CN213416274U - Coal fired power plant thermochemical water splitting hydrogen production coupling ozone denitration device - Google Patents
Coal fired power plant thermochemical water splitting hydrogen production coupling ozone denitration device Download PDFInfo
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- CN213416274U CN213416274U CN202021888235.6U CN202021888235U CN213416274U CN 213416274 U CN213416274 U CN 213416274U CN 202021888235 U CN202021888235 U CN 202021888235U CN 213416274 U CN213416274 U CN 213416274U
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000001257 hydrogen Substances 0.000 title claims abstract description 78
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 78
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001868 water Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 230000008878 coupling Effects 0.000 title claims abstract description 12
- 238000010168 coupling process Methods 0.000 title claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 12
- 239000003245 coal Substances 0.000 title claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 63
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 52
- 239000007789 gas Substances 0.000 claims abstract description 50
- 238000005406 washing Methods 0.000 claims abstract description 38
- 238000007132 Bunsen reaction Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000010790 dilution Methods 0.000 claims abstract description 11
- 239000012895 dilution Substances 0.000 claims abstract description 11
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 7
- 239000003500 flue dust Substances 0.000 claims abstract description 7
- 239000007921 spray Substances 0.000 claims abstract description 6
- GOIGHUHRYZUEOM-UHFFFAOYSA-N [S].[I] Chemical compound [S].[I] GOIGHUHRYZUEOM-UHFFFAOYSA-N 0.000 claims description 25
- 238000000909 electrodialysis Methods 0.000 claims description 23
- 238000004821 distillation Methods 0.000 claims description 19
- 239000003546 flue gas Substances 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 15
- 238000002347 injection Methods 0.000 abstract description 10
- 239000007924 injection Substances 0.000 abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 38
- 239000000243 solution Substances 0.000 description 23
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 20
- 238000000354 decomposition reaction Methods 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 13
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 9
- 229910052740 iodine Inorganic materials 0.000 description 9
- 239000011630 iodine Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 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
- 238000011156 evaluation Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The utility model relates to a coal fired power plant thermochemical water splitting hydrogen production coupling ozone denitrification facility. The device comprises a gas washing feed back tank, wherein the gas washing feed back tank is respectively connected with a Bunsen reaction kettle and the inlet end of an oxygen purification system through pipelines, and the oxygen purification system is connected with a compressor; the Bunsen reaction kettle is connected with a liquid-liquid separation tank, the liquid-liquid separation tank comprises an upper layer and a lower layer, and the upper layer and the lower layer are respectively connected with H2SO4Phase device and HIxA phase device; the outlet end of the compressor is sequentially connected with an oxygen storage tank and ozoneA generator and finally an ozone injection mixing system; ozone generator and dilution fan connect the ozone and spray the hybrid system, and the ozone sprays the hybrid system and connects flue reactor, and boiler system, power plant's flue dust remover and draught fan link to each other in proper order and connect to flue reactor entry end, and flue reactor exit end connects gradually power plant desulfurizing tower and power plant's chimney. The utility model provides high power plant's stability, security and economic nature have reduced the cost of active molecule ozone denitration technique.
Description
Technical Field
The utility model relates to a thermochemical sulfur iodine circulating water decomposes hydrogen manufacturing technique and active molecule ozone denitration technical field, especially relates to a coal fired power plant thermochemical water decomposes hydrogen manufacturing coupling ozone denitration device.
Background
In recent years, with the vigorous development of renewable energy technology, coal-fired units need to participate in deep peak regulation widely, and an economic and effective deep peak regulation technology will determine the market competitiveness of coal-fired power plants. The boiler load is often less than 50% during deep peak shaving, compared with dust removal and desulfurization, the control of nitrogen oxides is affected most, and the exhaust gas temperature is lower than the temperature range of the conventional SCR catalyst at the moment, so that NO is causedxThe emission can not meet the requirement of ultralow emission, the bypass of an economizer is often required to be modified, or the ammonia injection amount is increased to ensure the environmental protection index, but the subsequent problems of the reduction of the unit economy and the blockage of the ammonium bisulfate air preheater are increasingly serious. The active molecule ozone low-temperature denitration technology mainly aims at low-temperature flue gas with the temperature below 150 ℃ behind a dust remover, is irrelevant to the front-end combustion process, can effectively avoid the influence of boiler combustion and load change on the flue gas temperature, is applicable to fuel oil, fuel gas and coal-fired flue gas, has the optimal temperature range of 30-110 ℃, and can realize the aim of denitrationSO of low temperature flue gas2、NOxAnd Hg and other pollution gases, has the advantages of high efficiency, convenient implementation, small change amount of the existing unit and the like, and is very suitable for the deep peak regulation low-load operation and start-stop stage NO of the boilerxThe deep treatment of (2). However, the overall operating cost of this technology is high, with the operating cost of an air separation oxygen plant accounting for about 40%.
