CN103768910B - SO in a kind of flue gas during smelting 2with heavy metal synergistic purification method and device - Google Patents
SO in a kind of flue gas during smelting 2with heavy metal synergistic purification method and device Download PDFInfo
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- CN103768910B CN103768910B CN201410019587.0A CN201410019587A CN103768910B CN 103768910 B CN103768910 B CN 103768910B CN 201410019587 A CN201410019587 A CN 201410019587A CN 103768910 B CN103768910 B CN 103768910B
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- flue gas
- solution
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- absorption tower
- heavy metal
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- 239000003546 flue gas Substances 0.000 title claims abstract description 95
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 68
- 238000003723 Smelting Methods 0.000 title claims abstract description 48
- 238000000746 purification Methods 0.000 title claims abstract description 21
- 230000002195 synergetic Effects 0.000 title claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 69
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 48
- 230000003647 oxidation Effects 0.000 claims abstract description 45
- UYJXRRSPUVSSMN-UHFFFAOYSA-P Ammonium sulfide Chemical group [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 36
- 230000005712 crystallization Effects 0.000 claims abstract description 31
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 25
- 230000005591 charge neutralization Effects 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 24
- 230000001264 neutralization Effects 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 150000004763 sulfides Chemical class 0.000 claims abstract description 6
- XYXNTHIYBIDHGM-UHFFFAOYSA-N Ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 36
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 19
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 19
- 230000003197 catalytic Effects 0.000 claims description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 239000012141 concentrate Substances 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 13
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N Ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000000889 atomisation Methods 0.000 claims description 5
- 238000010410 dusting Methods 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 230000003472 neutralizing Effects 0.000 claims description 5
- 239000003337 fertilizer Substances 0.000 abstract description 18
- 229910052753 mercury Inorganic materials 0.000 abstract description 18
- 238000006477 desulfuration reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 13
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 10
- 229910052785 arsenic Inorganic materials 0.000 abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 abstract description 9
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 4
- 230000002745 absorbent Effects 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract description 3
- 229910052745 lead Inorganic materials 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000008247 solid mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 85
- 239000003570 air Substances 0.000 description 29
- 239000011701 zinc Substances 0.000 description 18
- 230000003009 desulfurizing Effects 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 239000005864 Sulphur Substances 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Ammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 6
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005201 scrubbing Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052949 galena Inorganic materials 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(II) oxide Inorganic materials [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001698 pyrogenic Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- -1 (Cd) Inorganic materials 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O Ammonium nitrate Chemical compound [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N CTK2H8874 Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000037250 Clearance Effects 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N Thiosulfuric acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-O azanium;sulfuric acid Chemical compound [NH4+].OS(O)(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 230000035512 clearance Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002588 toxic Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention discloses SO in a kind of flue gas during smelting
2with heavy metal synergistic purification method and device, belong to atmosphere pollution technical field; The method is with (NH
4)
2s solution is absorbent, absorption cleaning SO
2with heavy metal (Hg, As, Pb, Cd, Zn etc.); Flue gas during smelting after dust removal process, passes into secondary ammonium sulfide solution absorption tower, the SO in gas
2with heavy metal by absorbent absorption cleaning, wherein heavy metal precipitates with the form of solid sulfide, recycles after filtering; SO
2then be converted into NH
4hSO
3(NH
4)
2s
2o
3stay in absorbing liquid.After absorption reaction terminates, absorbing liquid, through neutralization, oxidation, evaporative crystallization process, obtains (NH
4)
2sO
4(NH
4)
2s
2o
3solid mixture, this mixture can directly be sold as fertilizer.Present invention process is simple, easy to operate, and desulfuration efficiency is high, and cost is low, is suitable for industrial applications.
Description
Technical field
The present invention relates to SO in a kind of flue gas during smelting
2with heavy metal synergistic purification method and device, belong to atmosphere pollution technical field.
Background technology
Non-ferrous metal is many generates sulphide ore with sulphur, and as zincblende, galena, vitreous copper, capillose etc., they are important source material of metallurgical industry.In nonferrous smelting industry, generally have pyrogenic process and wet method two kinds of metallurgical technologies, the overwhelming majority adopts the metallurgical ore deposit of pyrogenic attack now.In pyrometallurgical processes, sulphide ore makes sulphur and metal separation through high-temperature roasting, and sulphur is converted into sulfur dioxide and discharges with baking flue gas, in the flue gas of discharge, except containing SO
2outward, also containing heavy metal and toxic nonmetal, in heavy metal, there are mercury (Hg), arsenic (As), plumbous (Pb) cadmium, (Cd), zinc (Zn) etc.Spread in these mass emissions to air, or bring in desulfurization product, contaminated air, soil and water, work the mischief to environment.
