CN109173718A - Calcium method-based combined desulfurization, denitrification and demercuration method and device - Google Patents
Calcium method-based combined desulfurization, denitrification and demercuration method and device Download PDFInfo
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- CN109173718A CN109173718A CN201811324526.XA CN201811324526A CN109173718A CN 109173718 A CN109173718 A CN 109173718A CN 201811324526 A CN201811324526 A CN 201811324526A CN 109173718 A CN109173718 A CN 109173718A
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- hydrogen peroxide
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 31
- 230000023556 desulfurization Effects 0.000 title claims abstract description 28
- 239000011575 calcium Substances 0.000 title claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000007921 spray Substances 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 25
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010440 gypsum Substances 0.000 claims abstract description 16
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003546 flue gas Substances 0.000 claims abstract description 15
- 238000000889 atomisation Methods 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 13
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000001816 cooling Methods 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 17
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 11
- 229910001882 dioxygen Inorganic materials 0.000 description 11
- 239000003344 environmental pollutant Substances 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 231100000719 pollutant Toxicity 0.000 description 9
- -1 hydroxyl radical free radical Chemical class 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000001925 catabolic effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005367 electrostatic precipitation Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009692 water atomization Methods 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
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
本发明公开了一种基于钙法的联合脱硫脱硝脱汞的方法及其装置，该装置包括双氧水储罐，双氧水储罐出口连接双氧水喷射泵入口，促进剂罐出口连接促进剂计量泵入口，双氧水喷射泵出口与促进剂计量泵出口管路汇合后连接双氧水高温水冷雾化喷枪入口，喷枪插入锅炉尾部烟道中，烟气经除尘器进入吸收塔底部，浆液循环泵逆流喷淋含催化剂的吸收液洗涤烟气，吸收塔底部连接一二级旋流器，二级旋流器底部出口连接亚硝酸盐处理罐入口，亚硝酸盐处理罐出口连接石膏处理系统；本发明实现了单塔联合脱硫脱硝脱汞，工艺简单，脱除效率高，运行成本低廉，催化剂的损耗少；可应用于燃煤电站锅炉、工业锅炉、垃圾焚烧炉等，特别适用于改造已建成的中小型燃煤锅炉，具有广阔的市场应用前景。
The invention discloses a method and a device for combined desulfurization, denitrification and mercury removal based on a calcium method. The device comprises a hydrogen peroxide storage tank, the outlet of the hydrogen peroxide storage tank is connected to the inlet of a hydrogen peroxide jet pump, the outlet of the accelerator tank is connected to the inlet of the accelerator metering pump, and the outlet of the hydrogen peroxide storage tank is connected to the inlet of the accelerator metering pump. The outlet of the jet pump and the outlet pipeline of the accelerator metering pump are connected to the inlet of the high-temperature water-cooled atomization spray gun of hydrogen peroxide. The spray gun is inserted into the flue at the tail of the boiler. The flue gas is washed, the bottom of the absorption tower is connected to a first-level cyclone, the bottom outlet of the second-level cyclone is connected to the inlet of the nitrite treatment tank, and the outlet of the nitrite treatment tank is connected to the gypsum treatment system; the invention realizes the single-tower combined desulfurization and denitrification Mercury removal, the process is simple, the removal efficiency is high, the operating cost is low, and the catalyst loss is small; it can be used in coal-fired power station boilers, industrial boilers, waste incinerators, etc. Broad market application prospects.
Description
Technical field
The invention belongs to coal-fired plant flue gas purification techniques fields, and in particular to a kind of combined desulfurization and denitration based on calcium method
The method and device thereof of demercuration.
Background technique
A large amount of flue dust, SO are discharged in coal unit operational process2, the atmosphere pollutions such as NOx and Hg, bring serious
Therefore environmental problem, the sustainable development for affecting the physical and mental health and economic society of people develop efficient pollutant catabolic gene
It is of great significance with purification techniques.
Currently, coal unit discharges pollutants, main control object is SO2, NOx and dust.
