CN116889793A - Flue gas purification system and process for recycling deamination cooperated with calcium, sulfur and ammonia - Google Patents
Flue gas purification system and process for recycling deamination cooperated with calcium, sulfur and ammonia Download PDFInfo
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- CN116889793A CN116889793A CN202311107445.5A CN202311107445A CN116889793A CN 116889793 A CN116889793 A CN 116889793A CN 202311107445 A CN202311107445 A CN 202311107445A CN 116889793 A CN116889793 A CN 116889793A
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- flue gas
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- ammonium sulfate
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 239000003546 flue gas Substances 0.000 title claims abstract description 203
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 230000009615 deamination Effects 0.000 title claims abstract description 101
- 238000006481 deamination reaction Methods 0.000 title claims abstract description 101
- 238000004064 recycling Methods 0.000 title claims abstract description 53
- 239000011575 calcium Substances 0.000 title claims abstract description 48
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 47
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 40
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000000746 purification Methods 0.000 title claims description 34
- 239000010440 gypsum Substances 0.000 claims abstract description 132
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 132
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 114
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 99
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 99
- 238000001354 calcination Methods 0.000 claims abstract description 66
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000008929 regeneration Effects 0.000 claims abstract description 60
- 238000011069 regeneration method Methods 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 53
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 35
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 35
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 31
- 239000000292 calcium oxide Substances 0.000 claims abstract description 31
- 239000000428 dust Substances 0.000 claims description 52
- 239000002918 waste heat Substances 0.000 claims description 51
- 239000002253 acid Substances 0.000 claims description 39
- 230000003009 desulfurizing effect Effects 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 28
- 238000006477 desulfuration reaction Methods 0.000 claims description 22
- 230000023556 desulfurization Effects 0.000 claims description 22
- 230000029087 digestion Effects 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 238000003723 Smelting Methods 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- -1 fluorgypsum Substances 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims 2
- 238000003860 storage Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 235000019738 Limestone Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
Classifications
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
-
- 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
- B01D53/343—Heat recovery
-
- 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
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
-
- 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
- B01D53/58—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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- 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
-
- 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
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- 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
- C01B17/42—Sulfides or polysulfides of magnesium, calcium, strontium, or barium
- C01B17/44—Sulfides or polysulfides of magnesium, calcium, strontium, or barium by reduction of sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2067—Urea
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/40—Alkaline earth metal or magnesium compounds
- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
-
- 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
Abstract
The invention discloses a flue gas purifying system and a process for recycling deamination cooperated with calcium, sulfur and ammonia. In the deamination tower, 1-20% dilute sulfuric acid is sprayed into the flue gas, and the ammonia concentration in the flue gas after deamination reaches the emission standard by controlling the liquid-gas ratio. And introducing the reacted ammonium sulfate solution into an ammonium sulfate regeneration tower, replacing ammonia water and gypsum by using quick lime or CaS, circularly calcining the generated gypsum, desulfurized gypsum and the like, and returning the ammonia water to the SCR denitration system for recycling. The sulfuric acid, the quicklime or the CaS used in the process are all from gypsum reduction calcination, and the redundant quicklime, sulfuric acid or sulfur can be directly sold out as a product or used for other working procedures, so that the raw materials can be recycled, and the process has great economic and ecological environmental benefits.
Description
Technical Field
The invention relates to the field of environmental protection and circular economy, in particular to a flue gas purification system and a flue gas purification process by deamination and calcium, sulfur and ammonia recycling.
Background
In the pollution treatment of the 'two-high' industry in China at present, the treatment difficulty of ultralow emission of nitrogen oxides is the greatest. Nitrogen Oxides (NO) x ) Is one of main components of the atmospheric pollution, with the emphasis of the treatment of the atmospheric pollution in China being continuously enhanced, the concept of ultra-low emission is put forward in China, and strict requirements are firstly made on the atmospheric pollutants such as smoke dust, nitrogen oxides, sulfides, mercury and the like discharged by coal-fired power plants, and the method is continuously pushed to non-electric industries such as steel and cement industries.
In the denitration and emission reduction work, technical modes such as SCR, SNCR, staged combustion and the like are mainly used. The SCR denitration technology has the advantages of high denitration efficiency, stable operation and the like, can better meet the environmental protection requirement, and is widely applied to industrial flue gas denitration of thermal power plants, steel plants, cement plants, incineration plants and the like. According to statistics, in 2022, the application proportion of the SCR denitration technology in industries such as electric power, steel, coking and the like is over 95%, 70% and 90%, and the SCR denitration technology has important significance for national control of industrial waste gas emission, realization of industrial ultra-low emission standard and environmental protection treatment of atmospheric pollutants.