Hydrogen energy is used as an energy carrier, has the advantages of high efficiency, cleanness, safety, sustainability and the like, and is increasingly paid more attention by various countries in the world. The large-scale low-cost hydrogen production is the basis of future hydrogen energy economy, wherein the thermochemical sulfur-iodine circulating water decomposition hydrogen production technology is considered as the most promising hydrogen production mode after series evaluation and screening, and water is used as a hydrogen source, so that high-concentration oxygen can be obtained while hydrogen is produced. The thermochemical sulfur-iodine circulating water decomposition hydrogen production mainly comprises the following reaction processes: first, liquid H2O, solid state I2And gaseous SO2The gas generates a Bunsen reaction to generate a mixed solution of hydriodic acid and sulfuric acid, and the solution after the reaction is divided into two layers due to the existence of excessive iodine simple substance. Upper layer H2SO4Phase solution (containing H)2SO4、 H2O and small amounts of HI and I2) After purification and distillation, high-purity oxygen is obtained through decomposition at high temperature (923-1123K) under the action of a catalyst. Lower HI layerxPhase solution (containing HI and I)2、H2O and a small amount of sulfuric acid) is purified, concentrated and rectified to obtain high-concentration HI gas, and the HI gas is further decomposed under 573-773K to obtain hydrogen.
Therefore, under the background of deep peak regulation, the coal-fired power plant can utilize surplus high-temperature steam and surplus electric power of a unit during deep peak regulation as heat sources, utilize a thermochemical sulfur-iodine circulating water decomposition hydrogen production technology to obtain high-concentration oxygen while preparing hydrogen, wherein the oxygen can be used as an oxygen-rich source for preparing active molecules in a low-temperature ozone denitration technology, and the power plant is helped to realize ultralow emission of flue gas, so that the resources are fully utilized, and considerable economic benefits are obtained.
SUMMERY OF THE UTILITY MODEL
The to-be-solved technical problem of the utility model is to overcome the not enough among the prior art, provide a coal fired power plant thermochemical water split hydrogen manufacturing coupling ozone denitrification facility.
For solving the technical problem, the utility model discloses an adopted technical scheme is:
the coal-fired power plant hydrogen production and ultralow emission device for thermochemical cycle coupling active molecule denitration is provided, and comprises a thermochemical sulfur-iodine cycle hydrogen production part and an active molecule ozone denitration part;
the thermochemical sulfur-iodine cycle hydrogen production part comprises a gas washing material returning tank, two outlet ends of the gas washing material returning tank are respectively connected with the Bunsen reaction kettle and the inlet end of an oxygen purification system through pipelines, and the outlet end of the oxygen purification system is connected with a compressor; the outlet end of the Bunsen reaction kettle is connected with a liquid-liquid separation tank through a pipeline, the liquid-liquid separation tank comprises an upper layer and a lower layer, and the upper layer and the lower layer are respectively connected with H2SO4Phase device and HIxA phase device;
H2SO4the phase device comprises H2SO4The outlet end of the purification tower and the liquid-liquid separation tank is connected with H2SO4Inlet end of the purification column, H2SO4Outlet at the top of the purification column and H2SO4The condenser is connected to the inlet end of the gas washing feed back tank2SO4The top of the distillation column is connected with H2SO4Lower part of the decomposer, H2SO4Resolver upper connection H2SO4Inlet end of condenser, H2SO4The outlet end of the condenser is connected with two branches, one branch is connected with H2SO4The top of the purification tower is connected to the inlet end of the gas washing and returning tank, and the other branch is connected with the H2SO4The bottom outlet of the purification tower is connected to H through a pipeline2SO4A distillation column bottom inlet;
HIxthe phase device comprises an HI purification tower, the outlet end of the liquid-liquid separation tank is connected with the inlet end of the HI purification tower, the outlet end of the HI purification tower is connected with an electrodialysis HI concentration device, and the anode outlet of the electrodialysis HI concentration device and the top of the HI purification tower are connected to a washing gas recycling tank; the cathode outlet of the electrodialysis HI concentration device is connected with an HI rectifying tower through a pipelineThe top outlet of the tower is sequentially connected with an HI decomposer and an HI condenser inlet through pipelines, the outlet of the HI condenser is connected with two branches, one branch is connected with a hydrogen purification system, a compressor and a high-pressure hydrogen storage tank through pipelines, and the other branch is connected with the bottom inlet of an HI rectifying tower; the bottom of the HI rectifying tower and the bottom of the HI condenser are connected with an electrodialysis HI concentration device;
the active molecule ozone denitration part comprises an ozone spraying and mixing system; the outlet end of the compressor is sequentially connected with an oxygen storage tank and an ozone generator through pipelines and finally reaches an ozone jet mixing system; ozone generator and dilution fan pass through the pipe connection ozone and spray the hybrid system, and the ozone sprays the hybrid system and passes through the pipe connection flue reactor, and boiler system, power plant's flue dust remover and draught fan loop through the pipeline and link to each other and be connected to flue reactor entry end, and flue reactor exit end connects gradually power plant's desulfurizing tower and power plant's chimney through the pipeline.