In addition, coal-fired flue-gas removing heavy metal Hg is imperative, and China was in 2011 with the continuous improvement of environmental requirement
The emission limit of clear stipulaties mercury is in " fossil-fuel power plant atmospheric pollutant emission standard " (the GB 13223-2011) newly implemented
0.03mg/m3.Common power plant pollution object control method is desulfurization by lime gypsum method, SCR denitration, electrostatic precipitation.Due to every kind
Pollutant catabolic gene means are removed primarily directed to Single Pollution object, cause the initial cost of each environmental protection equipment larger, system complex, factory
Land used is more, and operating cost is excessively high.There is presently no mature flue gas demercuration technology, existing environmental protection equipment takes off heavy metal Hg
Removing solid capacity is also limited.Wet process multi-pollutant joint removing sulfuldioxide can be realized in single column to be removed while multiple pollutant, is had
The advantages such as simple process, operating cost is low, are the developing direction of the following pollutant control technology.Wherein, it is preposition oxidation with efficiently
Absorb the hot spot for combining and realizing that the joint removing of wet process multi-pollutant is even more power environment protection area research in recent years.
Chinese invention patent (CN103463978B) is disclosed based on catalytic oxidation of hydrogen peroxide flue gas and desulfurizing and denitrifying
Device and method, in that patent hydrogen peroxide by be injected in catalyst surface catalysis generate active material；Chinese invention is special
Sharp (CN104923049B) discloses a kind of light radiation ozone/hydrogen peroxide solution simultaneous SO_2 and NO removal demercuration method, dioxygen in the patent
Water generates oxidisability hydroxyl radical free radical under ultraviolet radiation；Chinese invention patent (CN1239235C) discloses while desulfurization is de-
The dry method flue gas cleaning technology and its system of nitre, do not specify specific hydrogen peroxide spray technology in that patent, and pollutant absorbs
Using individual dry desulfurization and Dry denitration technique.Chinese invention patent (CN100496675C) discloses simultaneous SO_2 and NO removal
Wet ammonia flue gas cleaning technology and its system, hydrogen peroxide is injected in after deduster in flue gas in that patent, is not mentioned
And demercuration effect, and using ammonium hydroxide as desulfurization denitrification agent, reaction product setting oxidation fan carries out pressure oxidation.
Summary of the invention
The present invention existing pollutant combined removal technology there are aiming at the problem that, a kind of combined desulfurization based on calcium method is provided
The method and device thereof of denitration demercuration, using the efficiently preposition oxidation technology of flue, in conjunction with desulfurization by lime gypsum method, in addition organic
SO is realized in the effect of catalyst2、NOxIt is removed with the joint of Hg, present invention can apply to coal-fired power station boiler, Industrial Boiler, rubbish
Rubbish incinerator etc. has a vast market application prospect especially suitable for built middle and small burn coal boiler is transformed.
In order to realize above-mentioned goal of the invention, The technical solution adopted by the invention is as follows:
A kind of combined desulfurization and denitration mercury removal device based on calcium method, including dioxygen water storage tank 1, the outlet of dioxygen water storage tank 1 connect
3 entrance of dioxygen water stream injection pump is connect, further includes promotor storage tank 2, connection 4 entrance of promotor metering pump in the outlet of promotor storage tank 2 is double
The outlet of oxygen water stream injection pump 3 connects 5 entrance of hydrogen peroxide high-temperature water cooling atomizing lance after converging with 4 export pipeline of promotor metering pump,
Hydrogen peroxide high-temperature water cooling atomizing lance 5 is inserted into 13 back-end ductwork of boiler, and back-end ductwork is connected to absorption tower 6, cigarette through deduster 12
Gas enters 6 bottom of absorption tower through deduster 12, and slurry circulating pump 7 is connected to 6 bottom absorbing liquid of absorption tower and top spray layer, adverse current
Absorbing liquid of 6 bottom of spray absorber containing organic catalyst washs flue gas, enters at the top of 6 bottom of absorption tower connection level-one cyclone 8
Mouthful, 8 middle part serum outlet of level-one cyclone connects 6 bottom of absorption tower, and 8 outlet at bottom of level-one cyclone connects second cyclone 9
Top entry, 9 middle part serum outlet of second cyclone connect 6 bottom of absorption tower, and 9 outlet at bottom of second cyclone connects nitrous acid
10 entrance of salt treatment tank, the outlet of nitrite treatments tank 10 connection gypsum treatment system 11.
