CN105233647B - A kind of method of ammonium sulfide solution desulphurization denitration - Google Patents
A kind of method of ammonium sulfide solution desulphurization denitration Download PDFInfo
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- CN105233647B CN105233647B CN201510592576.6A CN201510592576A CN105233647B CN 105233647 B CN105233647 B CN 105233647B CN 201510592576 A CN201510592576 A CN 201510592576A CN 105233647 B CN105233647 B CN 105233647B
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- flue gas
- ammonium sulfide
- oxidation
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- UYJXRRSPUVSSMN-UHFFFAOYSA-P Ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 title claims abstract description 37
- 239000003546 flue gas Substances 0.000 claims abstract description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 35
- 230000003647 oxidation Effects 0.000 claims abstract description 31
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 claims abstract description 30
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 25
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 17
- 239000005864 Sulphur Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000005712 crystallization Effects 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 50
- XYXNTHIYBIDHGM-UHFFFAOYSA-N Ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 26
- 239000001099 ammonium carbonate Substances 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 9
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N azanium;hydron;carbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 239000007921 spray Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010410 dusting Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atoms Chemical class [H]* 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 44
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003337 fertilizer Substances 0.000 abstract description 14
- 229910052813 nitrogen oxide Inorganic materials 0.000 abstract description 10
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004140 cleaning Methods 0.000 abstract description 5
- 239000000428 dust Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 229910002089 NOx Inorganic materials 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 230000035507 absorption Effects 0.000 abstract 2
- 206010037660 Pyrexia Diseases 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000008247 solid mixture Substances 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 14
- 230000003009 desulfurizing Effects 0.000 description 13
- ZETCGWYACBNPIH-UHFFFAOYSA-N azane;sulfurous acid Chemical compound N.OS(O)=O ZETCGWYACBNPIH-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000003723 Smelting Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Ammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N Cyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003245 coal Substances 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- 238000000889 atomisation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- -1 titanium dioxide Nitrogen Chemical compound 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N Ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000005591 charge neutralization Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000001264 neutralization Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N Potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 241000196435 Prunus domestica subsp. insititia Species 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000003638 reducing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a kind of method of ammonium sulfide solution desulphurization denitration, belong to flue gases purification field.The method of the invention is using ammonium sulfide solution as absorbent, absorption cleaning sulfur dioxide（SO2）And nitrogen oxides（NOx）；Industrial furnace flue gas removing dust, after water-washing pre-treatment, appropriate air is blasted into flue, nitric oxide in nitrogen oxides under the conditions of low-grade fever is oxidized to nitrogen dioxide, flue gas is through two grades of absorptions of ammonium sulfide, sulfur dioxide and nitrogen oxides in gas, which are absorbed and is converted into salt, have been stayed in solution, after the completion of absorbing reaction, sulphur is recovered by filtration, filtrate is neutralized, oxidation, evaporative crystallization, drying process processing, the solid mixture of ammonium sulfate and ammonium nitrate is obtained, this mixture can be sold directly as fertilizer.Present invention process is simple, easy to operate, and denitrification efficiency is high, and cost is low, suitable for industrial applications.
Description
Technical field
The present invention relates to a kind of method of ammonium sulfide solution desulphurization denitration, belongs to flue gases purification field.
Background technology
The energy of China is based on fire coal, and accounting for the raw coal of coal production 75% is used to directly burn, and is produced in coal combustion process
Severe contamination, the sulfur dioxide of generation can cause acid rain, and nitrogen oxides is also one of acid rain Producing reason, while endangering people
The health of class, can also damage the ozone layer and produce under certain condition photochemical fog etc., and coal-fired flue-gas is to cause me in a word
One of greatest contamination source of state's environmental destruction.China's energy-consuming accounts for the 8% ~ 9% of the world, and the discharge capacity of sulfur dioxide is accounted for
The 15.1% of the world, the sulfur dioxide that fire coal is discharged accounts for the 87% of national discharge capacity again, therefore sulfur dioxide and nitrogen oxides are dirty
The problem of dye, is urgently to be resolved hurrily.Domestic coal-burning power plant, smeltery's flue gas desulfurization technique species is more, such as limestone-gypsum method, simply
Wet method, sodium sulfide method, wet-type ammonia, electronic beam method etc..It is at most SCR technology that denitrating flue gas, which is applied,（SCR）
With SNCR technology SNCR, the denitration reaction temperature of SCR technology is general at 280 ~ 400 DEG C, and denitration efficiency is up to 90%
More than；The reaction temperature of SNCR technologies is general at 850 ~ 1100 DEG C, and denitration efficiency is medium, typically 50% or so.