A coal-fired power plant hydrogen production and ultralow emission method by utilizing thermochemical cycle coupling active molecule denitration comprises the following steps:
(1) the thermal power generating unit inputs the electric load and the thermal load beyond deep peak regulation into thermochemical sulfur-iodine cycle hydrogen production H2SO4Decomposers, HI decomposers, etc.;
(2) purifying hydrogen generated by the thermochemical sulfur-iodine cycle hydrogen production part, and storing the purified hydrogen in a high-pressure hydrogen storage tank for sale;
(3) by-product O in the hydrogen production process2After purification, storing the product in an oxygen storage tank as an oxygen-rich source in an active molecule ozone denitration process;
(4) introducing oxygen in an oxygen storage tank into an ozone generator, and simultaneously using an electric load except for deep peak shaving of the thermal power generating unit for dielectric barrier discharge to generate ozone;
(5) mixing ozone generated by an ozone generator with air from a dilution fan to promote the mixing effect of the ozone in a flue reactor;
(6) the diluted ozone mixed gas enters an ozone injection mixing system through an ozone supply system, is injected into a flue reactor to be mixed and reacted with flue gas, and NO is addedxOxidizing;
(7) oxidized NOxWith SO2And other flue gas components enter the desulfurizing tower together to complete the washing and absorbing process, so that the synergistic desulfurization and denitrification is realized. Realizing the synergistic desulfurization and denitrification and discharging through a chimney of a power plant.
As a refinement, step (2) comprises the following sub-steps:
(a) inputting raw material water into a gas washing and returning tank, fully mixing the raw material water with raw material sulfur dioxide, iodine simple substance and unreacted water circulating in a part of thermochemical sulfur-iodine hydrogen production device, entering a Bunsen reaction kettle, and reacting at 333-393K to generate HIxPhase sum H2SO4And (4) phase(s).
(b) After the Bunsen reaction kettle finishes the reaction, the product is conveyed into a liquid-liquid separation tank, and HI is led to be settled by standingxPhase sum H2SO4Phase separation;
(c) heavy phase HI in liquid-liquid separation tankxThe solution enters a HI purification tower to perform a reverse reaction of a Bunsen reaction, SO as to remove contained sulfuric acid impurities and generate SO2、I2And H2Introducing the backwash gas back-charging tank;
(d) purified HIxDividing the solution flow into two equal parts and sending the two parts to the anode and the cathode of an electrodialysis HI concentration device, leading the HI solution at the outlet of an anode pool back to a washing gas return tank, and sending the HI solution at the outlet of a cathode pool into an HI rectifying tower for rectification;
(e) feeding HI rectified at the top of the HI rectifying tower into an HI decomposer of 573-773K for decomposing into I2Steam and H2Then entering a HI condenser for condensation; h2And the hydrogen is stored in a high-pressure hydrogen storage tank through a hydrogen purification system and a compressor.
As an improvement, the step (e) is followed by the following substeps:
(f) circulating the condensed iodine-containing HI solution back to the electrodialysis HI concentration device, and collecting HI at the bottom of the HI rectifying towerxThe solution is also circulated back to the electrodialysis HI concentration device;
(g) light phase H in liquid-liquid separation tank2SO4The phase is firstly put into a sulfuric acid purification tower for purification reaction to remove the content in the materialsHI of (3), SO generated2、I2And H2Feeding O back to a washing gas material returning tank;
(h) the purified sulfuric acid solution is subjected to H2SO4Concentrating in distillation tower to 65% concentration, and feeding into H2SO4The water vapor discharged by the decomposer is sent back to the washing gas return tank;
(i)H2SO4the decomposer decomposes the sulfuric acid into SO at a sulfuric acid decomposition stage of 673-773K3And H2O, and H2O and SO3Are all converted into gaseous, SO3Decomposing into SO under the action of a catalyst at 923-1123K2And O2SO formed2And O2Via H2SO4Cooling the condenser, returning the cooled sulfuric acid solution to the washing gas tank, and circulating the undecomposed sulfuric acid solution back to the H tank via the condenser2SO4A distillation column;
as an improvement, the purification in the step (3) means that the oxygen washed by the washing gas return tank is sent to an oxygen purification system, and the purified oxygen is input into an oxygen storage tank through a compressor.