The conical nozzle 14 of the hydrogen peroxide high-temperature water cooling atomizing lance 5 is symmetrical above and below, is mounted on hydrogen peroxide height at equal intervals
On the cold atomizing lance of warm water, for the narrow head of conical nozzle 14 as solution jet entrance and hydrogen peroxide solution pipeline connection, dioxygen is water-soluble
Liquid pipeline is connected to hydrogen peroxide inlet tube 15, and hydrogen peroxide solution pipeline is arranged in hydrogen peroxide high-temperature water cooling atomizing lance innermost layer；Spray
Rifle jet air pipeline 16 is arranged in hydrogen peroxide solution pipeline outer layer, and jet air enters from 14 side of conical nozzle, carries double
Oxygen aqueous solution is atomized from 14 wide opening position of conical nozzle to be sprayed；Spray gun water-cooled inner tube road connection spray gun water cooling tube inlet 17 is wrapped in
16 outer layer of spray gun jet air pipeline, the outer pipeline connection spray gun water cooling tube outlet 18 of spray gun water cooling are in hydrogen peroxide high-temperature water harl
Change the outermost layer arrangement of spray gun.
It is 300~500 DEG C that the hydrogen peroxide high-temperature water cooling atomization spray spray gun 5, which is inserted into the temperature section of 13 back-end ductwork of boiler,
The pressure limit of hydrogen peroxide solution is 0.1~0.3MPa, the pressure of spray gun jet air in hydrogen peroxide high-temperature water cooling atomizing lance 5
Range is 0.6MPa~0.8MPa, and spray gun water cooling tube exports the control of 18 temperature at 30~50 DEG C.
Hydrogen peroxide solution concentration is 20%~50wt% in the dioxygen water storage tank 1, and the amount of injection of hydrogen peroxide is H2O2/NO
Molar ratio=1.05~2；Promotor in the promotor storage tank 2 is sodium peroxydisulfate, sodium bicarbonate, hydroxylamine hydrochloride, resists
Bad hematic acid and sodium sulfite are one such or a variety of, and concentration range is 0.01% to 2% after mixing with hydrogen peroxide solution.
The organic catalyst contained in absorbing liquid in the absorption tower 6 is a kind of organic matter with aliphatic hydrocarbon, fat
Hydrocarbon includes any one of methyl, ethyl, propyl, butyl etc., and the addition concentration of organic catalyst is 0.1%~5%；
The catalyst recovery yield of the level-one cyclone 8 is greater than 95%, and the catalyst recovery yield of second cyclone 9 is greater than
90%.
6 bottom of absorption tower is not provided with oxidation fan.
A kind of combined desulfurization and denitration demercuration method of combined desulfurization and denitration mercury removal device based on calcium method, dioxygen
Water is sprayed into 13 tail portion high-temperature flue of boiler after mixing with promotor by hydrogen peroxide high-temperature water cooling atomizing lance 5, moment orientation
Strong oxidizing property free radical OH is generated by the NO and Hg in flue gas0It is oxidized to NO2And Hg2+, the absorbing liquid in absorption tower 6, which contains, to be had
Machine catalyst absorbs SO by spraying layer countercurrent spray2、NO2And Hg2+, realize combined desulfurization and denitration demercuration, having in absorbing liquid
Machine catalyst passes through 9 recycling and reusing of level-one cyclone 8 and second cyclone；The slurries of absorb the bottom of the tower are introduced into level-one eddy flow
Device 8 contains a large amount of organic catalyst, pumps after being extracted since organic catalyst is not soluble in water in the slurries of upper layer after eddy flow
Absorption tower 6 is gone back to, the slurries containing a large amount of gypsum enter second cyclone 9 in lower layer's slurries；Second cyclone 9 continues separation catalysis
Upper layer is contained the slurries of a small amount of catalyst, further returns absorption tower by agent, guarantees the rate of recovery of catalyst, second level eddy flow
9 lower layer's slurries of device enter gypsum treatment system 11 after the processing of nitrite treatments tank 10, and nitrite anions end reaction generates nitrogen
Gas, sulfur dioxide and nonvalent mercury generate gypsum and bivalent mercury discharge system.