At present, the improvement of flue gas during smelting, general employing flue gas during smelting desulfurization relieving haperacidity or other sulphur product:
(1) the mainly sulfur dioxide of the gaseous contaminant in flue gas during smelting, the flue gas of sulfur dioxide concentration more than 2%, can adopt contact method to make sulfuric acid, but SO in relieving haperacidity tail gas
2concentration still higher, be difficult to reach increasingly strict environmental requirement.If mercurous in flue gas, special mercury removal device need be established in purification process, add cost of investment.
(2) the scrubbing CO_2 technology of industrial applications has tens of kinds, wherein Limestone-gypsum Wet Flue Gas Desulfurization Process technology is the most ripe, application at most, these technology are used for coal fired power plant flue gas desulfurization, the flue gas produced due to nonferrous smelting process have narrow-minded, fluctuation is large, containing features such as harmful and valuable metals, simply indiscriminately imitate coal-fired flue gas desulfurization process infeasible.Although also have some wet desulphurization method desulfurized effects fine, exist and produce solid waste, equipment investment is large, consume energy high, the problems such as post processing is complicated, if application number is the Chinese invention patent " a kind of method of flue gas desulfurizing and hydrargyrum-removing " of 200910244547.5, the method is to SO
2higher with the clearance of mercuryvapour, also can remove plumbous grade for heavy metal, but there is the problem to the process of solid waste Desulphurization; Application number is the Chinese invention patent " flue gas desulfurization and denitrification removing heavy-metal integral method and special equipment " of 201110091281.2, integrated apparatus realizes flue gas desulfurization and denitrification removing heavy-metal integrated purifying function, and accessory substance is chemical fertilizer composition ammonium sulfate and ammonium nitrate.But there is blend absorbent complicated components and add cost of investment, the problem that heavy metal removing effect is general.
(3) nineteen eighty-three Outokumpu proposition Na
2s solution absorbs SO
2produce the method for sulphur simple substance.When pH value is too large, absorb SO
2h can be discharged in flue gas
2s gas, so regulate Na with the flue gas washing liquid that pH value is 2-5 before it is absorbed
2the pH value of S.The contained substance classes of cleaning solution and Na
2s absorbs SO
2after to obtain solution main matter kind identical.After having reacted, mixed liquor enters autoclave, at 160 DEG C, automatic oxidation reduction reaction occurs and generates S simple substance and Na
2sO
4, then regenerate Na with BaS
2sO
4, the Na obtained
2s returns the absorption stage and recycles, BaSO
4obtain BaS with C reduction and return Na
2sO
4regeneration stage.Shu Yu morals in 1997 etc. are improved sodium sulfide method, with Outokumpu Oyj unlike, in the absorption stage not to Na
2s solution carries out the adjustment of pH value, adopts two-stage to absorb; Reduction phase is by adding dense H in absorbing liquid
2sO
4and Na
2s, the component when 50-60 DEG C and in solution reacts and produces S simple substance, the H that the reaction of reduction phase discharges
2s gas, then use Na
2s absorbs.
There is following problem in existing method: (1) prior art is only for flue gas middle and high concentration SO
2reclaim, do not consider low concentration SO
2remove with while heavy metal; (2) solid waste produced after absorption cleaning sulfur dioxide is difficult to recycle.(3) problems such as sodium sulfide method sulfur dioxide absorption, exists post processing complexity, and investment is large, and power consumption is high, are difficult to industrial applications.
Summary of the invention
For SO in flue gas during smelting
2concentration is high, the problem of tolerance fluctuation greatly, simultaneously containing various heavy such as Hg, As, Cd, Pb, Zn, the object of the invention is to propose SO in a kind of flue gas during smelting
2with heavy metal synergistic purification method and device, adopt (NH
4)
2s solution absorption method removes SO simultaneously
2with Hg, As, Cd, Pb, Zn etc., specifically comprise the steps:
(1) by after flue gas during smelting rough dusting, further flue-gas temperature is cooled to less than 50 DEG C;
(2) be that the ammonium sulfide solution of atomization between 7 ~ 3 fully contacts by cooled flue gas and pH value, to containing SO
2sO in flue gas during smelting
2absorb with metal oxide, the flue gas of purification is discharged after degree of depth removing heavy-metal;
(3) SO is absorbed
2after passing through press filtration with the rich solution of heavy metal, filter the sediment of heavy metal sulfide in solution, filter residue centralized recovery also turns back to smelting furnace, during the one added in filtrate in ammoniacal liquor, ammonium carbonate, carbonic hydroammonium is carried out and, adjust ph, to 5.8 ~ 6.5, obtains the solution after neutralizing;
(4) neutralization after solution in temperature be add under passing into air oxidation or normal temperature under the condition of 40 DEG C ~ 50 DEG C mass percent concentration be 27.5% ~ 50% hydrogen peroxide be oxidized, a kind of adjust ph in solution interpolation ammoniacal liquor after oxidation, ammonium carbonate, carbonic hydroammonium, to 5.8 ~ 6.5, obtains the solution after being oxidized;
(5) by the solution after oxidation in 45 DEG C ~ 50 DEG C evaporation and concentration to 40% ~ 60% of original solution volume, be then cooled to 20 DEG C ~ 30 DEG C crystallizations, be separated mixture and the concentrate of obtained ammonium sulfate and ATS (Ammonium thiosulphate).