The denitration agent used by SCR is ammonia water or urea. In order to meet the emission requirement of nitrogen oxides in industrial flue gas, excessive ammonia water is often sprayed into the industrial flue gas, and ammonia water which does not participate in the reaction can form ammonia gas to enter the atmosphere due to the fact that the ammonia gas is easy to volatilize, so that ammonia gas pollution is caused. Ammonia pollution is always ignored by the public, but is an important part of air quality environmental pollution in China and is an important reason for continuously increasing PM2.5 index. The method is a large industrial country, and economic development is rapid in recent years, especially in the industries of steel, cement, power plants and the like, and the method is rapid in development or heavy pollutant generation place, wherein ammonia pollution is one of the problems to be solved in the current industry.
Among the flue gas desulfurization processes, the limestone-gypsum flue gas desulfurization technology is most widely applied, the technology is most mature, and the installed capacity of the limestone-gypsum flue gas desulfurization technology accounts for more than 85% of the total flue gas desulfurization unit. The technology takes limestone slurry as a desulfurizing agent and byproducts low-grade desulfurized gypsum, and annual yield of desulfurized gypsum in China is about 1 hundred million tons, so that the limestone slurry becomes one of important industrial solid wastes. Because the moisture content of the desulfurized gypsum is higher, the grain composition is unreasonable, the viscosity is stronger, the secondary utilization of the desulfurized gypsum is difficult, and secondary pollution is caused to the environment after long-term stacking or landfill. In addition, gypsum is a large and inexpensive mineral product, often at a cost far exceeding the cost of the gypsum itself. Therefore, the technology for realizing the in-situ recycling of the desulfurized gypsum is attracting more and more attention.
If the invention can be used for effectively combining the recycling utilization of the desulfurized gypsum (or other industrial byproduct gypsum) with the ammonia pollution treatment, the ammonia emission concentration in the flue gas can be reduced, and the flue gas can reach the emission standard. Meanwhile, ammonia water can be prepared by recycling low-concentration ammonia in the flue gas, and the ammonia water can be returned to the SCR denitration reactor for recycling as a denitration agent.
Disclosure of Invention
The invention provides a flue gas purification system and a process for recycling ammonia gas and byproduct desulfurized gypsum in flue gas, which aims to solve the problem of recycling the ammonia gas and byproduct desulfurized gypsum in the flue gas. In the deamination tower, 1-20% of dilute sulfuric acid is sprayed into the flue gas, and the ammonia concentration in the flue gas after deamination reaches the emission standard by controlling the liquid-gas ratio (the liquid-gas ratio is more than or equal to 1 and less than or equal to 15). And (3) discharging the ammonium sulfate solution after the reaction reaches a certain concentration out of the deamination tower, introducing the ammonium sulfate solution into an ammonia water regenerator, replacing ammonia water and gypsum by using quicklime or CaS, mixing the generated gypsum with desulfurized gypsum (or other industrial byproduct gypsum), and circularly calcining, wherein the ammonia water returns to the SCR denitration system to be used as a denitration agent for recycling. The sulfuric acid, the quicklime or the CaS used for deamination in the process are all from gypsum reduction calcination, and the redundant quicklime, sulfuric acid or sulfur can be directly sold as a product or used for other working procedures according to the requirement. The technology belongs to a part of the circular economy category, and has important significance in both economic and ecological environmental benefits.
The research finds that:
CaS can react with water to produce Ca (OH) by digestion 2 Solution and high concentration H 2 S, the reaction is shown as a formula (1).
CaS+2H 2 O→Ca(OH) 2 +H 2 S (1)
The reaction of CaS with ammonium sulfate solution can produce calcium sulfate and high-concentration H 2 S, the reaction is shown as a formula (2).
CaS+2H 2 O+(NH 4 ) 2 SO 4 →CaSO 4 +2NH 3 ·H 2 O+H 2 S (2)
High concentration H 2 S can be used for preparing sulfuric acid or sulfur, and high-concentration SO 2 The flue gas may produce sulfuric acid. The diluted sulfuric acid can react with ammonia in the flue gas to generate ammonium sulfate ((NH) 4 ) 2 SO 4 ) The reaction is shown in formula (3).