At present, the desulfurization and denitrification integral technology of use is the joint of desulphurization and denitration two ways, i.e. SO mostly2And NOX
Respectively handle.There are various problems in existing desulphurization denitration technology, the fixed investment of such as limestone-gypsum method is big, desulfurization
Cost is high, and a large amount of gypsum of generation are difficult to processing etc.；SCR technology has that catalyst investment is big, smoke components influence is big, run into
The problems such as this is high, it is high to there is reaction temperature in SNCR technologies, reducing agent with flue gas mixability is poor, denitration efficiency is low, ammonia spilling
A series of problems, such as measuring big.Therefore, there is high fixed investment, operation and maintenance cost height, operation behaviour in united desulphurization denitration technology
The problems such as making complicated.ZL201410290112.5 " method that flue gas desulfurization and denitrification is carried out using urea co-production technology of preparing " is carried
Go out：The ammonia produced with urea co-production technology of preparing can be individually used for flue gas desulfurization and denitrification, and obtained cyanuric acid also can be independent
For flue gas desulfurization and denitrification, ammonia and cyanuric acid may also be combined with while being used for desulphurization denitration, and ammonia desulfurization, ammonia takes off
Nitre, cyanuric acid desulfurization, cyanuric acid denitration is all separate, and desulfurization need to be combined to progress with denitration two parts
Desulphurization denitration purpose can be reached, reaction temperature also needs to control ammonia, cyanuric acid and sulfur dioxide between 500 DEG C ~ 1100 DEG C
Air inlet ratio with nitrogen oxides, although improve denitrification efficiency, but complex operation, consume energy higher.ZL200710052129.7
The patent of invention of " wet ammonia flue gas cleaning technology and its system of simultaneous SO_2 and NO removal " is proposed：First make the oxidation in flue gas
Nitrogen carries out oxidation reaction generation nitrogen dioxide, sulfur dioxide and nitrogen dioxide in flue gas is reacted respectively with ammoniacal liquor
Ammonium sulfite, ammonium nitrate and ammonium nilrite are generated, then ammonium sulfite therein and ammonium nilrite is occurred oxidation reaction generation pair
Product ammonium sulfate and ammonium nitrate, while carrying out demisting to the flue gas after desulphurization denitration, finally obtain clean flue gas, nitrogen in this invention
Oxide is absorbed while can produce nitric oxide again, there is the problem of denitration efficiency is not high.Therefore a kind of operation letter is developed
Single, operating cost is low, and the good technology of simultaneous SO_2 and NO removal effect is the striving direction of environmentally friendly research work.
The content of the invention
It is an object of the invention to provide a kind of ammonium sulfide solution desulfurization denitration method, industrial furnace tail gas removing dust is washed,
After air oxidation pretreatment, sulfur dioxide and nitrogen oxides in two grades of ammonium sulfide solution absorption towers, absorption cleaning flue gas are passed through,
Reach the purpose of tail gas cleaning discharge；Absorbing liquid is recovered by filtration after sulphur, neutralized, oxidation, evaporative crystallization and drying process
The mixed fertilizer of ammonium sulfate and ammonium nitrate is obtained after processing；This method can simultaneous SO_2 and NO removal, and recycle, energy-conservation subtracted
Arrange, environmental protection, the technology such as comprehensive utilization of resources is all important breakthrough.
