CN104803416A - Arsenic collecting method for arsenic-containing flue gas - Google Patents
Arsenic collecting method for arsenic-containing flue gas Download PDFInfo
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- CN104803416A CN104803416A CN201510163358.0A CN201510163358A CN104803416A CN 104803416 A CN104803416 A CN 104803416A CN 201510163358 A CN201510163358 A CN 201510163358A CN 104803416 A CN104803416 A CN 104803416A
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Abstract
The invention discloses an arsenic collecting method of arsenic-containing flue gas, which comprises the following steps: after being sequentially treated by an air cooling tower cooling procedure, a dynamic wave washing procedure, a two-stage packed tower purifying procedure and a two-stage electric defogging procedure, the arsenic-containing flue gas is sent into an acid making system to be made into acid conventionally; the arsenic-containing solution discharged from each step is returned to the previous step as a circulating liquid for the previous step, and the high arsenic-containing solution discharged from the air cooling tower cooling stepThe arsenic solution is sent into a desorption tower for desorption treatment; feeding the high-arsenic solution after desorption treatment into a thickener for concentration separation, performing solid-liquid separation, returning the arsenic-containing filtrate obtained by solid-liquid separation and the supernatant liquid obtained by concentration separation to the circulating liquid of the dynamic wave washing process, wherein the solid obtained by solid-liquid separation is As2O3Thereby realizing arsenic collection. The embodiment of the invention has low acid concentration, can effectively avoid high acid from corroding equipment and blocking a pipeline, has high arsenic collecting efficiency, simple operation flow, safety and environmental protection, and can greatly improve the recovery rate of arsenic in flue gas.
Description
Technical field
The present invention relates to environment-protecting clean production technical field, particularly relate to a kind of receipts arsenic method of arsenical fume.
Background technology
At present, the method reclaimed the arsenic in flue gas during smelting mainly contains dry bag-type and receives arsenic technique and wet arsenic technique.The domestic dry bag-type generally adopted receives arsenic technique, and this technical maturity is reliable, but workman contacts more with arsenic in process of production, and this not only can cause damage to the healthy of workman, and the airborne dust produced can cause sizable harm to environment.Wet arsenic technique avoids the above-mentioned shortcoming existing for dry bag-type receipts arsenic technique, is a kind of process for cleanly preparing of safety and environmental protection.
In recent years, domestic wet arsenic technique mainly contains following two kinds: the wet arsenic technique that the first Chinese patent being publication number is CN101734718A is set forth, and it is the sulfuric acid scrubbing cooling flue gas during smelting with 50 ~ 60%wt, then by As
2o
3wet method is collected, but this technique adopts high acid elution, and require high to equipment material, a lot of equipment needs import, and equipment cost is higher, and As in peracid
2o
3solubleness is low, a large amount of As
2o
3crystallization meeting out blocking pipe and nozzle, causes production normally not carry out; The second is three grades of washing wet arsenic techniques that Chinese patent that publication number is CN202099361U is set forth, the acid that it adopts is dense lower, but this technique is too simple, receive arsenic not thorough, cause the crystallization on tube wall and electrode of most of arsenic, need the electric demist of cleaning of often stopping, the conversion system simultaneously also having part arsenic can enter relieving haperacidity destroys catalyzer.
Summary of the invention
For above-mentioned weak point of the prior art, and in conjunction with As
2o
3the slow-footed characteristic of crystal growth, the invention provides a kind of receipts arsenic method of arsenical fume, not only sour dense low, can effectively avoid peracid etching apparatus and blocking pipe, and receipts arsenic efficiency is high, operating process simple, safety and environmental protection, significantly can improve the rate of recovery of arsenic in flue gas.