2NH 3 +H 2 SO 4 →(NH 4 ) 2 SO 4 (3)
Quicklime inCan react with ammonium sulfate solution at normal temperature to generate gypsum (CaSO) 4 ) And ammonia water, so that the escaped ammonia gas is recovered into ammonia water, and the reaction is shown in the formula (4).
CaO+1H 2 O+(NH 4 ) 2 SO 4 →CaSO 4 +2NH 3 ·H 2 O (4)
The gypsum generated by the reaction is mixed with desulfurized gypsum (or other industrial byproduct gypsum) and then circularly calcined, and ammonia water is returned to the SCR denitration system to be used as a denitration agent for recycling.
The invention adopts the following technical scheme to realize the aim of the invention:
the invention provides a flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia, which comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse. According to the invention, the reduction calcination system is connected with the acid making system through a digestion device, and a liquid outlet of the digestion device is connected with a liquid inlet of the desulfurizing tower.
According to a preferred embodiment of the invention, the gas outlet of the digestion vessel is also connected to a claus reactor.
According to the invention, the air outlet of the ammonium sulfate regeneration tower is connected with an acid making system and a Claus reactor respectively.
According to the invention, the waste heat utilization system is a direct or indirect heat exchange device, and is selected from a multi-stage cyclone separator or a waste heat boiler.
According to the invention, the deamination tower and the ammonium sulfate regeneration tower are preferably spray-type, fixed-type, concurrent-type, cross-flow-type or fluidization-type devices.
According to a preferred embodiment of the invention, the dust separator is selected from the group consisting of a high temperature cyclone, a high temperature axial flow separator, a metal mesh filter, a ceramic filter, a bag-type dust separator and an electric dust separator.
The invention also provides a flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia, which comprises the following steps:
s1: firstly, industrial flue gas enters a waste heat utilization system, heat in high-temperature flue gas is recovered, and the temperature of the flue gas is reduced to 300-450 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 50-100 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, dilute sulfuric acid with the weight percent of 1-20% is sprayed in the deamination tower, SO that the dilute sulfuric acid reacts with ammonia in the flue gas to generate ammonium sulfate, when the concentration of an ammonium sulfate solution reaches 1-20% by weight percent, the ammonium sulfate solution is discharged out of the deamination tower and enters an ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by a desulfurizing tower and discharged into the atmosphere by a chimney, and SO in the flue gas in the desulfurizing tower is discharged 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding a displacer into the ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting in a temperature range of 0-100 ℃ (excluding 0) to generate gypsum and ammonia water, storing the generated gypsum into a gypsum warehouse, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: delivering gypsum in the gypsum warehouse to a reduction calcining system for calcining to obtain a reaction product, wherein the reaction product at least comprises quicklime and/or CaS;
s8: the reaction product in the step S7 is used as a displacer in the step S6.
According to the preferred embodiment of the present invention, the liquid-gas ratio of the dilute sulfuric acid to the flue gas in S5: the liquid-gas ratio is not less than 1 and not more than 15.
According to the invention, the industrial flue gas is flue gas containing NOx generated in the industrial production process and is selected from coal-fired flue gas, cement kiln flue gas or metal smelting flue gas.
According to a preferred embodiment of the present invention, in S7, when the reaction product includes quicklime:
the reduction calcining system is used for calcining at a high temperature of more than or equal to 950 ℃, and reducing gas and CO 2 The partial pressure ratio of the gas is less than 0.2; the reaction product also comprises high concentration SO 2 Flue gas, high concentration SO 2 The flue gas is used for preparing a sulfuric acid product through a flue gas acid making system, and the sulfuric acid product is diluted by an acid diluter and then is used for deaminizing the flue gas.
According to a preferred embodiment of the present invention, in S7, when the reaction product comprises CaS:
the reduction calcination system in the S7 performs low-temperature calcination at 600-950 ℃, and the reducing gas and CO 2 The partial pressure ratio of the gas is more than or equal to 0.2; the CaS is sent to a digestion device for preparing Ca (OH) 2 Solution and high concentration H 2 S，Ca(OH) 2 The solution is returned to the desulfurizing tower as a desulfurizing agent for cyclic utilization, and high-concentration H 2 S enters an acid making system to prepare sulfuric acid, and the sulfuric acid is diluted by an acid diluter and then returns to a flue gas purifying system as a flue gas deamination agent, or high-concentration H 2 S, introducing the sulfur product into a Claus reactor to prepare a sulfur product;
sulfur is sold as a product or used in other processes.