A kind of method of ammonium sulfide solution desulphurization denitration of the present invention, specifically includes following steps：
（1）By industrial furnace flue gas after rough dusting and washing, flue-gas temperature is cooled to less than 50 DEG C；
（2）To step（1）The nitric oxide being passed through in flue gas after processing in air, nitrogen oxides is oxidized to titanium dioxide
Nitrogen；
（3）The mixed solution regulation pH value of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is added in ammonium sulfide solution
It is 10%-25% to 7 ~ 7.5 mass percent concentrations for obtaining ammonium sulfide in ammonium sulfide spray liquid, ammonium sulfide spray liquid；
（4）Will be through step（2）Flue gas after middle air oxidation and ammonium sulfide spray liquid haptoreaction, absorbing reaction process
In add ammonium sulfide control absorbing liquid pH value between 5 ~ 7.5, after the completion of absorption, SO2And NOXGot off by absorption, absorbing liquid
Referred to as rich solution；
（5）Rich solution, which is recovered by filtration, obtains sulphur, and ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate regulation pH value are added in filtrate and is dropped to
Less than 7.5, the ammonium bisulfite in solution is converted into ammonium sulfite；It is passed through under conditions of solution temperature is 40 DEG C ~ 80 DEG C
Add mass percent under air oxidation or normal temperature to be aoxidized for 27.5%-50% hydrogen peroxide, ammonium sulfite is oxidized to sulphur
Sour ammonium, ATS (Ammonium thiosulphate) is oxidized to ammonium hydrogen sulfate, and pH value can be reduced；Ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate is added after oxidation to adjust
Save pH to 6-7.
（6）By step（5）Obtained mixed liquor is concentrated by evaporation to the 30% ~ 40% of original volume in 110 DEG C ~ 120 DEG C, then at 30
DEG C ~ 40 DEG C of crystallizations, the mixture of separation dry obtained ammonium sulfate and ammonium nitrate.
It is preferred that, step（2）The amount that the air oxidation is passed through air is the 10% ~ 20% of exhaust gas volumn.
It is preferred that, step（3）The ATS (Ammonium thiosulphate) and ammonium nitrate mixed solution sulfite hydrogen ammonium, ATS (Ammonium thiosulphate) and
The mass ratio of ammonium nitrate is 2:1:1~5:1:1.
When reaction starts, solution ph is larger, and H can be discharged in sulfur dioxide absorption and nitrogen oxide containing gas2S gases,
In order to avoid secondary pollution, the regulation liquid that pH value is 4 ~ 7 is added into premature cure ammonium absorbing liquid, makes the pH of ammonium sulfide absorbing liquid
Value is reduced to less than 7.5；Adjust the mixed solution of liquid ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate, the quality of three kinds of materials
Concentration ratio is 2:1:1~5:1:1；With the progress of absorbing reaction, the pH of absorbing liquid can be reduced, when pH is reduced to 5, to
Ammonium sulfide solution is added in absorbing liquid, controls the pH value of absorbing liquid in the range of 5 ~ 7.5, this scope assimilation effect is optimal；
It is atomized in absorption tower by special whirlpool shower nozzle, flue gas is handled by vaporific two grades of absorption cleanings of ammonium sulfide solution, SO2And NOX
Got off by absorption, absorbing liquid is referred to as rich solution, rich solution is mainly ATS (Ammonium thiosulphate), ammonium bisulfite, sulphur, ammonium sulfate and ammonium nitrate
Mixed liquor.