Described in step of the present invention (2), the mass percent concentration of ammonium sulfide solution is 8% ~ 25%.
Another object of the present invention is to provide SO in flue gas during smelting
2with heavy metal synergistic purification method equipment therefor, this device comprises air exhauster I 1, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9, demister 10, fixed-bed catalytic removing heavy-metal device 11, ammonium sulfide reservoir 12, filter pump 13, filter press 14, neutralization chamber 15, air exhauster II 16, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22, air exhauster 1 is connected with absorption tower I 2, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5 circulates connection successively, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9 circulates connection successively, absorption tower I 2, absorption tower II 6, demister 10, fixed-bed catalytic removing heavy-metal device 11 is communicated with successively, and ammonium sulfide reservoir 12 is connected with circulation reservoir II 7, and circulation reservoir II 7 is connected with circulation reservoir I 3, and circulation reservoir I 3 is connected with filter pump 13 with circulation reservoir II 7 simultaneously, filter pump 13, filter press 14, neutralization chamber 15, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22 is communicated with successively, and air exhauster II 16 is connected with oxidation trough 17, and reservoir 18 is connected with centrifuge 22.
Inventive principle:
(1) flue gas during smelting SO
2with heavy metal contaminants synergistic purification principle: SO
2react with oxygen and some heavy metallic oxides and generate insoluble matter, facilitate removing of heavy metal substance; Part heavy metallic oxide in flue gas, to SO
2liquid phase scrubbing transform have catalytic action, reactive chemistry equation is as follows:
SO
2+ H
2O → H
2SO
3
H
2SO
3 + (NH
4)
2S → (NH
4)
2SO
3 + H
2S
H
2S + (NH
4)
2S → NH
4HS
2H
2S + SO
2→ 3S + 2H
2O
S + (NH
4)
2SO
3→ (NH
4)
2S
2O
3
(NH
4)
2SO
3 + 0.5O
2 → (NH
4)
2SO
4
(NH
4)
2SO
3 + SO
2+ H
2O→ 2NH
4HSO
3
(NH
4)
2S + HgO + H
2O → HgS↓+ 2NH
4OH
SO
2 + 0.5O
2+ HgO → HgSO
4↓
(NH
4)
2S + CdO + H
2O → CdS↓+ 2NH
4OH
4(NH
4)
2S + As
2O
3 + 3H
2O → As
2S
3↓+ 3NH
4OH + NH
4HS
(NH
4)
2S + PbO + H
2O → PbS↓+ 2NH
4OH
SO
2 + 0.5O
2+ PbO → PbSO
4↓
(NH
4)
2S + ZnO + H
2O → ZnS↓+ 2NH
4OH
NH
4OH + SO
2 → NH
4HSO
3
(2) neutralization of filtrate is absorbed: after absorbing liquid is drawn absorption tower, the NH containing higher concentration in solution
4hSO
3(NH
4)
2s
2o
3, by the one neutralization in absorbing liquid 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 5.8 ~ 6.5, 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
(3) be oxidized: in the ammonium sulfate that this method is produced, ATS (Ammonium thiosulphate) content is very high, be not suitable for producing pure ammonium sulfate product, ammonium sulfite is oxidized to ammonium sulfate further, and the mixed fertilizer making ammonium sulfate and ATS (Ammonium thiosulphate) uses, and the oxidation of ammonium sulfite solution has two kinds of methods:
1. hydrogen peroxide oxidation: other impurity can not be brought into hydrogen peroxide oxidation, oxidation effectiveness is good, and because the oxidisability of hydrogen peroxide is comparatively strong, the ATS (Ammonium thiosulphate) having part is oxidized, 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 part is oxidized, produce hydrogen ion, the pH value of solution reduces, and now needs to add ammoniacal liquor, ammonium carbonate or the carbonic hydroammonium adjust ph scope to 5.8 ~ 6.5.
Sulfite oxidation is ammonium sulfate with air by 2. air oxidation process: utilize the oxidizable principle of ammonium sulfite, containing (NH in the ammonium sulfite that this method is produced
4)
2s
2o
3there is 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; Ammoniacal liquor is added, ammonium carbonate or the carbonic hydroammonium adjust ph scope to 5.8 ~ 6.5 after oxidation.