As an improvement, the energy required by the whole process flow comes from 800-1500K high-temperature flue gas or 350-900K high-temperature steam of a coal-fired unit.
As an improvement, in the reaction step (a), H2O、I2And SO2The molar ratio of (A) to (B) is: (13-15): 5-7): 1; carrying out heat tracing in a pipeline in the whole reaction process, and controlling the temperature to be 360K; h2SO4Catalysts are arranged in both the decomposer and the HI decomposer.
The thermochemical sulfur-iodine circulating water decomposition hydrogen production technology mainly comprises a Bunsen reaction module, and H2SO4The decomposition module and the HI decomposition module respectively correspond to the following three reaction processes:
wherein the sulfuric acid decomposition is divided into two steps:
in the first Bunsen reaction, liquid H2O, solid state I2And gaseous SO2The gas is 333-393K, and the optimal molar ratio is H2O:I2:SO2And (13-15) reacting under the condition of (5-7) 1 to generate hydriodic acid and sulfuric acid, and separating the solution after the Bunsen reaction into two layers in the presence of excessive iodine simple substance. Upper layer H2SO4Phase solution (containing H)2SO4、H2O and small amounts of HI and I2) After purification and distillation, the product enters a sulfuric acid decomposer to be decomposed into sulfur dioxide, oxygen and water under the action of 923-1123K high temperature and a catalyst, and the lower layer HI isxPhase solution (containing HI and I)2、H2O and a small amount of H2SO4) After purification, concentration and rectification, high-concentration hydrogen iodide gas is obtained, and is further decomposed at the high temperature of 573-773K under the action of a catalyst to obtain hydrogen and iodine simple substances. In order to prevent the problems of excessive iodine blockage and the precipitation of the side reaction elemental sulfur, the whole process of pipeline heat tracing is carried out, and the temperature is controlled at 360K.
The utility model further provides a thermochemical sulfur iodine circulating water decomposition hydrogen production technology for realizing the method, coupled with active molecule ozone denitration, for realizing deep peak regulation of coal-fired power plant, hydrogen production and NOxThe equipment in the system comprises a gas washing material returning tank, a Bunsen reaction kettle, a liquid-liquid separation tank and HIxPhase device, H2SO4The system comprises a phase device, an oxygen purification system, an oxygen storage tank, a hydrogen purification system, a compressor, a high-pressure hydrogen storage tank, an ozone generator, a dilution fan, an ozone injection mixing system, a flue reactor and a power plant desulfurizing tower. The washing gas feed back tank is respectively connected with the Bunsen reaction kettle and the oxygen purification system through pipelines, the oxygen purification system is connected with the compressor, the compressor is connected with the oxygen storage tank through an oxygen pipeline, the oxygen storage tank is connected with the ozone generator, the ozone generator and the dilution fan are connected with the ozone injection mixing system through pipelines, the ozone injection mixing system is connected with the flue reactor through a pipeline, the front and the back of a flue dust remover of the power plant are respectively connected with the boiler system and the induced draft fan, and the flue reactor is respectively connected with the induced draft fan and the desulfurization tower of; the Bunsen reaction kettle is connected with a liquid-liquid separation tank through a pipeline, and the upper layer and the lower layer of the liquid-liquid separation tank are respectively connected with a H2SO4Phase device and HIxPhase device, H2SO4The phase device is connected with a backwash gas recycling tank, HI through a pipelinexThe phase device is connected with a hydrogen purification system, the hydrogen purification system is connected with a compressor, and the compressor is connected with a high-pressure hydrogen storage tank through a hydrogen pipeline.
HIxThe phase device comprises a HI purification tower, an electrodialysis HI concentration device, a HI rectifying tower, a HI decomposer and a HI condenser. The HI purification tower, the electrodialysis HI concentration device, the HI rectifying tower, the HI decomposer and the HI condenser are sequentially connected; and meanwhile, the top of the HI purification tower and the anode outlet of the electrodialysis HI concentration device are connected with a washing gas return tank, and the bottom of the HI rectifying tower and the bottom of the HI condenser are connected with the electrodialysis HI concentration device.