Simultaneous SO_2 and NO removal principle of the present invention is as follows：
Absorb：Using (NH4)2S solution absorbs the SO in flue gas2And NOX, absorbing reaction process is as follows：
NO2+(NH4)2S→(NH4)2SO4+N2
SO2 + H2O → H2SO3
3NO2+H2O→ 2HNO3+NO
2NO+O2→2NO2
H2SO3 + (NH4)2S → (NH4) 2SO3 + H2S
2NO+2(NH4)2SO3→2(NH4)2SO4+N2
2HNO3+(NH4)2S → 2NH4NO3 + H2S
H2S + (NH4) 2S → 2NH4HS
2H2S + SO2 → 3S + 2H2O
2 H2S + NO2 → 2S + N2 + 2H2O
S + (NH4)2SO3 → (NH4)2S2O3
(NH4)2S2O3+2NO2+NH4OH→4(NH4)2SO4+N2
(NH4)2SO3 + 0.5O2 → (NH4)2SO4
(NH4)2SO3 + SO2 + H2O→ 2NH4HSO3
4(NH4)2SO3+2NO2→4(NH4)2SO4+N2
Neutralize：Absorbing liquid is brought out, and is recovered by filtration in sulphur, filtrate and is contained NH4HSO3, (NH4)2S2O3, (NH4)2SO4With
NH4NO3, add ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate and neutralize, make the NH in absorbing liquid4HSO3All it is transformed into (NH4)2SO3And adjust
PH value is saved between 6-7.Course of reaction is as follows：
NH3 + NH4HSO3 = (NH4)2SO3
Or
NH4HCO3 + NH4HSO3 = (NH4)2SO3 + CO2 + H2O
Oxidation：Different salts are mixed with absorbing liquid, are not suitable for producing pure ammonium sulfate or ammonium nitrate products, by sulfurous
Sour ammonium and ATS (Ammonium thiosulphate) are further aoxidized, and the mixed fertilizer for making ammonium sulfate and ammonium nitrate is used；Ammonium sulfite solution and sulphur
The oxidation of ammonium thiosulfate has two methods：
（1）Hydrogen peroxide oxidation hydrogen peroxide oxidation will not bring other impurity into, and oxidation effectiveness is good, due to the oxygen of hydrogen peroxide
The property changed is stronger, and ATS (Ammonium thiosulphate) is oxidized to ammonium hydrogen sulfate, and reaction equation is as follows：
(NH4)2SO3 + H2O2 = (NH4)2SO4 + H2O
(NH4)2S2O3 + 4H2O2 = 2NH4HSO4 + 3H2O
After the completion of oxidation reaction, because thiosulfate anion is oxidized, hydrogen radical ion is produced, the pH value of solution is reduced, now
Need to add ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate adjust pH value to 6-7 scope.
（2）Air oxidation process utilizes the oxidizable principle of ammonium sulfite, by sulfite oxidation is ammonium sulfate with air, should
Contain (NH in the ammonium sulfite of method production4)2S2O3With certain catalysed oxidn, the oxidation to ammonium sulfite is favourable, instead
Should be as follows：
(NH4)2SO3 + 0.5O2 = (NH4)2SO4
(NH4)2S2O3 + H2O + 2O2 = 2NH4HSO4
Air oxidation is relatively slow, need to improve the temperature of solution at 40 DEG C ~ 50 DEG C, using aerator aerating oxidation or adopts
Spray mode from top to bottom with oxidizing tower to be aoxidized, that is, increase the contact area of oxygen and solution, accelerate entering for oxidation reaction
OK.Ammoniacal liquor is added after oxidation, ammonium carbonate or ammonium hydrogen carbonate adjust pH value to 6-7 scope.
It is concentrated by evaporation：The mixed liquor of ammonium sulfate, ATS (Ammonium thiosulphate) and ammonium nitrate is concentrated by evaporation to substance in 110 DEG C ~ 120 DEG C
Long-pending 30% ~ 40%.
Crystallization：Ammonium sulfate after concentration, ATS (Ammonium thiosulphate) and ammonium nitrate mixed liquor, which are put, is cooled to 30 DEG C ~ 40 DEG C crystallizations.Will
Crystalline mother solution is centrifuged, and obtains the ammonium sulfate that water content is 3-5%, the crystallization of ATS (Ammonium thiosulphate) and ammonium nitrate, wherein thio sulphur
Sour ammonium hygroscopicity is stronger, is difficult crystallization and separates out, has been partially left in concentrate, so obtained crystallization is with ammonium sulfate and nitric acid
Mixture based on ammonium, concentrate can be sold as liquid fertilizer.
Advantages of the present invention：
（1）Removal efficiency is high simultaneously with sulfur dioxide for nitrogen oxides in industrial furnace flue gas, and flue gas can be with qualified discharge.
The mixed fertilizer of desulfuration efficiency >=99%, denitration efficiency >=90%, byproduct sulfur purity >=98%, ammonium sulfate and ammonium nitrate is nitrogenous
Amount >=20%.
（2）From the SO in flue gas during smelting2The byproducts such as sulphur and nitrogenous fertilizer are produced with NOx, denitrification efficiency is high, runs into
This is low, and sulphur have with other sulphur products compared with it is widely used, it is easy to the advantages of storage and transport.Therefore, the present invention is solution
Certainly flue gas during smelting purifies the key technology with utilizing, and it is suitable to industrial applications.