According to a further preferred embodiment of the invention, the high concentration SO 2 The flue gas comprising SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, the temperature is 700-1200 ℃, and the SO is high in concentration 2 SO in flue gas 2 The volume fraction is 2-20%, and the volume fraction of the reducing gas is 2-20%. The reducing gas comprises CO and H 2 。
According to the present invention, it is preferable that the gypsum described in S7 has a particle diameter of 20 μm to 3mm and a water content of 0% to 20% (excluding 0) and is natural gypsum or industrial by-product gypsum selected from desulfurized gypsum, phosphogypsum, fluorogypsum, titanium gypsum and neutralized gypsum.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the deamination technology has the reaction principle of acid-base neutralization reaction, and the deamination efficiency can reach more than 98% by adjusting the liquid-gas ratio and the sulfuric acid concentration; not only can reduce the ammonia gas emission concentration in the flue gas to enable the ammonia gas emission concentration to reach the emission standard; meanwhile, ammonia water can be prepared by recycling low-concentration ammonia in the flue gas, and can be returned to the SCR denitration reactor for recycling as a denitration agent, so that the problem of ammonia pollution caused by ammonia escape in the SCR denitration reactor is solved.
2. The method prepares quicklime and sulfuric acid or CaS through reduction and calcination; the quick lime can be used as a displacer for ammonia recovery, can also be used as a product for industries such as chemical industry, steel, metallurgy, environmental protection and the like or can be used for producing other calcium-based products according to requirements; part of the sulfuric acid is diluted and then used as a deamination agent for flue gas deamination, and the redundant sulfuric acid can be used as a chemical raw material for other industries; part of the CaS can be used as a displacer of ammonium sulfate, and the excess CaS is sent to a digestion device for preparing Ca (OH) 2 Solution and high concentration H 2 S，Ca(OH) 2 The solution can be used as a desulfurizing agent to return to a desulfurizing tower for recycling, and the high-concentration H 2 S is used for preparing sulfuric acid or sulfur, the sulfuric acid is used as a deamination agent for recycling, the self-sufficiency is achieved, outsourcing sulfuric acid is not needed, the sulfur is used as a product for sale or used for other working procedures, and the problem that the sulfuric acid is difficult to store and transport is solved.
3. The invention realizes the recycling of ammonia, calcium and sulfur, belongs to a part of recycling economy, and has important significance in both economic benefit and environmental benefit.
4. Through the second process, the yields of sulfuric acid and sulfur can be regulated and controlled according to actual needs. Compared with sulfuric acid, the sulfur product is convenient to transport and store. If the factory has no sulfuric acid requirement, the factory can be transported and sold in a sulfur form, so that the problem that the excessive sulfuric acid yield is difficult to treat is solved.
Drawings
FIG. 1 is a process flow of example 1 of the present invention using quicklime as the displacer.
FIG. 2 is a process flow for example 2 of the present invention using CaS as the displacer.
Detailed Description
One embodiment of the present invention will be described in detail below with reference to the attached drawings, but it should be understood that the scope of the present invention is not limited by the embodiment.
Example 1
The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse.
The waste heat utilization system is a multi-stage cyclone separator; the deamination tower and the ammonium sulfate regeneration tower are both spray type devices; the dust remover is a high-temperature cyclone separator.
The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia comprises the following steps as shown in figure 1:
s1: firstly, enabling the coal-fired flue gas to enter a waste heat utilization system, recovering heat in the high-temperature flue gas, and simultaneously cooling the flue gas to 330 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 80 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, 10% dilute sulfuric acid is sprayed in the deamination tower, and the flue gas reacts with ammonia in the flue gas to generate ammonium sulfate, wherein the temperature is 90 ℃; when the liquid-gas ratio is 5 and the concentration of the ammonium sulfate solution reaches 10%, the ammonium sulfate solution is discharged out of the deamination tower and enters the ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by the desulfurization tower and discharged into the atmosphere through a chimney, and SO is contained in the flue gas in the desulfurization tower 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding quicklime into an ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting at 50 ℃ to generate gypsum and ammonia water, mixing the generated gypsum with the desulfurized gypsum, circularly calcining, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: the gypsum in the gypsum warehouse is conveyed to a reduction calcining system for calcining, the calcining temperature is 1000 ℃, and the reducing gas and CO 2 The partial pressure ratio of the gas is 0.15; obtaining quicklime and high-concentration SO 2 Flue gas, high concentration SO 2 The sulfuric acid product is prepared from the flue gas through a flue gas acid making system, one part of sulfuric acid is diluted by an acid diluter and then is used for deamination of the flue gas, and the other part of sulfuric acid can be used for other working procedures or industries.