H2SO4The phase device comprises H2SO4Purification column, H2SO4Distillation column, H2SO4A decomposer and a condenser. H2SO4Purification column, H2SO4Distillation column, H2SO4The decomposer and the condenser are connected in sequence; at the same time H2SO4Purification column, H2SO4The distillation tower is connected with a gas washing feed back tank H2SO4The upper part of the decomposer is connected with a condenser, and the condenser is also connected with H2SO4Distillation columns are connected so that H2SO4And (4) circularly decomposing, and simultaneously connecting the air outlet of the condenser with a gas washing return tank.
The system of the utility model is divided into a thermochemical sulfur-iodine cycle hydrogen production flow and an active molecule ozone denitration flow. The thermochemical sulfur-iodine circulation hydrogen production process comprises a Bunsen reaction module, HIxModule and H2SO4And (5) modules. SO for recycling2、I2Reacted with water in a Bunsen reaction module and layered to produce HIxPhase (containing HI and I)2、H2O and a small amount of H2SO4) And H2SO4Phase (containing H)2SO4、H2O and small amounts of HI and I2)，HIxPhase in HIxFurther purifying, concentrating and rectifying in a module, and finally obtaining hydrogen and H from HI through catalytic decomposition2SO4Phase is at H2SO4Further purification, distillation and decomposition in the module give oxygen. In the active molecule ozone denitration process, oxygen from the thermochemical sulfur-iodine cycle hydrogen production process is introduced into an ozone generator, ozone is generated through dielectric barrier discharge, the ozone and air from a dilution fan are mixed and diluted and then enter an ozone spraying and mixing system, the ozone and the air are sprayed into a flue reactor to perform denitration reaction with flue gas, and finally the oxidized flue gas component enters a power plant desulfurization tower to complete the washing and absorption process, so that the synergistic desulfurization and denitration can be realized. The raw material of the whole system is water, energy is derived from electric load and heat load of the thermal power generating unit except deep peak shaving, and finally ultra-low NOx emission of the coal-fired unit under deep peak shaving can be realized, and meanwhile, a hydrogen product with a high added value is obtained.
Compared with the prior art, the beneficial effects of the utility model reside in that:
1. the electric load and the heat load required by the thermochemical sulfur-iodine cycle hydrogen production system are matched with the heat source provided by the coal-fired unit of the power plant, and the electric load and the heat load outside the deep peak shaving of the thermal power unit can be directly used.
2. In the process of deep peak regulation of the boiler of the power plant, surplus electric energy and heat energy of the boiler are converted into hydrogen energy, so that the stability, safety and economy of the power plant are improved.
3. The operation cost of the air separation oxygen production equipment in the active molecule ozone denitration technology accounts for about 40%, and the byproduct oxygen of the thermochemical sulfur-iodine circulating water decomposition hydrogen production technology is used as the oxygen-rich source of the active molecules, so that the cost of the active molecule ozone denitration technology is reduced.
Drawings
FIG. 1 is a flow diagram of the apparatus and process of the present invention;
reference numerals: 1-washing gas returning tank; 2-Bunsen reaction kettle; 3-liquid separation tank; 4-H2SO4A purification column; 5-H2SO4A distillation column; 6-H2SO4A resolver; 7-H2SO4A condenser; 8-an oxygen purification system; a 9-HI purification column; 10-electrodialysis HI concentration unit; 11-HI rectification column; a 12-HI decomposer; a 13-HI condenser; 14-a hydrogen purification system; 15-a compressor; 16-a high pressure hydrogen storage tank; 17-a compressor; 18-an oxygen storage tank; 19-an ozone generator; 20-a dilution fan; 21-ozone jet mixing system; 22-a boiler system; 23-power plant flue dust collector; 24-a draught fan; 25-flue reactor; 26-a power plant desulfurization tower; 27-chimney of power plant.
Detailed Description
The following detailed description of the embodiments of the present invention will be made with reference to the accompanying drawings.
