calcium carbonate, carbon dioxide is generated while the calcium hydroxide is obtained, meanwhile, the operation cost of a desulfurization system is higher, and the economic value of byproducts such as gypsum and the like is lower.
The technology of capturing carbon dioxide is also a hot spot of current research, but no economically feasible capturing scheme or an economically feasible carbon dioxide utilization scheme is found at present.
Disclosure of Invention
The invention aims to solve the problems of sulfur dioxide removal and carbon dioxide emission in the prior coal-fired boiler flue gas emission, and provides a system and a method for boiler flue gas desulfurization and carbon dioxide resource utilization.
The invention is realized by adopting the following technical scheme:
a system for boiler flue gas desulfurization and carbon dioxide resource utilization comprises a boiler flue, a flue gas booster fan, a flue gas washing device, a carbon dioxide absorbing device, a water supplementing device, a sediment treatment device and a sulfurous acid pump;
the boiler flue is a flue after boiler denitration and dust removal, the outlet of the boiler flue is connected to the inlet of a flue gas booster fan, the outlet of the flue gas booster fan is connected to the first inlet of a flue gas washing device, the outlet of a water supplementing device is connected to the second inlet of the flue gas washing device, the first outlet of the flue gas washing device is connected to the first inlet of a carbon dioxide absorbing device, the second outlet of the flue gas washing device is connected to the inlet of a thionic acid pump, and the third outlet of the flue gas washing device is connected to the inlet of a sediment treatment device.
The invention is further improved in that the water replenishing device provides water with pressure, and the water is sprayed into the flue gas washing device from top to bottom through an atomizing nozzle arranged at the upper part of the flue gas washing device.
The invention is further improved in that the flue gas at the outlet of the flue gas booster fan is introduced into the flue gas washing device from top to bottom through the flow equalizing plate arranged at the upper part of the flue gas washing device.
The invention is further improved in that the first outlet of the flue gas washing device is arranged at the top of the flue gas washing device, the second outlet of the flue gas washing device is arranged at the lower part of the flue gas washing device, and the third outlet of the flue gas washing device is arranged at the bottom of the flue gas washing device.
The invention is further improved in that the invention also comprises an electrochemical workstation, an anode chamber, an anolyte collecting device and a sulfuric acid concentration collecting device;
the output of the electrochemical workstation is a direct current power supply, the anode of the electrochemical workstation is connected to an anode, the anode is arranged in an anode chamber to provide electric energy for the anode chamber, the anode chamber consists of a runner layer, a diffusion layer and a catalyst layer, the outlet of a sulfurous acid pump is connected to the inlet of the anode chamber, the inlet of the anode chamber is connected with the inlet of the runner layer of the anode chamber, the outlet of the runner layer of the anode chamber is connected with the first outlet of the anode chamber, the first outlet of the anode chamber is connected to the inlet of an anode electrolyte collecting device, the first outlet of the anode electrolyte collecting device is connected to the third inlet of a flue gas washing device, and the second outlet of the anode electrolyte collecting device is connected to the inlet of a sulfuric acid concentration collecting device.
The invention is further improved in that the invention also comprises a cathode chamber, an electrolyte catholyte separating device, a preparation collecting device and a gas discharging device;
the cathode of the electrochemical workstation is connected to the cathode, the cathode is arranged in a cathode chamber to provide electric energy for the cathode chamber, the cathode chamber consists of a runner layer, a diffusion layer and a catalyst layer, a first outlet of a carbon dioxide absorbing device is arranged at an inlet of the cathode chamber, the inlet of the cathode chamber is connected with a runner layer inlet of the cathode chamber, a runner layer outlet of the cathode chamber is connected with a first outlet of the cathode chamber, the first outlet of the cathode chamber is connected to an inlet of an electrolyte catholyte separating device, the first outlet of the electrolyte catholyte separating device is connected to an inlet of a preparation collecting device, a second outlet of the electrolyte catholyte separating device is connected to a second inlet of the carbon dioxide absorbing device, and a second outlet of the carbon dioxide absorbing device is connected to an inlet of a gas discharging device.
