CN105233647A - Desulphurization denitration method for ammonium sulfide solution - Google Patents
Desulphurization denitration method for ammonium sulfide solution Download PDFInfo
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- CN105233647A CN105233647A CN201510592576.6A CN201510592576A CN105233647A CN 105233647 A CN105233647 A CN 105233647A CN 201510592576 A CN201510592576 A CN 201510592576A CN 105233647 A CN105233647 A CN 105233647A
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- Prior art keywords
- ammonium
- flue gas
- solution
- ammonium sulfide
- oxidation
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- 238000000034 method Methods 0.000 title claims abstract description 40
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 title claims abstract description 34
- 239000003546 flue gas Substances 0.000 claims abstract description 60
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 32
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 30
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 18
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 8
- 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 48
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 9
- 239000001099 ammonium carbonate Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010410 dusting Methods 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 43
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 24
- 238000005516 engineering process Methods 0.000 abstract description 17
- 239000003337 fertilizer Substances 0.000 abstract description 14
- 238000006386 neutralization reaction Methods 0.000 abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000008247 solid mixture Substances 0.000 abstract 2
- 239000002250 absorbent Substances 0.000 abstract 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 238000007664 blowing Methods 0.000 abstract 1
- 239000000428 dust Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 12
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- -1 thiosulfate anion Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention discloses a desulphurization denitration method for ammonium sulfide solution, and belongs to the technical field of flue gas purification. The method comprises employing an ammonium sulfide solution as an absorbent to absorb sulfur dioxide (SO2) and nitrogen oxides (NOx); performing dust removal and water-washing pretreatment on industrial kiln and furnace flue gas, and blowing proper amount of air into a flue gas pipe, so as to oxidize nitrogen monoxide in the nitrogen oxides into nitrogen dioxide under a slight hot condition, performing two-stage absorption on the flue gas by ammonium sulfide, so as to enable sulfur dioxide and nitrogen oxides in the gas to be absorbed and converted into salts and left in the solution; after the absorption reaction is finished, filtering and recovering sulfur, and performing neutralization, oxidation, evaporation crystallization and drying processing on the filtrate, so as to obtain a solid mixture of ammonium sulfate and ammonium nitrate, wherein the solid mixture can be sold directly as a fertilizer. The method is simple in technology, easy to operate, high in desulphurization denitration efficiency, low in cost and suitable for industrialized application.
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, account for the raw coal of coal production 75% for direct burning, severe contamination is produced in coal combustion process, the sulfur dioxide produced can cause acid rain, nitrogen oxide is also one of acid rain Producing reason, endanger the health of the mankind simultaneously, also can damage the ozone layer under certain condition and produce photochemical fog etc., coal-fired flue-gas is one of greatest contamination source of causing China's environmental destruction in a word.China's energy-consuming accounts for 8% ~ 9% of the world, and the discharge capacity of sulfur dioxide accounts for 15.1% of the world, and the coal-fired sulfur dioxide discharged accounts for again 87% of national discharge capacity, and therefore the problems demand of sulfur dioxide and nitrogen oxides pollution solves.Domestic coal-burning power plant, smeltery's flue gas desulfurization technique kind is more, as limestone-gypsum method, simply wet constructed, sodium sulfide method, wet-type ammonia, electronic beam method etc.Denitrating flue gas application is maximum be the denitration reaction temperature of SCR technology (SCR) and SNCR technology SNCR, SCR technology generally at 280 ~ 400 DEG C, denitration efficiency reaches more than 90%; The reaction temperature of SNCR technology is generally at 850 ~ 1100 DEG C, and denitration efficiency is medium, generally about 50%.