(4) evaporation and concentration: the concentrated solution of ATS (Ammonium thiosulphate) is when being greater than 50 DEG C, easy decomposition produces sulphur and ammonium sulfite, in order to avoid the decomposition of ATS (Ammonium thiosulphate), by the ammonium sulfate that obtains and ATS (Ammonium thiosulphate) mixed liquor after oxidation in 45 DEG C ~ 50 DEG C evaporation and concentration to 40% ~ 60% of original volume.React as follows:
(NH
4)
2S
2O
3 = S + (NH
4)
2SO
3
(5) ammonium sulfate after concentrating and ATS (Ammonium thiosulphate) mixed liquor put into crystallization tank at 20 DEG C ~ 30 DEG C crystallisation by cooling, crystalline mother solution is continuously separated in centrifuges, obtain ammonium sulfate and the thiosulfuric acid crystalline ammonium of moisture 3 ~ 5%, 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, the concentrate after crystallization returns evaporation and concentration or directly sells as liquid fertilizer.
Advantage of the present invention is as follows:
(1) SO in flue gas during smelting
2remove with heavy metallic oxide synergistic purification: SO
2facilitate removing of heavy metallic oxide, heavy metallic oxide is to SO
2liquid phase scrubbing transform there is catalytic action;
(2) SO in flue gas during smelting
2high with heavy metal removing efficiency, flue gas can qualified discharge, desulfuration efficiency>=99%, SO in exiting flue gas
2content≤50mg/m
3; Mercury, arsenic, cadmium, lead, zinc five heavy metal species removal efficiency are stable is greater than 90%, Hg≤0.012mg/m in exiting flue gas
3, As≤0.1mg/m
3, Cd≤0.1mg/m
3, Pb≤0.1mg/m
3, Zn≤0.1mg/m
3nitrogen content>=20% of mixed fertilizer, the comprehensive recovery of mercury is greater than 80%, and the comprehensive recovery of lead, arsenic, cadmium, zinc is greater than 70%;
(3) from the SO flue gas during smelting
2the mixed fertilizer of Sulphuric acid ammonium and ATS (Ammonium thiosulphate), desulfurization degree is high, and operating cost is low, and the ammonium sulfate fertilizer having added ATS (Ammonium thiosulphate) has the reaction of suppression soil nitrification, keep the effect of nitrogen content in soil, and economic worth is high, is easy to storage and transport; Concentrate after crystallization can directly use as liquid fertilizer, be sprayed on crops and can effectively extend the utilization of pesticides time, contribute to the efficient absorption of crops to nitrogen element sulphur simultaneously, therefore, the present invention solves flue gas during smelting purification and the key technology of recycling, can bring good economic benefit for enterprise;
(4) heavy metal in the recyclable flue gas during smelting of the present invention, achieves the recycling of metal sulfide, avoids the heavy metals emission of flue gas during smelting simultaneously and transfers in waste water and produce secondary pollution.
Accompanying drawing explanation
Fig. 1 is present invention process schematic flow sheet;
In figure: 1-air exhauster I, 2-absorption tower I, 3-circulation reservoir I, 4-circulating pump I, 5-jet pipe I, 6-absorption tower II, 7-circulation reservoir II, 8-circulating pump II, 9-jet pipe II, 10-demister, 11-fixed-bed catalytic removing heavy-metal device, 12-ammonium sulfide reservoir, 13-filter pump, 14-filter press, 15-neutralization chamber, 16-air exhauster II, 17-oxidation trough, 18-reservoir, 19-circulating pump III, 20-evaporimeter, 21-crystallization tank, 22-centrifuge.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but scope is not limited to described content.
Embodiment 1
The present embodiment is handling object with zinc smelting flue gas, SO in zinc smelting flue gas
2: 4 ~ 8%, Hg:5mg/m
3, As:1 ~ 5mg/m
3, Pb:5 ~ 8 mg/m
3, Cd:2 ~ 7 mg/m
3, Zn:20 ~ 30 mg/m
3; Specifically comprise the steps:
(1) by after flue gas during smelting rough dusting, further flue-gas temperature is cooled to 50 DEG C;
(2) ammonium sulfide solution being the atomization of 7 by cooled flue gas and pH value fully contacts, to containing SO
2flue gas during smelting absorbs, the metal oxide in simultaneously stability flue gas, and the flue gas of purification is discharged after fixed-bed catalytic removing heavy-metal device degree of depth removing heavy-metal, and wherein ammonium sulfide solution mass percent concentration is 8%;
(3) SO is absorbed
2with the rich solution of heavy metal by after press filtration, filter the sediment of heavy metal sulfide in solution, filter residue centralized recovery also turns back to smelting furnace, add in filtrate ammoniacal liquor carry out in and, adjust ph, to 5.8, obtains the solution after neutralizing;
(4) solution after neutralization is pass into air under the condition of 40 DEG C to be oxidized in temperature, and the solution after oxidation adds ammoniacal liquor adjust ph to 5.8, obtains the solution after being oxidized;
(5) by the solution after oxidation in 45 DEG C of evaporation and concentration to 40% of original solution volume, be then cooled to 20 DEG C of crystallizations, be separated mixture and the concentrate of obtained ammonium sulfate and ATS (Ammonium thiosulphate).