The invention is further improved in that the invention also comprises a proton membrane; the proton membrane is installed between the catalyst layer of the anode chamber and the catalyst layer of the cathode chamber, and can lead protons generated in the anode chamber to the cathode chamber while blocking the passage of other substances.
The invention is further improved in that the heating device and the cooling device are arranged in the flue gas washing device, so that the internal temperature of the flue gas washing device can be regulated to be 50-150 ℃.
The invention is further improved in that the concentration of sulfur dioxide in the flue gas washing device is determined by the water supplementing amount of the water supplementing device, the quantity of returned liquid of the anolyte collecting device and the sulfur dioxide content of flue gas of the boiler.
The method for boiler flue gas desulfurization and carbon dioxide resource utilization is based on the system for boiler flue gas desulfurization and carbon dioxide resource utilization, and comprises the following steps:
1) The flue gas containing sulfur dioxide, which is subjected to denitration and dust removal from a boiler flue, enters a flue gas washing device after being pressurized by a flue gas booster fan;
2) Sulfur dioxide in the flue gas fully contacts and reacts with atomized water from the water supplementing device and return liquid of the anolyte collecting device to generate a mixed solution of sulfurous acid and sulfuric acid;
3) The nitrogen and carbon dioxide gas with smaller solubility in the flue gas enter a carbon dioxide absorption device, and the mixed solution of sulfurous acid and sulfuric acid enters an anode chamber through a sulfurous acid pump;
4) The mixed solution entering the anode chamber is electrified for electrolysis under the action of a catalyst to generate H + 、e - And sulfuric acid, H+ enters the cathode chamber through the proton membrane, e - The cathode is reached by an electrochemical workstation;
5) The solution which consumes sulfur dioxide and generates sulfuric acid enters an anolyte collecting device, and the solution in the anolyte collecting device returns to a flue gas washing device to start the next cycle of circulation, absorption and electrolysis;
6) Along with the circulation, the concentration of sulfuric acid in the anolyte collecting device is gradually increased, and according to the process requirement, a part of sulfuric acid enters the sulfuric acid concentration collecting device;
7) The nitrogen and carbon dioxide gas with smaller solubility in the flue gas enter a carbon dioxide absorbing device, carbon dioxide is absorbed by electrolyte solution, and the rest of the gas enters a flue gas discharging device to be discharged after reaching the standard;
8) The catholyte absorbing carbon dioxide enters a cathode chamber, under the action of a catalyst, the carbon dioxide and H+ penetrating into the cathode chamber from a proton membrane reach a cathode e-reaction through an electrochemical workstation to generate a preparation, the preparation consists of C, O, H atoms with different numbers, and different electrolytes, catalysts and reaction conditions generate different preparations;
9) After the mixture of the preparation and the anionic electrolyte flows out of the cathode chamber, the mixture enters a catholyte separating device, the anionic electrolyte is separated and returns to the carbon dioxide absorbing device again to start the next cycle, and the preparation enters a preparation collecting device.
The invention has at least the following beneficial technical effects:
the system and the method for boiler flue gas desulfurization and carbon dioxide resource utilization have the following obvious advantages:
(1) Sulfur dioxide in the boiler flue gas is removed;
(2) The method comprises the steps of recycling the sulfur dioxide in the pollution waste gas in the boiler flue gas to generate industrial product sulfuric acid and clean energy hydrogen (H+);
(3) No additional carbon emissions are produced during sulfur dioxide removal;
(4) Carbon dioxide in the boiler flue gas is captured;
(5) H+ and e-generated by depolarized electrolysis of sulfur dioxide are directly transmitted to electrocatalytic reduction of carbon dioxide, so that the efficiency of carbon dioxide reduction is improved, and the energy consumption of carbon dioxide reduction is reduced;
(6) The carbon dioxide is prepared into high-value industrial products such as potassium formate, formic acid, methane, acetone and the like, so that the recycling utilization of the carbon dioxide is realized;
(7) The method can utilize the boiler flue gas, electric energy and heat energy of the coal-fired power plant, improve the operation flexibility of the coal-fired power plant and improve the peak regulation capacity of the coal-fired power plant;
(8) The method has the advantages of high desulfurization and carbon dioxide trapping efficiency, low energy consumption and good economy.
