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 PDF

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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
reservoir
absorption tower
heavy metal
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CN103768910A (en
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王学谦
王郎郎
宁平
殷在飞
马懿星
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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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

SO in a kind of flue gas during smelting 2with heavy metal synergistic purification method and device
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).
CN201410019587.0A 2014-01-16 2014-01-16 SO in a kind of flue gas during smelting 2with heavy metal synergistic purification method and device Expired - Fee Related CN103768910B (en)

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