The object of the invention is to be achieved through the following technical solutions:
A receipts arsenic method for arsenical fume, comprises following operation:
Air cooling tower refrigerating work procedure: arsenical fume is passed in air cooling tower and carries out cooling process, in air cooling tower, spray acid concentration is 2 ~ 10% (by mass percentage), the high arsenic solution that the liquid outlet of air cooling tower is discharged is sent to solution receipts arsenic operation, and after the cooling that the air outlet of air cooling tower is discharged, flue gas sends into dynamic wave scrubbing operation;
Dynamic wave scrubbing operation: after the cooling of discharge air cooling tower, flue gas is sent in dynamic wave scrubber and carries out dynamic wave scrubbing process, in dynamic wave scrubber, spray acid concentration is 2 ~ 10% (by mass percentage), the arsenic containing solution that the liquid outlet of dynamic wave scrubber is discharged turns back to air cooling tower, as the circulation fluid of air cooling tower, and after the washing that the air outlet of dynamic wave scrubber is discharged, flue gas sends into two-stage packing tower cleaning section;
Two-stage packing tower cleaning section: after the washing of discharge dynamic wave scrubber, flue gas carries out two-step purification process by one-level packing tower and secondary packing tower successively, in two packing towers, spray acid concentration is 2 ~ 10% (by mass percentage), the arsenic containing solution that the liquid outlet of two packing towers is discharged all turns back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and after the purification that the air outlet of secondary packing tower is discharged, flue gas sends into two-stage electricity demist operation;
Two-stage electricity demist operation: after the purification of discharge secondary packing tower, flue gas carries out two-stage electricity demist process by two electrostatic precipitators successively, the acid solution that the leakage fluid dram of these two electrostatic precipitators is discharged all turns back to two packing towers, as the circulation fluid of two packing towers, and the flue gas feeding acid making system after two-stage electricity demist process carries out conventional relieving haperacidity;
Solution receives arsenic operation: the high arsenic solution of being discharged by the liquid outlet of air cooling tower is sent in desorption tower and carried out desorption process, and the high arsenic solution feeding thickener after desorption process is carried out dense separation, again solid-liquid separation is carried out to isolated thickener underflow arsenic minerals slurry, what solid-liquid separation obtained turns back to dynamic wave scrubber containing arsenic filtrate with the dense supernatant liquid obtained that is separated, as the circulation fluid of dynamic wave scrubber, and the solid that solid-liquid separation obtains is As
2o
3, namely realize receiving arsenic.
Preferably, receive in arsenic operation at solution, what solid-liquid separation obtained is divided into two to process branch containing arsenic filtrate with the dense supernatant liquid obtained that is separated: a part turns back to dynamic wave scrubber, and as the circulation fluid of dynamic wave scrubber, and another part is sent to wastewater treatment operation;
Wastewater treatment operation: what obtain solid-liquid separation carries out sulfuration containing arsenic filtrate sink arsenic process with the dense supernatant liquid obtained that is separated, thus obtains containing solution after arsenic minerals slag and heavy arsenic; Be smelting arsenic raw material containing the reuse of arsenic minerals slag, and after heavy arsenic, solution carries out neutralizing treatment, thus obtain gypsum tailings and reuse water.
Preferably, receive in arsenic operation at solution, what solid-liquid separation obtained is gathered together with the dense supernatant liquid obtained that is separated containing arsenic filtrate, is formed containing arsenic mixed solution; When receiving that circulation fluid in arsenic system is superfluous maybe should be greater than 8% containing the acid of arsenic mixed solution is dense, should can deliver to wastewater treatment operation containing arsenic mixed solution, otherwise only should can turn back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber containing arsenic mixed solution.
Preferably, in wastewater treatment operation, arsenic process is sunk in sulfuration need to containing add sodium sulfide solution and sulfuric acid, until the pH value of mixed solution entirety is 1 ~ 3 in arsenic mixed solution; Neutralizing treatment need add milk of lime and molysite in solution after heavy arsenic, until the pH value of solution is 7 ~ 9 after heavy arsenic, and the mol ratio of Fe and As is 7:1 ~ 30:1.