At present, the desulfurization and denitrification integral technology of employing is the associating of desulphurization and denitration two kinds of modes mostly, i.e. SO
2and NO
xto process respectively.There is various problems in existing desulphurization denitration technology, the fixed investment as limestone-gypsum method is large, desulphurization cost is high, and a large amount of gypsum of generation are difficult to process etc.; There is the problems such as catalyst investment is large, smoke components impact is large, operating cost is high in SCR technology, it is high that SNCR technology exists reaction temperature, reducing agent and the series of problems such as flue gas mixability is poor, denitration efficiency is low, ammonia spill-out is large.Therefore, there is the problems such as fixed investment is high, operation and maintenance cost is high, operation is complicated in the desulphurization denitration technology of associating.ZL201410290112.5 " utilizes urea co-production technology of preparing to carry out the method for flue gas desulfurization and denitrification " and proposes: the ammonia produced by urea co-production technology of preparing can separately for flue gas desulfurization and denitrification, the cyanuric acid obtained also can separately for flue gas desulfurization and denitrification, ammonia and cyanuric acid also can combine simultaneously for desulphurization denitration, ammonia desulfurization, ammonia denitration, cyanuric acid desulfurization, cyanuric acid denitration is all separate, desulfurization need be combined with denitration two parts and carry out just reaching desulphurization denitration object, reaction temperature is between 500 DEG C ~ 1100 DEG C, also need to control ammonia, the air inlet ratio of cyanuric acid and sulfur dioxide and nitrogen oxide, although raising denitrification efficiency, but complicated operation, consume energy higher.The patent of invention of ZL200710052129.7 " wet ammonia flue gas cleaning technology of simultaneous SO_2 and NO removal and system thereof " proposes: first make the nitric oxide in flue gas carry out oxidation reaction and generate nitrogen dioxide, then make the sulfur dioxide in flue gas and nitrogen dioxide carry out reaction with ammoniacal liquor respectively and generate ammonium sulfite, ammonium nitrate and ammonium nilrite, ammonium sulfite wherein and ammonium nilrite generation oxidation reaction is made to generate byproduct of ammonium sulfate and ammonium nitrate again, demist is carried out to the flue gas after desulphurization denitration simultaneously, final acquisition clean flue gas, nitric oxide can be produced again the while that nitrogen oxide being absorbed in this invention, there is the problem that denitration efficiency is not high.Therefore exploitation is a kind of simple to operate, and operating cost is low, and the effective technology of simultaneous SO_2 and NO removal is the striving direction of environmental protection research work.
Summary of the invention
The object of this invention is to provide a kind of ammonium sulfide solution desulfurization denitration method, industrial furnace tail gas, through dedusting, is washed, after air oxidation pretreatment, pass into secondary ammonium sulfide solution absorption tower, the sulfur dioxide in absorption cleaning flue gas and nitrogen oxide, reach the object that tail gas cleans discharge; After absorbing liquid filtered and recycled sulphur, after neutralization, oxidation, evaporative crystallization and drying process process, obtain the mixed fertilizer of ammonium sulfate and ammonium nitrate; The method can simultaneous SO_2 and NO removal, and recycles, and to energy-saving and emission-reduction, environmental protection, the technology such as comprehensive utilization of resources are all important breakthroughs.
The method of a kind of ammonium sulfide solution desulphurization denitration of the present invention, specifically comprises the following steps:
(1) by industrial furnace flue gas through rough dusting and washing after, flue-gas temperature is cooled to less than 50 DEG C;
(2) in the flue gas after step (1) process, pass into air, the nitric oxide in nitrogen oxide is oxidized to nitrogen dioxide;
(3) the mixed solution adjust ph adding ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate in ammonium sulfide solution obtains ammonium sulfide spray liquid to 7 ~ 7.5, and in ammonium sulfide spray liquid, the mass percent concentration of ammonium sulfide is 10%-25%;
(4) by the flue gas after air oxidation in the step (2) and ammonium sulfide spray liquid haptoreaction, add ammonium sulfide in absorption reaction process and control the pH value of absorbing liquid between 5 ~ 7.5, after having absorbed, SO
2and NO
xabsorbed, absorbing liquid is called rich solution;
(5) rich solution filtered and recycled obtains sulphur, adds ammoniacal liquor, ammonium carbonate or carbonic hydroammonium adjust ph and drops to less than 7.5, make the ammonium bisulfite in solution be converted into ammonium sulfite in filtrate; Be that to add mass percent under passing into air oxidation or normal temperature under the condition of 40 DEG C ~ 80 DEG C be that the hydrogen peroxide of 27.5%-50% is oxidized at solution temperature, ammonium sulfite is oxidized to ammonium sulfate, and ATS (Ammonium thiosulphate) is oxidized to ammonium hydrogen sulfate, and pH value can reduce; Add ammoniacal liquor, ammonium carbonate or carbonic hydroammonium after oxidation and regulate pH to 6-7.