Embodiment
The present invention is described in further detail below by embodiment, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
SO in industrial furnace flue gas2And NOXRecycling method, particular content is as follows：
（1）Pending flue gas is zinc smelting flue gas in the present embodiment, and exhaust gas volumn is 30000m3Contain in/h, stove mouthful flue gas
SO2：3% ~ 4%, NOX：1300~1700mg/m3, flue-gas temperature is cooled to less than 50 DEG C by flue gas during smelting removing dust after washing, drum
Enter air（The amount of air is the 10% of exhaust gas volumn）；
（2）By the ammonium sulfide solution that mass percent concentration is 25%, pH=7.2（ATS (Ammonium thiosulphate), ammonium bisulfite are used
With the regulation of ammonium nitrate mixed liquor, the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 3:1:1）Pass through absorption tower
Whirlpool shower nozzle is atomized, and flue gas enters two-level absorption tower adverse current and fully contacted with the ammonium sulfide solution of atomization after cooling, to containing SO2With
NOXThe pH value of ammonium sulfide control absorbing liquid is added during flue gas during smelting progress efficient absorption, absorbing reaction between 7.5, only
Change flue gas emptying；
（3）Absorb SO2And NOXRich solution by press filtration Recovered sulphur, into filtrate add ammonium carbonate neutralized, tune
PH value is saved to 6.5, air oxidation is passed through under conditions of solution temperature is 60 DEG C, oxidation completes addition ammonium hydrogen carbonate regulation pH value
For 6；
（4）Solution after oxidation is concentrated by evaporation at a temperature of 115 DEG C to the 30% of original solution volume, is cooled to 30 DEG C of crystallizations,
Centrifuge, produce ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate is used as liquid fertilizer.
By implementing SO in the above method, smoke desulfurization efficiency >=99%, denitration efficiency >=90%, exiting flue gas2Content≤
100mg/m3；NOXContent≤100mg/m3, byproduct sulfur purity >=98%, mixed fertilizer nitrogen content >=20%.
Embodiment 2
SO in smelting lead2And NOXThe method of recycling, particular content is as follows：
（1）Pending flue gas is smelting lead in the present embodiment, and exhaust gas volumn is 10000m3Contain in/h, stove mouthful flue gas
SO2：0.8% ~ 1%, NOX：1000~1300mg/m3, industrial furnace flue gas removing dust, after washing by flue-gas temperature be cooled to 50 DEG C with
Under, blast air（The amount of air is the 15% of exhaust gas volumn）；
（2）By the ammonium sulfide solution that mass percent concentration is 10%, pH=7.5（ATS (Ammonium thiosulphate), ammonium bisulfite are used
With the regulation of ammonium nitrate mixed liquor, the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 5:1:1）Pass through absorption tower
Whirlpool shower nozzle is atomized, and flue gas enters two-level absorption tower adverse current and fully contacted with the ammonium sulfide solution of atomization after cooling, to containing SO2With
NOXFlue gas during smelting carries out the pH value for adding ammonium sulfide control absorbing liquid during efficient absorption, absorbing reaction between 6, purifies
Flue gas is emptied；
（3）Absorb SO2And NOXRich solution by press filtration Recovered sulphur, into filtrate add ammonium hydrogen carbonate neutralized,
PH value is adjusted to 7, the solution hydrogen peroxide after neutralization（Mass percent is 48%）Oxidation, oxidation completes addition ammonium carbonate regulation
PH value is 7；
（4）Solution after oxidation is concentrated by evaporation at a temperature of 110 DEG C to the 35% of original solution volume, is cooled to 35 DEG C of crystallizations,
Centrifuge, produce ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate is used as liquid fertilizer.
By implementing SO in the above method, smoke desulfurization efficiency >=99%, denitration efficiency >=90%, exiting flue gas2Content≤
100mg/m3；NOXContent≤100mg/m3, byproduct sulfur purity >=98%, mixed fertilizer nitrogen content >=20%.