Drawings
FIG. 1 is a block diagram of a system for boiler flue gas desulfurization and carbon dioxide recycling in accordance with the present invention.
Reference numerals illustrate:
1. the boiler comprises a boiler flue, 2 parts of a flue gas booster fan, 3 parts of a flue gas washing device, 4 parts of a thionic acid pump, 5 parts of an anode chamber, 6 parts of an anode, 7 parts of a proton membrane, 8 parts of a cathode chamber, 9 parts of a cathode, 10 parts of an electrochemical workstation, 11 parts of a carbon dioxide absorbing device, 12 parts of an electrolyte collecting device, 13 parts of a sulfuric acid concentration collecting device, 14 parts of a sediment treatment device, 15 parts of a preparation collecting device, 16 parts of a flue gas discharging device, 17 parts of a water supplementing device, 18 parts of a catholyte separating device.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The invention will be described in detail below with reference to the drawings in connection with embodiments.
As shown in fig. 1, the system for boiler flue gas desulfurization and carbon dioxide recycling provided by the invention comprises a boiler flue 1, a flue gas booster fan 2, a flue gas washing device 3, a carbon dioxide absorbing device 11, a water supplementing device 17, a sediment treatment device 14, a sulfurous acid pump 4, an electrochemical workstation 10, an anode 6, an anode chamber 5, an anolyte collecting device 12, a sulfuric acid concentration collecting device 13, a cathode chamber 8, an electrolyte catholyte separating device 18, a preparation collecting device 15, a gas discharging device 16 and a proton membrane 7.
The boiler flue 1 is a flue after boiler denitration and dust removal, the outlet of the flue is connected to the inlet of a flue gas booster fan 2, the outlet of the flue gas booster fan 2 is connected to the first inlet of a flue gas washing device 3, the outlet of a water supplementing device 17 is connected to the second inlet of the flue gas washing device 3, the first outlet of the flue gas washing device 3 is connected to the first inlet of a carbon dioxide absorbing device 11, the second outlet of the flue gas washing device 3 is connected to the inlet of a sulfurous acid pump 4, and the third outlet of the flue gas washing device 3 is connected to the inlet of a sediment treatment device 14; the output of the electrochemical workstation 10 is a direct current power supply, the anode of the electrochemical workstation is connected to an anode 6, the anode 6 is arranged in an anode chamber 5 to provide electric energy for the anode chamber 5, the anode chamber 5 consists of a runner layer, a diffusion layer and a catalyst layer, the outlet of a sulfurous acid pump 4 is connected to the inlet of the anode chamber 5, the inlet of the anode chamber 5 is connected with the inlet of the runner layer of the anode chamber 5, the outlet of the runner layer of the anode chamber 5 is connected with the first outlet of the anode chamber 5, the first outlet of the anode chamber 5 is connected to the inlet of an anode electrolyte collecting device 12, the first outlet of the anode electrolyte collecting device 12 is connected to the third inlet of the flue gas washing device 3, and the second outlet of the anode electrolyte collecting device 12 is connected to the inlet of a sulfuric acid concentration collecting device 13; the cathode 9 is arranged in the cathode chamber 8 to provide electric energy for the cathode chamber 8, the cathode chamber 8 is composed of a runner layer, a diffusion layer and a catalyst layer, a first outlet of a carbon dioxide absorbing device 11 is arranged at an inlet of the cathode chamber 8, the inlet of the cathode chamber 8 is connected with the runner layer inlet of the cathode chamber 8, a runner layer outlet of the cathode chamber 8 is connected with the first outlet of the cathode chamber 8, the first outlet of the cathode chamber 8 is connected with an inlet of an electrolyte catholyte separating device 18, the first outlet of the electrolyte catholyte separating device 18 is connected with an inlet of a preparation collecting device 15, a second outlet of the electrolyte catholyte separating device 18 is connected with a second inlet of the carbon dioxide absorbing device 11, a second outlet of the carbon dioxide absorbing device 11 is connected with an inlet of a gas discharging device 16; the proton membrane 7 is installed between the catalyst layer of the anode chamber 5 and the catalyst layer of the cathode chamber 8, and can guide protons generated in the anode chamber 5 to the cathode chamber 8 while blocking the passage of other substances.