(6) mixed liquor step (5) obtained in 110 DEG C ~ 120 DEG C evaporation and concentration to 30% ~ 40% of original volume, then in 30 DEG C ~ 40 DEG C crystallizations, is separated the mixture of dry obtained ammonium sulfate and ammonium nitrate.
Preferably, step (2) described air oxidation passes into the amount of air is 10% ~ 20% of exhaust gas volumn.
Preferably, the mass ratio of step (3) described ATS (Ammonium thiosulphate) and ammonium nitrate mixed solution sulfite hydrogen ammonium, ATS (Ammonium thiosulphate) and ammonium nitrate is 2:1:1 ~ 5:1:1.
When reaction starts, solution ph is comparatively large, can discharge H in sulfur dioxide absorption and nitrogen oxide containing gas
2s gas, in order to avoid secondary pollution, adds the regulator solution that pH value is 4 ~ 7, makes the pH value of ammonium sulfide absorbing liquid be reduced to less than 7.5 in premature cure ammonium absorbing liquid; The mixed solution of regulator solution ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate, the mass concentration ratio of three kinds of materials is 2:1:1 ~ 5:1:1; Along with the carrying out of absorption reaction, the pH of absorbing liquid can reduce, and is reduced to when 5 at pH, in absorbing liquid, add ammonium sulfide solution, and control the pH value of absorbing liquid in the scope of 5 ~ 7.5, this scope assimilation effect is best; In absorption tower by special whirlpool shower nozzle be atomized, flue gas by the process of vaporific ammonium sulfide solution secondary absorption cleaning, SO
2and NO
xabsorbed, absorbing liquid is called rich solution, and rich solution is mainly ATS (Ammonium thiosulphate), ammonium bisulfite, sulphur, the mixed liquor of ammonium sulfate and ammonium nitrate.
Simultaneous SO_2 and NO removal principle of the present invention is as follows:
Absorb: adopt (NH
4)
2s solution absorbs the SO in flue gas
2and NO
x, absorption reaction process is as follows:
NO
2+(NH
4)
2S→(NH
4)
2SO
4+N
2
SO
2+H
2O→H
2SO
3
3NO
2+H
2O→2HNO
3+NO
2NO+O
2→2NO
2
H
2SO
3+(NH
4)
2S→(NH
4)
2SO
3+H
2S
2NO+2(NH
4)
2SO
3→2(NH
4)
2SO
4+N
2
2HNO
3+(NH
4)
2S→2NH
4NO
3+H
2S
H
2S+(NH
4)
2S→2NH
4HS
2H
2S+SO
2→3S+2H
2O
2H
2S+NO
2→2S+N
2+2H
2O
S+(NH
4)
2SO
3→(NH
4)
2S
2O
3
(NH
4)
2S
2O
3+2NO
2+NH
4OH→4(NH
4)
2SO
4+N
2
(NH
4)
2SO
3+0.5O
2→(NH
4)
2SO
4
(NH
4)
2SO
3+SO
2+H
2O→2NH
4HSO
3
4(NH
4)
2SO
3+2NO
2→4(NH
4)
2SO
4+N
2
Neutralization: absorbing liquid is drawn, filtered and recycled sulphur, containing NH in filtrate
4hSO
3, (NH
4)
2s
2o
3, (NH
4)
2sO
4and NH
4nO
3, add the neutralization of ammoniacal liquor, ammonium carbonate or carbonic hydroammonium, make the NH in absorbing liquid
4hSO
3all be transformed into (NH
4)
2sO
3and between adjust ph to 6-7.Course of reaction is as follows:
NH
3+NH
4HSO
3=(NH
4)
2SO
3
Or
NH
4HCO
3+NH
4HSO
3=(NH
4)
2SO
3+CO
2+H
2O
Oxidation: be mixed with different salts in absorbing liquid, is not suitable for producing pure ammonium sulfate or ammonium nitrate products, ammonium sulfite and ATS (Ammonium thiosulphate) is oxidized further, and the mixed fertilizer making ammonium sulfate and ammonium nitrate uses; The oxidation of ammonium sulfite solution and ATS (Ammonium thiosulphate) has two kinds of methods:
(1) hydrogen peroxide oxidation hydrogen peroxide oxidation can not bring other impurity into, and oxidation effectiveness is good, and because the oxidisability of hydrogen peroxide is comparatively strong, ATS (Ammonium thiosulphate) is oxidized to ammonium hydrogen sulfate, and reaction equation is as follows:
(NH
4)
2SO
3+H
2O
2=(NH
4)
2SO
4+H
2O
(NH
4)
2S
2O
3+4H
2O
2=2NH
4HSO
4+3H
2O
After oxidation reaction completes, because thiosulfate anion is oxidized, produce hydrogen radical ion, the pH value of solution reduces, and now needs to add ammoniacal liquor, and ammonium carbonate or carbonic hydroammonium adjust ph are to the scope of 6-7.