Embodiment 3
SO in nickel fibers flue gas2And NOXThe method of recycling, particular content is as follows：
（1）Pending flue gas is nickel fibers flue gas in the present embodiment, and exhaust gas volumn is 20000m3Contain in/h, stove mouthful flue gas
SO2：1% ~ 2%, NOX：900~1200mg/m3, flue-gas temperature is cooled to less than 50 DEG C after washing, blasts air by flue gas removing dust
（The amount of air is the 20% of exhaust gas volumn）；
（2）By the ammonium sulfide solution that mass percent concentration is 17%, pH=7（Use ATS (Ammonium thiosulphate), ammonium bisulfite and
Ammonium nitrate mixed liquor is adjusted, and the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 2:1:1）Pass through the whirlpool on absorption tower
Whirlpool shower nozzle atomization, flue gas enters two-level absorption tower adverse current and fully contacted with the ammonium sulfide solution of atomization after cooling, to containing SO2And NOX
The pH value of ammonium sulfide control absorbing liquid is added during flue gas during smelting progress efficient absorption, absorbing reaction between 5, purifying smoke
Emptying；
（3）Absorb SO2And NOXRich solution by press filtration Recovered sulphur, into filtrate add ammoniacal liquor neutralized, regulation
PH value is to 6, the solution hydrogen peroxide after neutralization（Mass percent is 32%）Oxidation, oxidation completes addition ammoniacal liquor regulation pH value and is
7.5；
（4）Solution after oxidation is concentrated by evaporation at a temperature of 120 DEG C to the 40% of original solution volume, is cooled to 40 DEG C of crystallizations,
Centrifuge, produce ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate is used as liquid fertilizer.
By implementing SO in the above method, smoke desulfurization efficiency >=99%, denitration efficiency >=90%, exiting flue gas2Content≤
100mg/m3；NOXContent≤100mg/m3, byproduct sulfur purity >=98%, mixed fertilizer nitrogen content >=20%.
Claims (4)
1. a kind of method of ammonium sulfide solution desulphurization denitration, it is characterised in that specifically include following steps：
（1）By industrial furnace flue gas after rough dusting and washing, flue-gas temperature is cooled to less than 50 DEG C；
（2）To step（1）Air is passed through in flue gas after processing；
（3）Ammonium bisulfite is added in ammonium sulfide solution, the mixed solution of ATS (Ammonium thiosulphate) and ammonium nitrate adjust pH value to 7 ~
7.5 mass percent concentrations for obtaining ammonium sulfide in ammonium sulfide spray solution, ammonium sulfide spray solution are 10%-25%；
（4）Will be through step（2）Mended during flue gas and ammonium sulfide spray solution haptoreaction after middle air oxidation, absorbing reaction
Plus the pH value of ammonium sulfide control absorbing liquid, between 5 ~ 7.5, after the completion of absorption, absorbing liquid is referred to as rich solution；
（5）Rich solution, which is recovered by filtration, obtains sulphur, and ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate are added in filtrate and adjusts pH value to 6-7, so
It is afterwards to be passed through under air oxidation or normal temperature that to add mass percent concentration be 27.5%- under conditions of 40 DEG C ~ 80 DEG C in solution temperature
50% hydrogen peroxide is aoxidized, and ammoniacal liquor, ammonium carbonate or ammonium hydrogen carbonate regulation pH to 6-7 are added after oxidation；
（6）By step（5）Obtained mixed liquor is concentrated by evaporation, crystallized, separating the mixing that ammonium sulfate and ammonium nitrate are obtained after drying
Thing.
2. the method for ammonium sulfide solution desulphurization denitration according to claim 1, it is characterised in that：Step（2）Middle air oxygen
The amount that change is passed through air is the 10% ~ 20% of exhaust gas volumn.
3. the method for ammonium sulfide solution desulphurization denitration according to claim 1, it is characterised in that：Step（3）The sulfurous
The mass ratio of the mixed solution sulfite hydrogen ammonium of sour hydrogen ammonium, ATS (Ammonium thiosulphate) and ammonium nitrate, ATS (Ammonium thiosulphate) and ammonium nitrate is
2:1:1~5:1:1。
4. the method for ammonium sulfide solution desulphurization denitration according to claim 1, it is characterised in that：Step（6）Middle evaporation temperature
Spend for 110 DEG C ~ 120 DEG C, crystallization temperature is 30 DEG C ~ 40 DEG C.
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