Wherein the water replenishing device 17 provides pressurized water which is sprayed into the flue gas washing device 3 from top to bottom through an atomizing nozzle mounted at the upper part of the flue gas washing device 3.
The flue gas at the outlet of the flue gas booster fan 2 is introduced into the flue gas washing device 3 from top to bottom through a flow equalizing plate arranged at the middle upper part of the flue gas washing device 3.
The first outlet of the flue gas washing device 3 is arranged at the top of the flue gas washing device 3, the second outlet of the flue gas washing device 3 is arranged at the lower part of the flue gas washing device 3, and the third outlet of the flue gas washing device 3 is arranged at the bottom of the flue gas washing device 3.
A heating device and a cooling device are arranged in the flue gas washing device 3, so that the internal temperature can be regulated to 50-150 ℃.
The concentration of sulfur dioxide in the flue gas washing device 3 is determined by the water supplementing amount of the water supplementing device 17, the amount of returned liquid of the anolyte collecting device 12 and the content of sulfur dioxide in the flue gas of the boiler flue 1.
The invention provides a method for desulfurizing boiler flue gas and recycling carbon dioxide, which comprises the following steps:
1) The flue gas containing sulfur dioxide after denitration and dust removal from the boiler flue 1 enters a flue gas washing device 3 after being pressurized by a flue gas booster fan 2;
2) The sulfur dioxide in the flue gas fully contacts and reacts with atomized water from the water supplementing device 17 and return liquid of the anolyte collecting device 12 to generate a mixed solution of sulfurous acid and sulfuric acid;
3) The nitrogen and carbon dioxide gas with smaller solubility in the flue gas enter a carbon dioxide absorption device 11, and the mixed solution of sulfurous acid and sulfuric acid enters an anode chamber 5 through a sulfurous acid pump 4;
4) The mixed solution entering the anode chamber 5 is electrified and electrolyzed under the action of a catalyst to generate H + 、e - And sulfuric acid, H+ enters the cathode chamber 8 through the proton membrane 7, e - The cathode 9 is reached by means of an electrochemical workstation 10;
5) The solution which consumes sulfur dioxide and generates sulfuric acid enters the anolyte collecting device 12, and the solution in the anolyte collecting device 12 returns to the flue gas washing device 3 to start the next cycle of circulation, absorption and electrolysis;
6) With the circulation, the concentration of sulfuric acid in the anolyte collecting device 12 is gradually increased, and according to the process requirement, a part of sulfuric acid enters the sulfuric acid concentration collecting device 13;
7) The nitrogen and carbon dioxide gas with smaller solubility in the flue gas enter the carbon dioxide absorbing device 11, the carbon dioxide is absorbed by the electrolyte solution, and the rest gas enters the flue gas discharging device 16 to be discharged after being treated to reach the standard;
8) Carbon dioxide absorbed catholyte enters a cathode chamber 8, under the action of a catalyst, carbon dioxide reacts with H+ permeated into the cathode chamber 8 from a proton membrane 7 and reaches a cathode 9 e-through an electrochemical workstation 10 to generate a preparation, wherein the preparation consists of C, O, H atoms with different numbers, and different electrolytes, catalysts and reaction conditions generate different preparations, and the preparation is potassium formate, formic acid, methane or acetone;
9) After the mixture of preparation and anionic electrolyte flows out of the cathode chamber 8, the mixture enters the catholyte separating device 18, the anionic electrolyte is separated and returns to the carbon dioxide absorbing device 11 again to start the next cycle, and the preparation enters the preparation collecting device 15.