S8: the quicklime in S7 can be used as a displacer for ammonium sulfate.
The quicklime product in S7 can also be used as a product in other industries.
The gypsum in the step S7 has the particle size of 20 mu m-3mm and the water content of 0% -20%, and is desulfurized gypsum
The high concentration SO 2 Flue gas, SO 2 10% by volume, 15% by volume of a reducing gas (including but not limited to CO) at 1100 ℃ and a main component of SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, etc.
Example 2:
the invention provides a flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia, which comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower through a digestion device; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse. The liquid outlet of the digestion device is connected with the liquid inlet of the desulfurizing tower; the gas outlet of the digestion device is also connected with the claus reactor. And the air outlet of the ammonium sulfate regeneration tower is respectively connected with an acid making system and a Claus reactor.
The waste heat utilization system is a waste heat boiler. The deamination tower and the ammonium sulfate regeneration tower are cross-flow devices. The dust remover is a cloth bag dust remover.
A flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia is shown in figure 2, and comprises the following steps:
s1: firstly, metal smelting flue gas enters a waste heat utilization system, heat in high-temperature flue gas is recovered, and the flue gas is cooled to 420 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 60 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, dilute sulfuric acid with the mass fraction of 2% is sprayed in the deamination tower, and the dilute sulfuric acid reacts with ammonia in the flue gas to generate ammonium sulfate, wherein the temperature is 60 ℃; the liquid-gas ratio is 14; when the mass fraction of the ammonium sulfate solution reaches 5%, the ammonium sulfate solution is discharged from the deamination tower to enter an ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by the desulfurization tower and discharged into the atmosphere through a chimney, and SO is contained in the flue gas of the desulfurization tower 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding CaS into the ammonium sulfate solution in an ammonium sulfate regeneration tower, and reacting at 90 ℃ to generate gypsum, ammonia water and high-concentration H 2 S, the generated gypsum is conveyed to a reduction calcining system, ammonia water returns to the SCR denitration system to be used as a denitration agent for recycling, and high-concentration H is formed 2 S, a part of the S enters an acid making system to prepare sulfuric acid, the sulfuric acid is diluted by an acid diluter and then returns to a flue gas purifying system as a flue gas deamination agent, and redundant H 2 S, introducing the sulfur product into a Claus reactor to prepare a sulfur product;
s7: the gypsum in the gypsum warehouse is calcined in a reduction calcining system, the reduction calcining system is calcined at a low temperature, and the calcining conditions are as follows: 900 ℃, reducing gas and CO 2 The partial pressure ratio of the gas is 0.5; obtaining a mixture of quicklime and CaS;
s8: part of CaS is used as a displacer of ammonium sulfate, and the redundant CaS is sent to a digestion device for preparing Ca (OH) 2 Solution and high concentration H 2 S，Ca(OH) 2 The solution can be used as a desulfurizing agent to return to a desulfurizing tower for recycling, and high-concentration H 2 S, sulfuric acid or sulfur is prepared, the sulfuric acid is used as a deamination agent for recycling, and the sulfur is used as a product for sale or other working procedures.
And S7, the gypsum with the particle size of 20 mu m-3mm and the water content of 0% -20% is phosphogypsum.
The high concentration SO 2 Flue gas, SO 2 Is 5% by volume, the reducing gas (including but not limited to CO) is 10% by volume, the temperature is 750 ℃, and the main component is SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, etc.
Example 3
The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse.
The waste heat utilization system is a multi-stage cyclone separator; the deamination tower and the ammonium sulfate regeneration tower are both spray type devices; the dust remover is a high-temperature cyclone separator.