SO in flue gas during smelting described in the present embodiment
2with heavy metal synergistic purification method equipment therefor, this device comprises air exhauster I 1, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9, demister 10, fixed-bed catalytic removing heavy-metal device 11, ammonium sulfide reservoir 12, filter pump 13, filter press 14, neutralization chamber 15, air exhauster II 16, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22, air exhauster 1 is connected with absorption tower I 2, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5 circulates connection successively, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9 circulates connection successively, absorption tower I 2, absorption tower II 6, demister 10, fixed-bed catalytic removing heavy-metal device 11 is communicated with successively, and ammonium sulfide reservoir 12 is connected with circulation reservoir II 7, and circulation reservoir II 7 is connected with circulation reservoir I 3, and circulation reservoir I 3 is connected with filter pump 13 with circulation reservoir II 7 simultaneously, filter pump 13, filter press 14, neutralization chamber 15, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22 is communicated with successively, and air exhauster II 16 is connected with oxidation trough 17, and reservoir 18 is connected with centrifuge 22, as shown in Figure 1.
The using method of device described in the present embodiment: flue gas is pumped in absorption tower I 2 through air exhauster I 1, ammonium sulfide solution enters in circulation reservoir I 3 and circulation reservoir II 7 from sending out ammonium sulfide reservoir 10 successively, ammonium sulfide solution in circulation reservoir I 3 fully contacts with flue gas after cooling by after jet pipe I 5 spray atomizing after circulating pump I 4 is extracted out, flue gas after absorbing in absorption tower I 2 enters in absorption tower II 6 and again absorbs, identical with in absorption tower I 2 of absorption process, flue gas after absorption enters demister 10 demist through the top on absorption tower II 6, flue gas is discharged after fixed-bed catalytic removing heavy-metal device 11 carries out degree of depth removing heavy-metal, absorb SO
2flow in circulation reservoir I 3 and circulation reservoir II 7 to mix with ammonium sulfide solution with the rich solution of heavy metal and again utilize, when in reservoir, rich solution pH reaches 3, part rich solution enters filter pump 13, add again in ammonium sulfide solution to reservoir and regulate solution ph to be 7, enter in neutralization chamber 15 by the filtrate after filter pump 13 filters, add ammoniacal liquor to neutralize, adjust ph is to 5.8, filter residue centralized recovery also turns back to smelting furnace, solution after neutralization is delivered to and passes into air in oxidation trough 17 and be oxidized, then ammoniacal liquor adjust ph is added to 5.8, solution after oxidation is sent in evaporimeter 20, 40% of original solution volume is concentrated at 45 DEG C, put into crystallization tank 21 and be cooled to 20 DEG C of crystallizations, be separated with centrifuge 22 after crystallization, obtain ammonium sulfate and ATS (Ammonium thiosulphate) mixed fertilizer and concentrate, concentrate turns back in evaporator tank 18.
By method described in the present embodiment, smoke desulfurization efficiency is 99.5%, SO in exiting flue gas
2content is 20mg/m
3; Mercury, arsenic, cadmium, lead, zinc five heavy metal species removal efficiency are 94%, and in exiting flue gas, Hg is 0.01 mg/m
3, As is 0.05mg/m
3, Cd is 0.01 mg/m
3, Pb is 0.07mg/m
3, Zn is 0.08mg/m
3mixed fertilizer nitrogen content is 23.6%, reaches chemical fertilizer products quality standard, and plumbous resource rate is 66%, and the comprehensive recovery of mercury is 75%.
Embodiment 2
The present embodiment is handling object with smelting lead, SO in smelting lead
2: 8 ~ 12%, Hg:2 ~ 5mg/m
3, As:1 ~ 5mg/m
3, Pb:35 ~ 45mg/m
3, Cd:1 ~ 3 mg/m
3, Zn:1 ~ 5 mg/m
3specifically comprise the steps:
(1) by after flue gas during smelting rough dusting, further flue-gas temperature is cooled to 40 DEG C;
(2) ammonium sulfide solution being the atomization of 7 by cooled flue gas and pH value fully contacts, to containing SO
2flue gas during smelting absorbs, the metal oxide in simultaneously stability flue gas, and the flue gas of purification is discharged after fixed-bed catalytic removing heavy-metal device degree of depth removing heavy-metal, and wherein ammonium sulfide solution mass percent concentration is 25%;
(3) SO is absorbed
2with the rich solution of heavy metal by after press filtration, filter the sediment of heavy metal sulfide in solution, filter residue centralized recovery also turns back to smelting furnace, add in filtrate ammonium carbonate carry out in and, adjust ph, to 6.5, obtains the solution after neutralizing;
(4) solution after neutralization in temperature be pass under the condition of 50 DEG C mass percent concentration be 27.5% hydrogen peroxide be oxidized, solution after oxidation adds ammonium carbonate adjust ph to 6.5, obtains the solution after being oxidized;
(5) by the solution after oxidation in 50 DEG C of evaporation and concentration to 60% of original solution volume, be then cooled to 30 DEG C of crystallizations, be separated mixture and the concentrate of obtained ammonium sulfate and ATS (Ammonium thiosulphate).