Examples:
a 1000MW unit, if the sulfur content of the flue gas is 5g/m 3 The total amount of flue gas is 390 ten thousand meters 3 By adopting the technology, 29.4t/h of sulfuric acid can be prepared, and 1 ton of sulfuric acid is calculated according to 500 yuan, and the value is about 1.5 ten thousand yuan; the potassium formate can be prepared by 16.8t/h, and 1 ton of potassium formate is calculated according to 6000 yuan, and the value is about 10 ten thousand yuan. Reducing the carbon dioxide emission by 8.8t/h, and generating good social benefit. The unstable sulfur dioxide is converted into the stable sulfuric acid which can be recycled, the consumption of limestone of a desulfurization system can be reduced, and the consumption of plant power is reduced. The system adopts electricity generated by a power plant to realize depolarized electrolysis of sulfur dioxide and electrocatalytic reduction of carbon dioxide, and the heat required by the system is provided by the extraction of boiler flue gas or steam turbines of the power plant. The production of sulfuric acid and potassium formate can be increased in the electricity consumption valley period to absorb the load of the power plant, avoid the peak shaving of the unit to be too low, and improve the stability and safety of the operation of the unit.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The system for desulfurizing boiler flue gas and recycling carbon dioxide is characterized by comprising a boiler flue (1), a flue gas booster fan (2), a flue gas washing device (3), a carbon dioxide absorbing device (11), a water supplementing device (17), a sediment treatment device (14) and a thionic acid pump (4);
the boiler flue (1) is a flue after boiler denitration and dust removal, the outlet of the flue is connected to the inlet of a flue gas booster fan (2), the outlet of the flue gas booster fan (2) is connected to the first inlet of a flue gas washing device (3), the outlet of a water supplementing device (17) is connected to the second inlet of the flue gas washing device (3), the first outlet of the flue gas washing device (3) is connected to the first inlet of a carbon dioxide absorbing device (11), the second outlet of the flue gas washing device (3) is connected to the inlet of a sulfurous acid pump (4), and the third outlet of the flue gas washing device (3) is connected to the inlet of a sediment treatment device (14).
2. A system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 1, characterized in that the water supplementing device (17) provides water with pressure, which is sprayed in the flue gas washing device (3) from top to bottom through an atomizing nozzle arranged at the upper part of the flue gas washing device (3).
3. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 1, wherein flue gas at the outlet of the flue gas booster fan (2) is introduced into the flue gas washing device (3) from top to bottom through a flow equalizing plate arranged at the upper middle part of the flue gas washing device (3).
4. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 1, wherein the first outlet of the flue gas washing device (3) is arranged at the top of the flue gas washing device (3), the second outlet of the flue gas washing device (3) is arranged at the lower part of the flue gas washing device (3), and the third outlet of the flue gas washing device (3) is arranged at the bottom of the flue gas washing device (3).
5. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 1, further comprising an electrochemical workstation (10), an anode (6), an anode chamber (5), an anolyte collecting device (12) and a sulfuric acid concentration collecting device (13);
the output of the electrochemical workstation (10) is a direct current power supply, the anode of the electrochemical workstation is connected to the anode (6), the anode (6) is arranged in the anode chamber (5) to provide electric energy for the anode chamber (5), the anode chamber (5) is composed of a runner layer, a diffusion layer and a catalyst layer, the outlet of the thionic acid pump (4) is connected to the inlet of the anode chamber (5), the inlet of the anode chamber (5) is connected to the runner layer inlet of the anode chamber (5), the runner layer outlet of the anode chamber (5) is connected to the first outlet of the anode chamber (5), the first outlet of the anode chamber (5) is connected to the inlet of the anolyte collecting device (12), the first outlet of the anolyte collecting device (12) is connected to the third inlet of the flue gas washing device (3), and the second outlet of the anolyte collecting device (12) is connected to the inlet of the sulfuric acid concentration collecting device (13).
6. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 5, further comprising a cathode chamber (8), an electrolyte catholyte separation device (18), a preparation collection device (15) and a gas discharge device (16);
the cathode (9) is arranged in a cathode chamber (8) to provide electric energy for the cathode chamber (8), the cathode chamber (8) consists of a runner layer, a diffusion layer and a catalyst layer, a first outlet of a carbon dioxide absorbing device (11) is arranged at an inlet of the cathode chamber (8), the inlet of the cathode chamber (8) is connected with the runner layer inlet of the cathode chamber (8), the runner layer outlet of the cathode chamber (8) is connected with the first outlet of the cathode chamber (8), the first outlet of the cathode chamber (8) is connected with the inlet of an electrolyte cathode electrolyte separating device (18), the first outlet of the electrolyte cathode electrolyte separating device (18) is connected with the inlet of a preparation collecting device (15), a second outlet of the electrolyte cathode electrolyte separating device (18) is connected with the second inlet of the carbon dioxide absorbing device (11), and a second outlet of the carbon dioxide absorbing device (11) is connected with the inlet of a gas discharging device (16).