(2) air oxidation process utilizes the oxidizable principle of ammonium sulfite, is ammonium sulfate with air by sulfite oxidation, containing (NH in the ammonium sulfite that this method is produced
4)
2s
2o
3there is certain catalysed oxidn, favourable to the oxidation of ammonium sulfite, react as follows:
(NH
4)
2SO
3+0.5O
2=(NH
4)
2SO
4
(NH
4)
2S
2O
3+H
2O+2O
2=2NH
4HSO
4
Air oxidation is relatively slow, and the temperature that need improve solution, at 40 DEG C ~ 50 DEG C, utilizes aerator aerating oxidation or employing oxidizing tower to spray mode from top to bottom and is oxidized, namely increase the contact area of oxygen and solution, accelerate the carrying out of oxidation reaction.Add ammoniacal liquor after oxidation, ammonium carbonate or carbonic hydroammonium adjust ph are to the scope of 6-7.
Evaporation and concentration: ammonium sulfate, the mixed liquor of ATS (Ammonium thiosulphate) and ammonium nitrate is in 110 DEG C ~ 120 DEG C evaporation and concentration to 30% ~ 40% of original volume.
Crystallization: the ammonium sulfate after concentrated, ATS (Ammonium thiosulphate) and ammonium nitrate mixed liquor are put and be cooled to 30 DEG C ~ 40 DEG C crystallizations.By crystalline mother solution centrifugation, obtain the ammonium sulfate that water content is 3-5%, the crystallization of ATS (Ammonium thiosulphate) and ammonium nitrate, wherein ATS (Ammonium thiosulphate) hygroscopicity is stronger, not easily crystallization, part has been stayed in concentrate, so the crystallization obtained is the mixture based on ammonium sulfate and ammonium nitrate, concentrate can be used as liquid fertilizer and sells.
Advantage of the present invention:
(1) removal efficiency is high simultaneously for the nitrogen oxide in industrial furnace flue gas and sulfur dioxide, and flue gas can qualified discharge.Desulfuration efficiency >=99%, denitration efficiency >=90%, byproduct sulfur purity >=98%, mixed fertilizer nitrogen content >=20% of ammonium sulfate and ammonium nitrate.
(2) from the SO flue gas during smelting
2produce the byproduct such as sulphur and nitrogenous fertilizer with NOx, denitrification efficiency is high, and operating cost is low, and sulphur has of many uses compared with other sulphur product, is easy to the advantages such as storage and transport.Therefore, the present invention solves flue gas during smelting purification and the key technology utilized, and it is suitable for industrial applications.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1
SO in industrial furnace flue gas
2and NO
xthe method of recycling, particular content is as follows:
(1) in the present embodiment, pending flue gas is zinc smelting flue gas, and exhaust gas volumn is 30000m
3/ h, containing SO in stove mouth flue gas
2: 3% ~ 4%, NO
x: 1300 ~ 1700mg/m
3, flue-gas temperature, through dedusting, is cooled to less than 50 DEG C after washing by flue gas during smelting, blasts air (amount of air is 10% of exhaust gas volumn);
(2) be 25% by mass percent concentration, the ammonium sulfide solution of pH=7.2 (regulates with ATS (Ammonium thiosulphate), ammonium bisulfite and ammonium nitrate mixed liquor, the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 3:1:1) be atomized by the whirlpool shower nozzle on absorption tower, the rear flue gas of cooling enters two-level absorption tower adverse current and fully contacts with the ammonium sulfide solution of atomization, to containing SO
2and NO
xflue gas during smelting carries out efficient absorption, and add ammonium sulfide in absorption reaction process and control the pH value of absorbing liquid between 7.5, purifying smoke is emptying;
(3) SO is absorbed
2and NO
xrich solution by press filtration Recovered sulphur, in filtrate, add ammonium carbonate neutralize, adjust ph, to 6.5, is pass into air oxidation under the condition of 60 DEG C at solution temperature, and be oxidized interpolation carbonic hydroammonium adjust ph is 6;
(4) the solution evaporation and concentration at 115 DEG C of temperature after oxidation, to 30% of original solution volume, is cooled to 30 DEG C of crystallizations, centrifugation, and namely obtain ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate uses as liquid fertilizer.