As shown in figure 1, the utility model discloses a coal fired power plant hydrogen production and ultra-low discharging equipment of denitration of thermochemical cycle coupling active molecule. The thermochemical sulfur-iodine cycle hydrogen production system comprises a thermochemical sulfur-iodine cycle hydrogen production part and an active molecule ozone denitration part, wherein the thermochemical sulfur-iodine cycle hydrogen production part comprises a gas washing material returning tank 1, the gas washing material returning tank 1 is connected with a Bunsen reaction kettle 2, the Bunsen reaction kettle 2 is connected with a liquid-liquid separation tank 3, and the liquid-liquid separation tank 3 is divided into an upper layer and a lower layer and is respectively connected with H2SO4A purifying tower 4 and an HI purifying tower 9, the HI purifying tower 9, an electrodialysis HI concentrating device 10, an HI rectifying tower 11, an HI decomposer 12 and an HI condenser 13 are sequentially connected, meanwhile, the anode of the electrodialysis HI concentrating device 10 and the HI purifying tower 9 are connected with a washing gas recycling tank 1, the bottom of the HI rectifying tower 11 is connected with the electrodialysis HI purifying device 10, the hydrogen outlet of the HI condenser 13 is sequentially connected with a hydrogen purifying system 14, a compressor 15 and a high-pressure hydrogen storage tank 16, and meanwhile, the HI rectifying tower 11 and the HI condenser 13 are connected with the electrodialysis HI concentrating device 10The HI residual liquid is recycled by the anode;
H2SO4purification column 4, H2SO4Distillation column 5, H2SO4Decomposers 6 and H2SO4The condensers 7 being connected in series, while H2SO4Purification column 4 and H2SO4The distillation tower 5 is also connected with a gas washing material returning tank 1, H2SO4Resolver 6 connection H2SO4The condensers 7 and 7 are respectively connected with H2SO4The distillation tower 5 and the gas washing material returning tank 1, the gas washing material returning tank 1 is connected with an oxygen purification system 8, the oxygen purification system 8 is connected with a compressor 17, and the compressor 17 is connected with an oxygen storage tank 18.
The active molecule ozone denitration part comprises an ozone spraying and mixing system 21; the oxygen storage tank 18 is connected with an ozone generator 19, the ozone generator 19 and a dilution fan 20 are connected with an ozone injection mixing system 21, an induced draft fan 24 and the ozone injection mixing system 21 are connected with a flue reactor 25, a boiler system 22 is connected with a flue dust remover 23 of a power plant, the flue dust remover 23 of the power plant is connected with the induced draft fan 24, the flue reactor 25 is connected with a desulfurizing tower 26 of the power plant, and the desulfurizing tower 26 of the power plant is connected with a chimney 27 of the power plant.
The utility model also provides a coal fired power plant hydrogen manufacturing and ultralow emission method of thermal chemical circulation coupling active molecule denitration's concrete step as follows:
(1) inputting electric load and thermal load out of deep peak regulation of thermal power unit into thermochemical sulfur-iodine circulating water decomposition hydrogen production system to obtain H in system2SO4The device such as a decomposer, an HI decomposer and the like provides required energy;
(2) inputting raw material water into a gas washing and returning tank 1, fully mixing the raw material water with raw material sulfur dioxide, iodine simple substance and unreacted water which circulate in a part of thermochemical sulfur-iodine hydrogen production device, entering a Bunsen reaction kettle 2, and reacting at 333-393K to generate HIxPhase sum H2SO4The reaction chemical equation of the phase is as follows:
(3) after the reaction in the Bunsen reaction kettle 2 is completed, the product is conveyed into a liquid-liquid separation tank 3, and HI is enabled to be settled by standingxPhase sum H2SO4Phase separation;
(4) heavy phase HI in liquid-liquid separation tank 3xThe solution enters a HI purification tower 9 to perform a reverse reaction of a Bunsen reaction, remove contained sulfuric acid impurities and generate SO2、I2And H2Introducing the backwash gas recycling tank 1;
(5) purified HIxDividing the phase solution flow into two equal parts and sending the two equal parts to the anode and the cathode of an electrodialysis HI concentration device 10, leading the low-concentration HI solution generated by an anode pool back to a washing gas return tank 1, and sending the high-concentration HI solution generated by a cathode pool into an HI rectifying tower 11 for rectification;
(6) HI distilled from the top of the HI rectifying tower 11 is sent to an HI decomposer 12 of 573-773K and decomposed into I2Steam and H2And then to HI condenser 13 for condensation. H2The condensed iodine-containing HI solution is circulated back to the electrodialysis HI concentration device 10 after being stored in a high-pressure hydrogen storage tank 16 through a hydrogen purification system 14 and a compressor 15. Meanwhile, HI at the bottom of the HI rectifying tower 11xThe solution is also recycled to the electrodialysis HI concentration unit 10.