Joint elimination reaction principle is as follows:
Hg+4·OH→Hg2++2H2O+O2
NO+·OH→NO2+·H
SO2+H2O→H2SO3
H2SO3+ catalyst → catalyst H2SO3
Catalyst H2SO3+2NO2+H2O→2HNO2+H2SO4+ catalyst
Ca(OH)2+H2SO4→CaSO4↓+2H2O
Ca(OH)2+HNO2→Ca(NO2)2+2H2O
Sulfur dioxide is dissolved in the inferior sulfate radical of water generation in absorption tower, is combined into more stable complexing with organic catalyst
Object, this complex compound and NO2Contact occurs redox reaction and generates nitrous acid, and the inferior sulfate radical of organic catalyst complexing occurs anti-
Ying Hou, organic catalyst can continue that H is complexed2SO3It completes to recycle, certain organic catalysis agent content can guarantee in absorbing liquid
A certain amount of inferior sulfate radical in absorbing liquid guarantees NO2Removal efficiency.
Absorb the bottom of the tower is not provided with oxidation fan, by NO2It is carried out freely with the inferior sulfate radical not being complexed by catalyst
Base chain reaction generates sulfate radical, and reaction speed is exceedingly fast, and is not required to setting oxidation fan i.e. and can guarantee that the crystallization of gypsum generates, reaction
Principle is as follows:
The present invention has a characteristic that
1) oxidation efficiency is high, and hydrogen peroxide waste is few: the present invention selects hydrogen peroxide to be atomized in high-temperature flue gas, moment excitation
The free group of strong oxidizing property aoxidizes NO and Hg0, oxidation efficiency height；Before dioxygen water atomization, by addition free radical scavenger,
It reduces atomizing pressure and increases the means such as spray gun cooling effect, reduce the invalid selfdecomposition of hydrogen peroxide, hydrogen peroxide waste is few.
2) simple process is widely used: the present invention only increases hydrogen peroxide on the basis of not changing power plant's existing equipment
Spraying system and catalyst recovery devices add a small amount of organic catalyst, and efficient combined desulfurization and denitration demercuration, work can be realized
Skill is simple, and operating cost is cheap, is widely used in existing limestone-gypsum method absorption tower transformation.
3) pollutant does not generate secondary pollution: sulfureous in flue gas oxide is finally reflected generation gypsum, nitrogen oxidation by this method
Object end reaction generates nitrogen, and bivalent mercury is finally discharged with gypsum, and content is extremely low not to generate secondary pollution.
Detailed description of the invention
Fig. 1 is a kind of method and device thereof system schematic of the combined desulfurization and denitration demercuration based on calcium method of the present invention.
Fig. 2 is the schematic diagram of hydrogen peroxide high-temperature water cooling atomizer of the present invention.
In figure, 1 is dioxygen water storage tank, and 2 be promotor storage tank, and 3 be dioxygen water stream injection pump, and 4 be promotor metering pump, and 5 are
Hydrogen peroxide high-temperature water cooling atomizing lance, 6 be absorption tower, and 7 be slurry circulating pump, and 8 be level-one cyclone, and 9 be second cyclone, 10
It is nitrite treatments tank, 11 be gypsum treatment system, and 12 be deduster, and 13 be boiler, and 14 be conical nozzle, and 15 be hydrogen peroxide
Inlet tube, 16 be spray gun jet air pipeline, 17 spray gun water cooling tube inlets, the outlet of 18 spray gun water cooling tubes.
Specific embodiment
Below in conjunction with drawings and the specific embodiments, the present invention is described in further detail.
Embodiment 1:
A kind of combined desulfurization and denitration demercuration method based on calcium method of the present embodiment, process flow is as shown in Figure 1, selection tail portion
Flue gas temperature installs hydrogen peroxide high-temperature water cooling atomization spray spray gun 5 at 350 DEG C, and the concentration of hydrogen peroxide solution is 27.5wt%, double
Oxygen water and NO and Hg0Injection molar ratio be 1.1:1, realize that the oxygenation efficiency of nitrogen oxides and nonvalent mercury is greater than 98%.