By implementing said method, smoke desulfurization efficiency>=99%, denitration efficiency>=90%, SO in exiting flue gas
2content≤100mg/m
3; NO
xcontent≤100mg/m
3, byproduct sulfur purity>=98%, mixed fertilizer nitrogen content>=20%.
Embodiment 2
SO in smelting lead
2and NO
xthe method recycled, particular content is as follows:
(1) in the present embodiment, pending flue gas is smelting lead, and exhaust gas volumn is 10000m
3/ h, containing SO in stove mouth flue gas
2: 0.8% ~ 1%, NO
x: 1000 ~ 1300mg/m
3, flue-gas temperature, through dedusting, is cooled to less than 50 DEG C after washing by industrial furnace flue gas, blasts air (amount of air is 15% of exhaust gas volumn);
(2) be 10% by mass percent concentration, the ammonium sulfide solution of pH=7.5 (uses ATS (Ammonium thiosulphate), ammonium bisulfite and ammonium nitrate mixed liquor regulate, the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 5:1:1) be atomized by the whirlpool shower nozzle on absorption tower, the rear flue gas of cooling enters two-level absorption tower adverse current and fully contacts with the ammonium sulfide solution of atomization, to containing SO
2and NO
xflue gas during smelting carries out efficient absorption, and add ammonium sulfide in absorption reaction process and control the pH value of absorbing liquid between 6, purifying smoke is emptying;
(3) SO is absorbed
2and NO
xrich solution by press filtration Recovered sulphur, in filtrate, add carbonic hydroammonium neutralize, adjust ph to 7, solution hydrogen peroxide (mass percent the is 48%) oxidation after neutralization, be oxidized interpolation ammonium carbonate adjust ph is 7;
(4) the solution evaporation and concentration at 110 DEG C of temperature after oxidation, to 35% of original solution volume, is cooled to 35 DEG C of crystallizations, centrifugation, and namely obtain ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate uses as liquid fertilizer.
By implementing said method, smoke desulfurization efficiency>=99%, denitration efficiency>=90%, SO in exiting flue gas
2content≤100mg/m
3; NO
xcontent≤100mg/m
3, byproduct sulfur purity>=98%, mixed fertilizer nitrogen content>=20%.
Embodiment 3
SO in nickel fibers flue gas
2and NO
xthe method recycled, particular content is as follows:
(1) in the present embodiment, pending flue gas is nickel fibers flue gas, and exhaust gas volumn is 20000m
3/ h, containing SO in stove mouth flue gas
2: 1% ~ 2%, NO
x: 900 ~ 1200mg/m
3, flue-gas temperature, through dedusting, is cooled to less than 50 DEG C after washing by flue gas, blasts air (amount of air is 20% of exhaust gas volumn);
(2) be 17% by mass percent concentration, the ammonium sulfide solution of pH=7 (uses ATS (Ammonium thiosulphate), ammonium bisulfite and ammonium nitrate mixed liquor regulate, the mass ratio of ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate is 2:1:1) be atomized by the whirlpool shower nozzle on absorption tower, the rear flue gas of cooling enters two-level absorption tower adverse current and fully contacts with the ammonium sulfide solution of atomization, to containing SO
2and NO
xflue gas during smelting carries out efficient absorption, and add ammonium sulfide in absorption reaction process and control the pH value of absorbing liquid between 5, purifying smoke is emptying;
(3) SO is absorbed
2and NO
xrich solution by press filtration Recovered sulphur, in filtrate, add ammoniacal liquor neutralize, adjust ph to 6, solution hydrogen peroxide (mass percent the is 32%) oxidation after neutralization, be oxidized interpolation ammoniacal liquor adjust ph is 7.5;
(4) the solution evaporation and concentration at 120 DEG C of temperature after oxidation, to 40% of original solution volume, is cooled to 40 DEG C of crystallizations, centrifugation, and namely obtain ammonium sulfate and ammonium nitrate mixed fertilizer after drying, concentrate uses as liquid fertilizer.