7. The system for boiler flue gas desulfurization and carbon dioxide resource utilization according to claim 6, further comprising a proton membrane (7); the proton membrane (7) is installed between the catalyst layer of the anode chamber (5) and the catalyst layer of the cathode chamber (8), and can lead protons generated in the anode chamber (5) to the cathode chamber (8) and block the passage of other substances.
8. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 6, wherein a heating device and a cooling device are arranged in the flue gas washing device (3), so that the internal temperature can be regulated to 50-150 ℃.
9. The system for boiler flue gas desulfurization and carbon dioxide recycling according to claim 6, wherein the concentration of sulfur dioxide in the flue gas washing device (3) is determined by the water supplementing amount of the water supplementing device (17), the amount of returned liquid of the anolyte collecting device (12) and the content of sulfur dioxide in the flue gas of the boiler flue (1).
10. A method for boiler flue gas desulfurization and carbon dioxide recycling, characterized in that the method is based on a system for boiler flue gas desulfurization and carbon dioxide recycling according to any one of claims 7 to 9, comprising the following steps:
1) flue gas containing sulfur dioxide after denitration and dust removal from a boiler flue (1) enters a flue gas washing device (3) after being pressurized by a flue gas booster fan (2);
2) Sulfur dioxide in the flue gas fully contacts and reacts with atomized water from a water supplementing device (17) and return liquid of an anolyte collecting device (12) to generate a mixed solution of sulfurous acid and sulfuric acid;
3) The nitrogen and carbon dioxide with smaller solubility in the flue gas enter a carbon dioxide absorption device (11), and a mixed solution of sulfurous acid and sulfuric acid enters an anode chamber (5) through a sulfurous acid pump (4);
4) The mixed solution entering the anode chamber (5) is electrified and electrolyzed under the action of a catalyst to generate H + 、e - And sulfuric acid, H+ enters the cathode chamber (8) through the proton membrane (7), e - The cathode (9) is reached by means of an electrochemical workstation (10);
5) The solution which consumes sulfur dioxide and generates sulfuric acid enters an anolyte collecting device (12), and the solution in the anolyte collecting device (12) returns to a flue gas washing device (3) to start the next cycle of circulation, absorption and electrolysis;
6) With the circulation, the concentration of sulfuric acid in the anolyte collecting device (12) is gradually increased, and according to the process requirement, a part of sulfuric acid enters the sulfuric acid concentration collecting device (13);
7) The nitrogen and carbon dioxide gas with smaller solubility in the flue gas enter a carbon dioxide absorbing device (11), carbon dioxide is absorbed by electrolyte solution, and the rest gas enters a flue gas discharging device (16) to be discharged after reaching the standard;
8) Carbon dioxide absorbed catholyte enters a cathode chamber (8), under the action of a catalyst, the carbon dioxide and H+ permeated into the cathode chamber (8) from a proton membrane (7) reach a cathode (9) through an electrochemical workstation (10) to perform e-reaction, so as to generate preparations, wherein the preparations consist of C, O, H atoms with different numbers, and different electrolytes, catalysts and reaction conditions generate different preparations;
9) After the mixture of the preparation and the anionic electrolyte flows out of the cathode chamber (8), the mixture enters a catholyte separating device (18), the anionic electrolyte is separated and returns to the carbon dioxide absorbing device (11) again to start the next cycle, and the preparation enters a preparation collecting device (15).
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| WO2024017053A1 (en) * | 2022-07-20 | 2024-01-25 | 深圳中科翎碳生物科技有限公司 | Ship carbon dioxide tail gas treatment system |
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