SO in flue gas during smelting described in the present embodiment
2with heavy metal synergistic purification method equipment therefor, this device comprises air exhauster I 1, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9, demister 10, fixed-bed catalytic removing heavy-metal device 11, ammonium sulfide reservoir 12, filter pump 13, filter press 14, neutralization chamber 15, air exhauster II 16, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22, air exhauster 1 is connected with absorption tower I 2, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5 circulates connection successively, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9 circulates connection successively, absorption tower I 2, absorption tower II 6, demister 10, fixed-bed catalytic removing heavy-metal device 11 is communicated with successively, and ammonium sulfide reservoir 12 is connected with circulation reservoir II 7, and circulation reservoir II 7 is connected with circulation reservoir I 3, and circulation reservoir I 3 is connected with filter pump 13 with circulation reservoir II 7 simultaneously, filter pump 13, filter press 14, neutralization chamber 15, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22 is communicated with successively, and air exhauster II 16 is connected with oxidation trough 17, and reservoir 18 is connected with centrifuge 22, as shown in Figure 1.
The using method of device described in the present embodiment: flue gas is pumped in absorption tower I 2 through air exhauster I 1, ammonium sulfide solution enters in circulation reservoir I 3 and circulation reservoir II 7 from sending out ammonium sulfide reservoir 10 successively, ammonium sulfide solution in circulation reservoir I 3 fully contacts with flue gas after cooling by after jet pipe I 5 spray atomizing after circulating pump I 4 is extracted out, flue gas after absorbing in absorption tower I 2 enters in absorption tower II 6 and again absorbs, identical with in absorption tower I 2 of absorption process, flue gas after absorption enters demister 10 demist through the top on absorption tower II 6, flue gas is discharged after fixed-bed catalytic removing heavy-metal device 11 carries out degree of depth removing heavy-metal, absorb SO
2flow in circulation reservoir I 3 and circulation reservoir II 7 to mix with ammonium sulfide solution with the rich solution of heavy metal and again utilize, when in reservoir, rich solution pH reaches 4, part rich solution enters filter pump 11, add again in ammonium sulfide solution to reservoir regulate solution ph be 7 by filter pump 13 filter after filtrate enter in neutralization chamber 15, add ammonium carbonate to neutralize, adjust ph is to 6.5, filter residue centralized recovery also turns back to smelting furnace, by neutralization after solution deliver in oxidation trough 17 pass into mass percent concentration be 27.5% hydrogen peroxide be oxidized, then ammonium carbonate adjust ph is added to 6.5, solution after oxidation is sent in evaporimeter 20, 60% of original solution volume is concentrated at 50 DEG C, put into crystallization tank 21 and be cooled to 30 DEG C of crystallizations, be separated with centrifuge 22 after crystallization, obtain ammonium sulfate and ATS (Ammonium thiosulphate) mixed fertilizer and concentrate, concentrate is sold as liquid fertilizer.
By method described in the present embodiment, smoke desulfurization efficiency is 99.7%, SO in exiting flue gas
2content is 35mg/m
3; Mercury, arsenic, cadmium, lead, zinc five heavy metal species removal efficiency are 95%, and in exiting flue gas, Hg is 0.011mg/m
3, As is 0.03mg/m
3, Cd is 0.06mg/m
3, Pb is 0.06mg/m
3, Zn is 0.01mg/m
3; Mixed fertilizer nitrogen content is 25.3%, reaches chemical fertilizer products quality standard, and plumbous resource rate is 80%, and the comprehensive recovery of mercury is 96%.