The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia comprises the following steps as shown in figure 1:
s1: firstly, enabling the coal-fired flue gas to enter a waste heat utilization system, recovering heat in the high-temperature flue gas, and simultaneously cooling the flue gas to 380 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 70 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, and 12% dilute sulfuric acid is sprayed in the deamination tower to react with ammonia in the flue gas to generate ammonium sulfate, wherein the temperature is 70 ℃; the liquid-gas ratio is 8; when the concentration of the ammonium sulfate solution reaches 12%, the ammonium sulfate solution is discharged out of the deamination tower and enters the ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by the desulfurization tower and discharged into the atmosphere through a chimney, and SO is contained in the flue gas in the desulfurization tower 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding quicklime into an ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting at 60 ℃ to generate gypsum and ammonia water, mixing the generated gypsum with the desulfurized gypsum, circularly calcining, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: the gypsum in the gypsum warehouse is conveyed to a reduction calcining system for calcining, the calcining temperature is 1100 ℃, and the reducing gas and CO are used for calcining 2 The partial pressure ratio of the gas is 0.05; obtaining quicklime and high-concentration SO 2 Flue gas, high concentration SO 2 The sulfuric acid product is prepared from the flue gas through a flue gas acid making system, one part of sulfuric acid is diluted by an acid diluter and then is used for deamination of the flue gas, and the other part of sulfuric acid can be used for other working procedures or industries.
S8: the quicklime in S7 can be used as a displacer for ammonium sulfate. The quicklime product in S7 can also be used as a product in other industries.
The gypsum in the step S7 has the particle size of 20 mu m-3mm and the water content of 0% -20%, and is desulfurized gypsum.
The high concentration SO 2 Flue gas, SO 2 15% by volume, 18% by volume of a reducing gas (including but not limited to CO) at 1150 ℃ and with a main component of SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, etc.
Example 4
The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower through a digestion device; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse. The liquid outlet of the digestion device is connected with the liquid inlet of the desulfurizing tower; the gas outlet of the digestion device is also connected with the claus reactor. And the air outlet of the ammonium sulfate regeneration tower is respectively connected with an acid making system and a Claus reactor.
The waste heat utilization system is a waste heat boiler. The deamination tower and the ammonium sulfate regeneration tower are all fixed devices. The dust remover is a ceramic filter.
The above system was operated according to the process in example 2.
Example 5
The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse.
The waste heat utilization system is a waste heat boiler; the deamination tower and the ammonium sulfate regeneration tower are all concurrent devices; the dust remover is an electric dust remover.
The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia comprises the following steps as shown in figure 1:
s1: firstly, enabling the coal-fired flue gas to enter a waste heat utilization system, recovering heat in the high-temperature flue gas, and simultaneously cooling the flue gas to 400 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 90 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, and 12% dilute sulfuric acid is sprayed in the deamination tower to react with ammonia in the flue gas to generate sulfuric acidAmmonium at 90 ℃; the liquid-gas ratio is 12; when the concentration of the ammonium sulfate solution reaches 19%, the ammonium sulfate solution is discharged out of the deamination tower and enters the ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by the desulfurization tower and discharged into the atmosphere through a chimney, and SO is contained in the flue gas in the desulfurization tower 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding quicklime into an ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting at 60 ℃ to generate gypsum and ammonia water, mixing the generated gypsum with the desulfurized gypsum, circularly calcining, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: the gypsum in the gypsum warehouse is conveyed to a reduction calcining system for calcining, the calcining temperature is 1200 ℃, and the reducing gas and CO are used for calcining 2 The partial pressure ratio of the gas is 0.15; obtaining quicklime and high-concentration SO 2 Flue gas, high concentration SO 2 The sulfuric acid product is prepared from the flue gas through a flue gas acid making system, one part of sulfuric acid is diluted by an acid diluter and then is used for deamination of the flue gas, and the other part of sulfuric acid can be used for other working procedures or industries.
S8: the quicklime in S7 can be used as a displacer for ammonium sulfate. The quicklime product in S7 can also be used as a product in other industries.
The gypsum in the step S7 has the particle size of 20 mu m-3mm and the water content of 0% -20%, and is phosphogypsum.
The high concentration SO 2 Flue gas, SO 2 14% by volume, 18% by volume of a reducing gas (including but not limited to CO) at 900 ℃ and a main component of SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, etc.
Example 6
The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia comprises a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower through a digestion device; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse. The liquid outlet of the digestion device is connected with the liquid inlet of the desulfurizing tower; the gas outlet of the digestion device is also connected with the claus reactor. And the air outlet of the ammonium sulfate regeneration tower is respectively connected with an acid making system and a Claus reactor.
The waste heat utilization system is a waste heat boiler. The deamination tower and the ammonium sulfate regeneration tower are all fixed devices. The dust remover is a ceramic filter.