Preferably, in air cooling tower refrigerating work procedure, the temperature entering the arsenical fume in air cooling tower is 250 ~ 400 DEG C, and by volume percentages, in this arsenical fume, As
2o
3content be 0.1 ~ 1.0%, and SO
2content be 5 ~ 10%.
Preferably, in air cooling tower refrigerating work procedure, the flue-gas temperature of the air outlet of air cooling tower is 70 DEG C ~ 110 DEG C, and the gas flow rate in air cooling tower is 0.5 ~ 2m/s, and the specific liquid rate in air cooling tower is 10 ~ 30m
3/ (m
2h).
Preferably, in dynamic wave scrubbing operation, the flue-gas temperature of the air outlet of dynamic wave scrubber is 50 DEG C ~ 85 DEG C, and the gas flow rate in dynamic wave scrubber is 10 ~ 20m/s, and the specific liquid rate in dynamic wave scrubber is 100 ~ 300m
3/ (m
2h).
Preferably, in two-stage packing tower cleaning section, the flue-gas temperature of the air outlet of two packing towers is 35 DEG C ~ 45 DEG C, and the gas flow rate in two packing towers is 0.5 ~ 1.5m/s, and the specific liquid rate in two packing towers is 20 ~ 35m
3/ (m
2h).
Preferably, in two-stage electricity demist operation, the flue-gas temperature of the air outlet of two electrostatic precipitators is all less than 40 DEG C, and the gas flow rate in two electrostatic precipitators is 0.3 ~ 1.0m/s.
Preferably, in the liquid circulation that air cooling tower refrigerating work procedure, dynamic wave scrubbing operation, two-stage packing tower cleaning section, two-stage electricity demist operation and solution receipts arsenic operation are formed, when the fluid low circulated, in the air cooling tower in air cooling tower refrigerating work procedure, fill into new water, and/or fill into new water in two electrostatic precipitators in two-stage electricity demist operation.
As seen from the above technical solution provided by the invention, the receipts arsenic method of the arsenical fume that the embodiment of the present invention provides makes arsenical fume have passed through air cooling tower refrigerating work procedure successively, dynamic wave scrubbing operation, two-stage packing tower cleaning section, the process of two-stage electricity demist operation, and the dynamic wave scrubber in the air cooling tower in air cooling tower refrigerating work procedure and dynamic wave scrubbing operation all have employed the dense circulation fluid of low acid that mass percentage concentration is 2 ~ 10%, therefore this receipts arsenic method significantly can not only alleviate the corrosion of circulation fluid to equipment, reduce the material requirement to equipment, and can ensure that arsenic is grown up step by step, equipment or pipeline can not be made to block, efficiently solve the halfway problem of low acid dense receipts arsenic in prior art.The high arsenic solution that air cooling tower is discharged removes SO by desorption tower
2after gas, send into thickener and carry out crystallisation by cooling-dense separation, and isolated thickener underflow arsenic minerals slurry carries out solid-liquid separation again, thus obtain the As of recovery
2o
3solid phase prod.Being gathered together containing arsenic filtrate that the supernatant liquid obtained by dense separation and solid-liquid separation obtain is formed containing arsenic mixed solution; Should turn back to dynamic wave scrubber containing arsenic mixed solution major part, as the circulation fluid of dynamic wave scrubber, this effectively reduces wastewater treatment and discharge; And excess electron excess fraction is fed into wastewater treatment operation carries out sulfuration and sink arsenic and neutralizing treatment, thus create containing arsenic minerals slag, gypsum tailings and backwater, should can return raw material workshop, smeltery batching containing arsenic minerals slag to use, and backwater meets the requirement of production reuse water, can turn back in other production processes in the smeltery such as to size mixing, therefore this Efficient Cycle that can realize waste liquid utilizes, without the need to outer row, safety and environmental protection, effectively reduces the pollution to environment.As can be seen here, the embodiment of the present invention is not only sour dense low, can effectively avoid peracid etching apparatus and blocking pipe, and receipts arsenic efficiency is high, operating process simple, safety and environmental protection, significantly can improve the rate of recovery of arsenic in flue gas.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, not paying under the capable prerequisite of creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
The schematic flow sheet of the receipts arsenic method of the arsenical fume that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Below the receipts arsenic method of the arsenical fume that the embodiment of the present invention provides is described in detail.