(7) Light phase H in liquid-liquid separation tank 32SO4The phase is firstly fed into a sulfuric acid purification tower 4 for purification reaction, a small amount of HI contained in the material is removed, and the generated SO2、I2And H2Feeding O back to the washing gas returning tank 1;
(8) the purified sulfuric acid solution is subjected to H2SO4The distillation column 5 is condensed to 65% concentration and fed into H2SO4The decomposer 6, the exhausted water vapor is sent back to the washing gas returning tank 1;
(9)H2SO4the decomposer 6 decomposes the sulfuric acid into SO at a sulfuric acid decomposition section of 673-773K3And H2O, and H2O and SO3Are all converted into gaseous, SO3Decomposing into SO under the action of a catalyst at 923-1123K2And O2SO formed2And O2Via H2SO4The cooled condenser 7 is sent to the back washing gas returning tank 1,the undecomposed sulfuric acid solution is recycled back to H via a condenser 72SO4A distillation column 5;
(10) feeding the oxygen washed by the washing gas returning tank 1 into an oxygen purification system 8, and inputting the obtained high-purity oxygen into an oxygen storage tank 18 through a compressor 17 to be used as an oxygen-enriched source of an ozone generator 19;
(11) ozone generated by an ozone generator 19 is firstly mixed with air from a dilution fan 20, diluted ozone mixed gas enters an ozone injection mixing system 21 and is injected into a flue reactor 25, flue gas discharged from a flue at the tail part of a boiler system 22 is dedusted by a flue deduster 23 of a power plant, and then is sent into the flue reactor 25 through an induced draft fan 24 to react with the ozone;
(12) the flue gas after reaction enters a power plant desulfurization tower 26 to realize cooperative desulfurization and denitrification, and finally ultralow emission is completed through a power plant chimney 27.
The utility model discloses the biggest innovation part is with thermochemistry sulfur iodine circulating water decomposition hydrogen manufacturing technique and active molecule ozone denitration technique coupled, and the required energy of entire system all comes from electrical load and thermal load beyond the thermal power unit degree of depth peak shaver simultaneously, has greatly reduced hydrogen manufacturing and denitration cost this to show stability, security and the economic nature that has improved the power plant.
The utility model adopts the thermochemical sulfur iodine circulating water decomposition hydrogen production technology to produce hydrogen, the purity of the obtained hydrogen is more than 99.99 percent, and the hydrogen comprises a Bunsen reaction module, and H2SO4The decomposition module is HI decomposition module, and the raw material of the whole reaction is SO2、I2And H2O, the product thereof is H2SO4And HI. In order to make the product separate smoothly, the reaction needs to be carried out in excess I2And H2O, with the optimal molar ratio of H2O:I2:SO21 is selected from (13-15) and (5-7). The utility model discloses in, for preventing that excessive iodine from blockking up and the problem that the secondary reaction elemental sulfur is appeared, need carry out the companion's heat to whole pipeline, temperature control is at 360K. To increase H2SO4And decomposition efficiency of HI, H2SO4The decomposer 6 and the HI decomposer 12 are both filled with respective catalysts. Energy required by three modulesThe quantities are from the electrical load and the thermal load of the thermal power generating unit except the deep peak shaving.
In the utility model, the oxygen washed by the gas washing material returning tank 1 is stored in the oxygen storage tank 18 through the oxygen purification system 8 and the compressor 17, and the purity of the obtained oxygen is more than 95%; as an oxygen-rich source of the ozone generator 19, the ozone generator 19 generates ozone through dielectric barrier discharge and mixes the ozone with air from a dilution fan 20, the diluted ozone mixed gas enters an ozone injection mixing system 21 and is injected into a flue reactor 25 to react with flue gas dedusted by a flue deduster 23 of the power plant, the reacted flue gas enters a desulfurization tower 26 of the power plant to realize synergistic desulfurization and denitrification, and finally ultralow emission is completed through a chimney 27 of the power plant, namely the concentration of NOx in the flue gas discharged by the chimney of the power plant reaches the ultralow emission standard, namely less than 50mg/Nm 3.
The foregoing description has been provided for the purpose of illustrating the general principles of the invention, and for the purpose of illustrating its general features and advantages, and is not intended to limit the scope of the invention. The foregoing description only describes the principles and features of the present invention, and further provides many modifications and improvements within the spirit and scope of the invention.