The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia comprises the following steps as shown in figure 1:
s1: firstly, enabling the coal-fired flue gas to enter a waste heat utilization system, recovering heat in the high-temperature flue gas, and simultaneously cooling the flue gas to 340 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 80 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, and 12% dilute sulfuric acid is sprayed in the deamination tower to react with ammonia in the flue gas to generate ammonium sulfate, wherein the temperature is 80 ℃; the liquid-gas ratio is 13; when the concentration of the ammonium sulfate solution reaches 19%, the ammonium sulfate solution is discharged out of the deamination tower and enters the ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by the desulfurization tower and discharged into the atmosphere through a chimney, and SO is contained in the flue gas in the desulfurization tower 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6, adding quicklime into an ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting at 80 ℃ to generate gypsum and ammonia water, mixing the generated gypsum with the desulfurized gypsum, circularly calcining, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: the gypsum in the gypsum warehouse is calcined in a reduction calcining system, the reduction calcining system is calcined at a low temperature, and the calcining conditions are as follows: 900 ℃, reducing gas and CO 2 The partial pressure ratio of the gas is 0.5; obtaining a mixture of quicklime and CaS;
s8: part of CaS is used as a displacer of ammonium sulfate, and the redundant CaS is sent to a digestion device for preparing Ca (OH) 2 Solution and high concentration H 2 S，Ca(OH) 2 The solution can be used as a desulfurizing agent to return to a desulfurizing tower for recycling, and high-concentration H 2 S, sulfuric acid or sulfur is prepared, the sulfuric acid is used as a deamination agent for recycling, and the sulfur is used as a product for sale or other working procedures.
The gypsum in the step S7 has the particle size of 20 mu m-3mm and the water content of 0% -20% (excluding 0) and is fluorine gypsum.
The high concentration SO 2 Flue gas, SO 2 13% by volume, 17% by volume of reducing gas (including but not limited to CO) at 1050 ℃ with SO as the main component 2 、CO、H 2 、N 2 、CO 2 H and H 2 O, etc.
The above disclosure is merely illustrative of specific embodiments of the present invention, but the present invention is not limited thereto, and any variations that can be considered by those skilled in the art should fall within the scope of the present invention.
Claims (10)
1. The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia is characterized by comprising a waste heat utilization system, a high-temperature dust remover, an SCR reactor denitration device, a waste heat boiler, a dust remover, a deamination tower, a desulfurizing tower and a chimney which are sequentially connected according to the flow direction of flue gas; the liquid outlet of the deamination tower is connected with the liquid inlet of the ammonium sulfate regeneration tower, and the liquid outlet of the ammonium sulfate regeneration tower is connected with the SCR reactor denitration device; the discharge port of the desulfurization tower is connected with a gypsum warehouse, the discharge port of the gypsum warehouse is connected with a reduction calcining system, and the gas outlet of the reduction calcining system is sequentially connected with an acid making system, an acid diluter and a deamination tower; the discharge port of the reduction calcining system is connected with the feed port of the ammonium sulfate regeneration tower, and the discharge port of the ammonium sulfate regeneration tower is connected with the gypsum warehouse.
2. The flue gas purification system for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 1, wherein the reduction calcination system is connected with an acid making system through a digestion device, and a liquid outlet of the digestion device is connected with a liquid inlet of a desulfurizing tower; preferably, the gas outlet of the digestion device is also connected with the claus reactor; preferably, the air outlet of the ammonium sulfate regeneration tower is respectively connected with an acid making system and a claus reactor.
3. A flue gas purification system for the deamination of co-calcium, sulfur and ammonia recycling according to claim 3, wherein:
the waste heat utilization system is a direct or indirect heat exchange device and comprises a multi-stage cyclone separator and a waste heat boiler; the deamination tower and the ammonium sulfate regeneration tower are all spray-type, fixed-type, concurrent-flow-type, cross-flow-type or fluidization-type devices.
4. The flue gas purification system for deamination and calcium, sulfur and ammonia recycling according to claim 1, wherein the flue gas purification system is characterized in that: the dust remover in the step S2 is selected from a high-temperature cyclone separator, a high-temperature axial flow separator, a metal mesh filter, a ceramic filter, a cloth bag dust remover or an electric dust remover.
5. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia is characterized by comprising the following steps:
s1: firstly, industrial flue gas enters a waste heat utilization system, heat in high-temperature flue gas is recovered, and the temperature of the flue gas is reduced to 300-450 ℃;
s2: the cooled flue gas enters a high-temperature dust remover to remove solid particles in the flue gas;
s3: the flue gas after dust removal enters an SCR reactor for denitration, and NOx in the flue gas is removed under the action of ammonia water or urea;
s4: the flue gas after removing NOx enters a waste heat boiler, waste heat in the flue gas is recovered for the second time, and the temperature of the flue gas is reduced to 50-100 ℃;
s5: the cooled flue gas enters a deamination tower after secondary dust removal, dilute sulfuric acid with the weight percent of 1-20% is sprayed in the deamination tower, SO that the dilute sulfuric acid reacts with ammonia in the flue gas to generate ammonium sulfate, when the concentration of an ammonium sulfate solution reaches 1-20% by weight percent, the ammonium sulfate solution is discharged out of the deamination tower and enters an ammonium sulfate regeneration tower, the deaminated flue gas is desulfurized by a desulfurizing tower and discharged into the atmosphere by a chimney, and SO in the flue gas in the desulfurizing tower is discharged 2 Reacting with a calcium-based desulfurizing agent to generate desulfurized gypsum, dehydrating the desulfurized gypsum, and storing the desulfurized gypsum in a gypsum warehouse;
s6: adding displacer quicklime and/or CaS into an ammonium sulfate solution in an ammonium sulfate regeneration tower, reacting at a temperature range of 0-100 ℃ and excluding 0 to generate gypsum and ammonia water, storing the generated gypsum into a gypsum storage bin, and returning the ammonia water to an SCR denitration system to be used as a denitration agent for recycling;
s7: delivering gypsum in the gypsum warehouse to a reduction calcining system for calcining to obtain a reaction product, wherein the reaction product at least comprises quicklime and/or CaS;
s8: the reaction product in the step S7 is used as a displacer in the step S6.
6. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 5, wherein the flue gas purification process is characterized in that: the industrial flue gas in the S1 is flue gas containing NOx generated in the industrial production process and is selected from coal-fired flue gas, cement kiln flue gas or metal smelting flue gas.
7. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 5, wherein the flue gas purification process is characterized in that: and in the step S5, the liquid-gas ratio of the dilute sulfuric acid to the flue gas is as follows: the liquid-gas ratio is not less than 1 and not more than 15.
8. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 5, wherein the flue gas purification process is characterized in that: the gypsum in S7 has a particle size of 20 μm-3mm, a water content of 0-20%, excluding 0, and is natural gypsum or industrial by-product gypsum selected from the group consisting of detached gypsum, phosphogypsum, fluorgypsum, titanium gypsum and neutralized gypsum.
9. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 5, wherein the flue gas purification process is characterized in that: in S7, when the reaction product contains quicklime but does not contain CaS:
high-temperature calcination of a reduction calcination system, wherein the conditions of the high-temperature calcination are as follows: the calcination temperature is not less than 950 ℃; reducing gas and CO 2 The partial pressure ratio of the gas is less than 0.2; the reaction product also comprises high concentration SO 2 Flue gas, high concentration SO 2 Preparing a sulfuric acid product from the flue gas through a flue gas acid making system, wherein the sulfuric acid product is diluted by an acid diluter and then is used for deamination of the flue gas;
in S7, when the reaction product comprises CaS:
the reduction calcination system in S7 performs low-temperature calcination, and the conditions of the low-temperature calcination are as follows: 600-950 ℃, reducing gas and CO 2 The partial pressure ratio of the gas is more than or equal to 0.2; the reaction product CaS is sent to a digestion device to prepare Ca (OH) 2 Solution and high concentration H 2 S；Ca(OH) 2 The solution is returned to the desulfurizing tower as a desulfurizing agent for cyclic utilization, and high-concentration H 2 S enters an acid making system to prepare sulfuric acid, and the sulfuric acid is diluted by an acid diluter and then returns to a flue gas purifying system as a flue gas deamination agent, or high-concentration H 2 S is fed into a Claus reactor to prepare a sulfur product, sulfuric acid is recycled as a deamination agent, and sulfur is sold as a product or used for other working procedures.
10. The flue gas purification process for recycling deamination cooperated with calcium, sulfur and ammonia according to claim 9, wherein the flue gas purification process is characterized in that: the high concentration SO 2 Flue gas, SO 2 The volume fraction is 2-20%, the concentration of the reducing gas is 2-20%, the temperature is 700-1200 ℃, and the SO concentration is high 2 The flue gas comprising SO 2 、CO、H 2 、N 2 、CO 2 H and H 2 O。
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