Embodiment 3
The present embodiment with nickel fibers flue gas for handling object, SO in nickel fibers flue gas
2: 0.8 ~ 2.0%, Hg:1 ~ 4mg/m
3, As:3 ~ 5mg/m
3, Pb:10 ~ 25mg/m
3, Cd:1 ~ 3 mg/m
3, Zn:2 ~ 6mg/m
3; Specifically comprise the steps:
(1) by after flue gas during smelting rough dusting, further flue-gas temperature is cooled to 30 DEG C;
(2) ammonium sulfide solution being the atomization of 6 by cooled flue gas and pH value fully contacts, to containing SO
2flue gas during smelting absorbs, the metal oxide in simultaneously stability flue gas, and the flue gas of purification is discharged after fixed-bed catalytic mercury removal device degree of depth removing heavy-metal, and wherein ammonium sulfide solution mass percent concentration is 15%;
(3) SO is absorbed
2with the rich solution of heavy metal by after press filtration, filter the sediment of heavy metal sulfide in solution, filter residue centralized recovery also turns back to smelting furnace, add in filtrate carbonic hydroammonium carry out in and, adjust ph, to 6, obtains the solution after neutralizing;
(4) neutralization after solution in temperature be pass under the condition of 45 DEG C mass percent concentration be 50% hydrogen peroxide be oxidized, the solution after oxidation adds carbonic hydroammonium adjust ph to 6.2, obtain be oxidized after solution;
(5) by the solution after oxidation in 48 DEG C of evaporation and concentration to 20% of original solution volume, be then cooled to 25 DEG C of crystallizations, be separated mixture and the concentrate of obtained ammonium sulfate and ATS (Ammonium thiosulphate).
SO in flue gas during smelting described in the present embodiment
2with heavy metal synergistic purification method equipment therefor, this device comprises air exhauster I 1, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9, demister 10, fixed-bed catalytic removing heavy-metal device 11, ammonium sulfide reservoir 12, filter pump 13, filter press 14, neutralization chamber 15, air exhauster II 16, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22, air exhauster 1 is connected with absorption tower I 2, absorption tower I 2, circulation reservoir I 3, circulating pump I 4, jet pipe I 5 circulates connection successively, absorption tower II 6, circulation reservoir II 7, circulating pump II 8, jet pipe II 9 circulates connection successively, absorption tower I 2, absorption tower II 6, demister 10, fixed-bed catalytic removing heavy-metal device 11 is communicated with successively, and ammonium sulfide reservoir 12 is connected with circulation reservoir II 7, and circulation reservoir II 7 is connected with circulation reservoir I 3, and circulation reservoir I 3 is connected with filter pump 13 with circulation reservoir II 7 simultaneously, filter pump 13, filter press 14, neutralization chamber 15, oxidation trough 17, reservoir 18, circulating pump III 19, evaporimeter 20, crystallization tank 21, centrifuge 22 is communicated with successively, and air exhauster II 16 is connected with oxidation trough 17, and reservoir 18 is connected with centrifuge 22, as shown in Figure 1.
The using method of device described in the present embodiment: flue gas is pumped in absorption tower I 2 through air exhauster I 1, ammonium sulfide solution enters in circulation reservoir I 3 and circulation reservoir II 7 from sending out ammonium sulfide reservoir 10 successively, ammonium sulfide solution in circulation reservoir I 3 fully contacts with flue gas after cooling by after jet pipe I 5 spray atomizing after circulating pump I 4 is extracted out, flue gas after absorbing in absorption tower I 2 enters in absorption tower II 6 and again absorbs, identical with in absorption tower I 2 of absorption process, flue gas after absorption enters demister 10 demist through the top on absorption tower II 6, flue gas is discharged after fixed-bed catalytic removing heavy-metal device 11 carries out degree of depth removing heavy-metal, absorb SO
2flow in circulation reservoir I 3 and circulation reservoir II 7 to mix with ammonium sulfide solution with the rich solution of heavy metal and again utilize, when in reservoir, rich solution pH reaches 4, part rich solution enters filter pump 11, add again in ammonium sulfide solution to reservoir regulate solution ph be 6 by filter pump 11 filter after filtrate enter in neutralization chamber 15, add carbonic hydroammonium to neutralize, adjust ph is to 6, filter residue centralized recovery also turns back to smelting furnace, by neutralization after solution deliver in oxidation trough 17 pass into mass percent concentration be 50% hydrogen peroxide be oxidized, then ammonium carbonate adjust ph is added to 6.2, solution after oxidation is sent in evaporimeter 18, 20% of original solution volume is concentrated at 48 DEG C, put into crystallization tank 21 and be cooled to 25 DEG C of crystallizations, be separated with centrifuge 22 after crystallization, obtain ammonium sulfate and ATS (Ammonium thiosulphate) mixed fertilizer and concentrate, concentrate turns back in evaporator tank 18.
By implementing said method, smoke desulfurization efficiency is 99.8%, SO in exiting flue gas
2content is 40mg/m
3; Mercury, arsenic, cadmium, lead, zinc five heavy metal species removal efficiency are 92%, and in exiting flue gas, Hg is 0.011mg/m
3, As is 0.06mg/m
3, Cd is 0.04mg/m
3, Pb is 0.08mg/m
3, Zn is 0.02mg/m
3; Mixed fertilizer nitrogen content is 24.1%, reaches chemical fertilizer products quality standard, and plumbous resource rate is 78%, and the comprehensive recovery of mercury is 96%.