By implementing said method, smoke desulfurization efficiency>=99%, denitration efficiency>=90%, SO in exiting flue gas
2content≤100mg/m
3; NO
xcontent≤100mg/m
3, byproduct sulfur purity>=98%, mixed fertilizer nitrogen content>=20%.
Claims (4)
1. a method for ammonium sulfide solution desulphurization denitration, is characterized in that, specifically comprises the following steps:
(1) by industrial furnace flue gas through rough dusting and washing after, flue-gas temperature is cooled to less than 50 DEG C;
(2) in the flue gas after step (1) process, air is passed into;
(3) the mixed solution adjust ph adding ammonium bisulfite, ATS (Ammonium thiosulphate) and ammonium nitrate in ammonium sulfide solution obtains ammonium sulfide spray solution to 7 ~ 7.5, and in ammonium sulfide spray solution, the mass percent concentration of ammonium sulfide is 10%-25%;
(4) by the flue gas after air oxidation in the step (2) and ammonium sulfide spray solution haptoreaction, add ammonium sulfide in absorption reaction process and control the pH value of absorbing liquid between 5 ~ 7.5, after having absorbed, absorbing liquid is called rich solution;
(5) rich solution filtered and recycled obtains sulphur, ammoniacal liquor, ammonium carbonate or carbonic hydroammonium adjust ph is added to 6-7 in filtrate, then be that the hydrogen peroxide adding 27.5%-50% under passing into air oxidation or normal temperature under the condition of 40 DEG C ~ 80 DEG C is oxidized at solution temperature, add ammoniacal liquor, ammonium carbonate or carbonic hydroammonium after oxidation and regulate pH to 6-7;
(6) mixture of ammonium sulfate and ammonium nitrate is obtained after mixed liquor evaporation and concentration step (4) obtained, crystallization, separation drying.
2. the method for industrial furnace flue gas according to claim 1 denitration simultaneously removing heavy-metal, is characterized in that: the amount that step (2) described air oxidation passes into air is 10% ~ 20% of exhaust gas volumn.
3. the method for industrial furnace flue gas according to claim 1 denitration simultaneously removing heavy-metal, is characterized in that: the mass ratio of step (3) described ATS (Ammonium thiosulphate) and ammonium nitrate mixed solution sulfite hydrogen ammonium, ATS (Ammonium thiosulphate) and ammonium nitrate is 2:1:1 ~ 5:1:1.
4. the method for industrial furnace flue gas according to claim 1 denitration simultaneously removing heavy-metal, is characterized in that: in step (5), evaporating temperature is 110 DEG C ~ 120 DEG C, and crystallization temperature is 30 DEG C ~ 40 DEG C.
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| CN108295641A (en) * | 2018-01-17 | 2018-07-20 | 毛思佳 | Low-temperature denitration solution and method of denitration |
| CN109126424A (en) * | 2018-09-07 | 2019-01-04 | 南通航泰船舶机械有限公司 | A kind of ship desulfurization and denitrification integral process |
| CN110124497A (en) * | 2019-05-27 | 2019-08-16 | 广东佳德环保科技有限公司 | A kind of desulphurization denitration absorbent and application thereof |
| CN114436703A (en) * | 2022-03-15 | 2022-05-06 | 南京沃野化工科技有限公司 | CO capture2Method for co-producing granular multi-element sulfur-carbon based composite nitrogen fertilizer |
| CN114713013A (en) * | 2022-03-18 | 2022-07-08 | 山东省科学院能源研究所 | Comprehensive low-temperature flue gas purification, desulfurization and denitrification method |
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|---|---|---|---|---|
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| CN110124497A (en) * | 2019-05-27 | 2019-08-16 | 广东佳德环保科技有限公司 | A kind of desulphurization denitration absorbent and application thereof |
| CN110124497B (en) * | 2019-05-27 | 2022-02-18 | 广东佳德环保科技有限公司 | Desulfurization and denitrification absorbent and application thereof |
| CN114436703A (en) * | 2022-03-15 | 2022-05-06 | 南京沃野化工科技有限公司 | CO capture2Method for co-producing granular multi-element sulfur-carbon based composite nitrogen fertilizer |
| CN114713013A (en) * | 2022-03-18 | 2022-07-08 | 山东省科学院能源研究所 | Comprehensive low-temperature flue gas purification, desulfurization and denitrification method |
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