As the preferred embodiment of the present invention, the promotor in promotor storage tank is sodium peroxydisulfate, and addition concentration is
0.1%.
As the preferred embodiment of the present invention, the pressure of jet stream compressed air is in dioxygen high-temperature water cooling atomizing lance
0.8MPa, the pressure for pumping hydrogen peroxide solution is 0.2MPa, adjusts the flow of cooling compressed air in spray gun, and control hydrogen peroxide enters
Temperature is lower than 40 DEG C in mouth pipeline.
As the preferred embodiment of the present invention, selecting the concentration of catalyst in absorption tower is 0.1%, is guaranteed in absorption tower
Desulfuration efficiency is greater than 99%, and denitration efficiency is greater than 95%, and demercuration efficiency is greater than 90%.
Level-one cyclone is chosen as the preferred embodiment of the present invention for the recovery efficiency for guaranteeing organic catalyst
Swirl velocity is greater than second cyclone, and the catalyst recovery yield of level-one cyclone is not less than 95%, catalyst in second cyclone
The rate of recovery be not less than 90%, it is ensured that the proportion of goods damageds of catalyst are smaller.
Embodiment 2:
The present embodiment selection back-end ductwork smoke temperature installs hydrogen peroxide high-temperature water cooling atomization spray spray gun 5, hydrogen peroxide at 500 DEG C
The concentration 50% of solution, addition promotor are sodium peroxydisulfate and sodium bicarbonate, concentration 0.5%, hydrogen peroxide and NO and Hg0Rub
, than being 1.05:1, the compressed air pressure of hydrogen peroxide high-temperature water cooling atomization spray spray gun 5 is 0.6MPa for you, pumps hydrogen peroxide solution pressure
Power is 0.3MPa, so that temperature is lower than 50 DEG C in hydrogen peroxide entrance pipe, nitrogen oxides and nonvalent mercury oxidation efficiency may be implemented
Not less than 98%, catalyst 1% is added in absorption tower, realizes that desulfuration efficiency is greater than 99%, denitration efficiency is greater than 95%, demercuration effect
Rate is greater than 95%.
Embodiment 3:
The present embodiment selection back-end ductwork smoke temperature installs hydrogen peroxide high-temperature water cooling atomization spray spray gun 5, hydrogen peroxide at 400 DEG C
The concentration 35% of solution, addition promotor are ascorbic acid and sodium sulfite, concentration 1%, hydrogen peroxide and NO and Hg0Mole
Than being 0.7MPa, pumping hydrogen peroxide solution pressure for the compressed air pressure of 1.1:1, hydrogen peroxide high-temperature water cooling atomization spray spray gun 5
Nitrogen oxides and nonvalent mercury oxidation efficiency may be implemented not so that temperature is lower than 30 DEG C in hydrogen peroxide entrance pipe for 0.25MPa
Lower than 99%, catalyst 3% is added in absorption tower, realizes that desulfuration efficiency is greater than 99%, denitration efficiency is greater than 95%, demercuration efficiency
Greater than 98%.
Claims (8)
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| CN201811324526.XA CN109173718A (en) | 2018-11-08 | 2018-11-08 | Calcium method-based combined desulfurization, denitrification and demercuration method and device |
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| CN201811324526.XA CN109173718A (en) | 2018-11-08 | 2018-11-08 | Calcium method-based combined desulfurization, denitrification and demercuration method and device |
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| CN109647146A (en) * | 2019-01-23 | 2019-04-19 | 华能国际电力股份有限公司 | System and method for desulfurization and denitrification of industrial boiler flue gas |
| CN111018082A (en) * | 2019-12-18 | 2020-04-17 | 中国环境科学研究院 | An in-situ agent injection system and method for zero-valent iron-activated persulfate |
| CN113041838A (en) * | 2021-05-06 | 2021-06-29 | 昆明理工大学 | Method for cooperatively removing low-concentration sulfur dioxide and mercury in smelting flue gas |
| WO2022047878A1 (en) * | 2020-09-01 | 2022-03-10 | 刘传林 | Liquid gas industrialized application system |
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Application publication date: 20190111 |