Claims (3)
1. SO in a flue gas during smelting
2with heavy metal synergistic purification method, it is characterized in that comprising the steps:
(1) by after flue gas during smelting rough dusting, further flue-gas temperature is cooled to less than 50 DEG C;
(2) be that the ammonium sulfide solution of atomization between 7 ~ 3 fully contacts by cooled flue gas and pH value, to containing SO
2flue gas during smelting in SO
2absorb with metal oxide, the flue gas after purification is discharged after degree of depth removing heavy-metal;
(3) SO is absorbed
2after passing through press filtration with the rich solution of heavy metal, filter the sediment of heavy metal sulfide in solution, filter residue centralized recovery also turns back to smelting furnace, during the one added in filtrate in ammoniacal liquor, ammonium carbonate, carbonic hydroammonium is carried out and, adjust ph, to 5.8 ~ 6.5, obtains the solution after neutralizing;
(4) neutralization after solution in temperature be add under passing into air oxidation or normal temperature under the condition of 40 DEG C ~ 50 DEG C mass percent concentration be 27.5% ~ 50% hydrogen peroxide be oxidized, a kind of adjust ph in solution interpolation ammoniacal liquor after oxidation, ammonium carbonate, carbonic hydroammonium, to 5.8 ~ 6.5, obtains the solution after being oxidized;
(5) by the solution after oxidation in 45 DEG C ~ 50 DEG C evaporation and concentration to 40% ~ 60% of original solution volume, be then cooled to 20 DEG C ~ 30 DEG C crystallizations, be separated mixture and the concentrate of obtained ammonium sulfate and ATS (Ammonium thiosulphate).
2. SO in flue gas during smelting according to claim 1
2with heavy metal synergistic purification method, it is characterized in that: described in step (2), the mass percent concentration of ammonium sulfide solution is 8% ~ 25%.
3. SO in flue gas during smelting according to claim 1
2with heavy metal synergistic purification method equipment therefor, it is characterized in that: this device comprises air exhauster I (1), absorption tower I (2), circulation reservoir I (3), circulating pump I (4), jet pipe I (5), absorption tower II (6), circulation reservoir II (7), circulating pump II (8), jet pipe II (9), demister (10), fixed-bed catalytic removing heavy-metal device (11), ammonium sulfide reservoir (12), filter pump (13), filter press (14), neutralization chamber (15), air exhauster II (16), oxidation trough (17), reservoir (18), circulating pump III (19), evaporimeter (20), crystallization tank (21), centrifuge (22), air exhauster I (1) is connected with absorption tower I (2), absorption tower I (2), circulation reservoir I (3), circulating pump I (4), jet pipe I (5) circulates connection successively, absorption tower II (6), circulation reservoir II (7), circulating pump II (8), jet pipe II (9) circulates connection successively, absorption tower I (2), absorption tower II (6), demister (10), fixed-bed catalytic removing heavy-metal device (11) is communicated with successively, ammonium sulfide reservoir (12) is connected with circulation reservoir II (7), circulation reservoir II (7) is connected with circulation reservoir I (3), circulation reservoir I (3) is connected with filter pump (13) with circulation reservoir II (7) simultaneously, filter pump (13), filter press (14), neutralization chamber (15), oxidation trough (17), reservoir (18), circulating pump III (19), evaporimeter (20), crystallization tank (21), centrifuge (22) is communicated with successively, and air exhauster II (16) is connected with oxidation trough (17), and reservoir (18) is connected with centrifuge (22).
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| CN104998530A (en) * | 2015-03-31 | 2015-10-28 | 武汉宇青环保科技有限公司 | Sulfuric acid tail gas desulphurization device and method |
| CN105214455B (en) * | 2015-09-17 | 2017-12-01 | 昆明理工大学 | A kind of while denitration removing heavy-metal method |
| CN105233647B (en) * | 2015-09-17 | 2017-09-08 | 昆明理工大学 | A kind of method of ammonium sulfide solution desulphurization denitration |
| CN105886777B (en) * | 2016-05-16 | 2017-08-25 | 兰州理工大学 | Relieving haperacidity tail gas cooperates with the method for administering simultaneously Call Provision lithium with useless cobalt acid lithium |
| CN106582247A (en) * | 2016-12-26 | 2017-04-26 | 合肥天翔环境工程有限公司 | Sulfur and metal removal method for metallurgical flue gas |
| CN109012109A (en) * | 2018-06-26 | 2018-12-18 | 昆明理工大学 | It is a kind of while removing the SO in flue gas2With the method and device of NO |
| CN109260928B (en) * | 2018-10-22 | 2021-05-28 | 湘潭大学 | Ammonium bicarbonate desulfurization method and device with synergy of lead plaster desulfurization and flue gas desulfurization |
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