Claims (3)
1. The utility model provides a coal fired power plant thermochemical water split hydrogen manufacturing coupling ozone denitrification facility which characterized in that: comprises a thermochemical sulfur-iodine circulating hydrogen production part and an active molecule ozone denitration part;
the thermochemical sulfur-iodine cycle hydrogen production part comprises a gas washing material returning tank, two outlet ends of the gas washing material returning tank are respectively connected with the Bunsen reaction kettle and the inlet end of an oxygen purification system through pipelines, and the outlet end of the oxygen purification system is connected with a compressor; the outlet end of the Bunsen reaction kettle is connected with a liquid-liquid separation tank through a pipeline, the liquid-liquid separation tank comprises an upper layer and a lower layer, and the upper layer and the lower layer are respectively connected with H2SO4Phase device and HIxA phase device;
said H2SO4The phase device comprises H2SO4The outlet end of the purification tower and the liquid-liquid separation tank is connected with H2SO4Inlet end of the purification column, H2SO4Purification ofOutlet at the top of the column and H2SO4The condenser is connected to the inlet end of the gas washing feed back tank2SO4The top of the distillation column is connected with H2SO4Lower part of the decomposer, H2SO4Resolver upper connection H2SO4Inlet end of condenser, H2SO4The outlet end of the condenser is connected with two branches, one branch is connected with H2SO4The top of the purification tower is connected to the inlet end of the gas washing and returning tank, and the other branch is connected with the H2SO4The bottom outlet of the purification tower is connected to H through a pipeline2SO4A distillation column bottom inlet;
the HIxThe phase device comprises an HI purification tower, the outlet end of the liquid-liquid separation tank is connected with the inlet end of the HI purification tower, the outlet end of the HI purification tower is connected with an electrodialysis HI concentration device, and the anode outlet of the electrodialysis HI concentration device and the top of the HI purification tower are connected to a washing gas recycling tank; a cathode outlet of the electrodialysis HI concentration device is connected with an HI rectifying tower through a pipeline, an outlet of the HI rectifying tower is sequentially connected with an HI decomposer and an inlet of an HI condenser through pipelines, an outlet of the HI condenser is connected with two branches, one branch is connected with a hydrogen purification system, a compressor and a high-pressure hydrogen storage tank through pipelines, and the other branch is connected with an inlet at the bottom of the HI rectifying tower; the bottom of the HI rectifying tower and the bottom of the HI condenser are connected with an electrodialysis HI concentration device;
the active molecule ozone denitration part comprises an ozone spraying and mixing system; the outlet end of the compressor is sequentially connected with an oxygen storage tank and an ozone generator through a pipeline and finally reaches an ozone jet mixing system; ozone generator and dilution fan pass through the pipe connection ozone and spray the hybrid system, and the ozone sprays the hybrid system and passes through the pipe connection flue reactor, and boiler system, power plant's flue dust remover and draught fan loop through the pipeline and link to each other and be connected to flue reactor entry end, and flue reactor exit end connects gradually power plant's desulfurizing tower and power plant's chimney through the pipeline.
2. The coal fired power plant thermochemical water splitting hydrogen production coupling ozone denitration device of claim 1, wherein: the energy required by the whole device comes from 800-1500K high-temperature flue gas or 350-900K high-temperature steam of the coal-fired unit.
3. The coal fired power plant thermochemical water splitting hydrogen production coupling ozone denitration device of claim 1, wherein: said H2SO4Catalysts are arranged in both the decomposer and the HI decomposer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994869A (en) * | 2020-09-02 | 2020-11-27 | 浙江大学 | Coal-fired power plant thermochemical water decomposition hydrogen production coupling ozone denitration device and method |
| CN113562692A (en) * | 2021-07-11 | 2021-10-29 | 浙江大学 | Method for producing hydrogen by deep peak regulation coupling thermochemical sulfur-iodine open-loop circulation of coal-fired power plant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111994869A (en) * | 2020-09-02 | 2020-11-27 | 浙江大学 | Coal-fired power plant thermochemical water decomposition hydrogen production coupling ozone denitration device and method |
| CN111994869B (en) * | 2020-09-02 | 2024-04-05 | 浙江大学 | Thermochemical water splitting hydrogen production coupling ozone denitration device and method for coal-fired power plant |
| CN113562692A (en) * | 2021-07-11 | 2021-10-29 | 浙江大学 | Method for producing hydrogen by deep peak regulation coupling thermochemical sulfur-iodine open-loop circulation of coal-fired power plant |
| CN113562692B (en) * | 2021-07-11 | 2023-11-10 | 浙江大学 | Method for producing hydrogen by deep peak regulation coupling thermochemical sulfur-iodine open circuit circulation of coal-fired power plant |
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