As shown in Figure 1, a kind of receipts arsenic method of arsenical fume, can comprise following operation:
(1) air cooling tower refrigerating work procedure: arsenical fume is passed in air cooling tower (i.e. atmospheric cooling tower) and carries out cooling process, by mass percentage, in air cooling tower, spray acid concentration is 2 ~ 10% (preferably meeting in actual applications: spray acid concentration < 5% in 2%≤air cooling tower), the high arsenic solution that the liquid outlet of air cooling tower is discharged is sent to solution receipts arsenic operation, and after the cooling that the air outlet of air cooling tower is discharged, flue gas is sent to dynamic wave scrubbing operation.
Wherein, the temperature entering the arsenical fume in air cooling tower is preferably 250 ~ 400 DEG C, and by volume percentages, in this arsenical fume, As
2o
3content be preferably 0.1 ~ 1.0%, and SO
2content be preferably 5 ~ 10%.The flue-gas temperature of the air outlet of air cooling tower is preferably 70 DEG C ~ 110 DEG C, and the gas flow rate in air cooling tower is preferably 0.5 ~ 2m/s, and the specific liquid rate in air cooling tower is preferably 10 ~ 30m
3/ (m
2h).In this air cooling tower refrigerating work procedure, when arsenical fume cools to below 120 DEG C, the As in arsenical fume
2o
3the As of solid-state form is transformed into by gaseous state
2o
3crystal grain, and entered into solution by the trapping of the diluted acid of circulated sprinkling in air cooling tower, form high arsenic solution, thus the most of arsenic in arsenical fume can be trapped in high arsenic solution, only need carry out solution receipts arsenic operation to high arsenic solution again and just can realize reclaiming arsenic.
(2) dynamic wave scrubbing operation: after the cooling of discharge air cooling tower, flue gas is sent in dynamic wave scrubber and carries out dynamic wave scrubbing process, by mass percentage, in dynamic wave scrubber, spray acid concentration is 2 ~ 10% (preferably meeting in actual applications: spray acid concentration < 5% in 2%≤dynamic wave scrubber), the arsenic containing solution that the liquid outlet of dynamic wave scrubber is discharged turns back to air cooling tower, as the circulation fluid of air cooling tower, and after the washing that the air outlet of dynamic wave scrubber is discharged, flue gas is sent to two-stage packing tower cleaning section.
Wherein, the flue-gas temperature of the air outlet of dynamic wave scrubber is preferably 50 DEG C ~ 85 DEG C, and the gas flow rate in dynamic wave scrubber is preferably 10 ~ 20m/s, and the specific liquid rate in dynamic wave scrubber is preferably 100 ~ 300m
3/ (m
2h).In this dynamic wave scrubbing operation, the diluted acid sprayed in dynamic wave scrubber efficiently can trap As entrained in the rear flue gas of cooling
2o
3crystal grain, and enter into solution, form arsenic containing solution, thus can further the arsenic in flue gas be trapped in arsenic containing solution, and turn back to air cooling tower, as the circulation fluid of air cooling tower.In actual applications, the liquid outlet of dynamic wave scrubber is preferably regularly discharged arsenic containing solution and turns back to air cooling tower (such as: the liquid inlet or the circulation groove that turn back to air cooling tower), as the circulation fluid of air cooling tower, and the concrete timed interval can be determined according to the demand of reality.
(3) two-stage packing tower cleaning section: after the washing of discharge dynamic wave scrubber, flue gas carries out two-step purification process by one-level packing tower and secondary packing tower successively, by mass percentage, in two packing towers, spray acid concentration is 2 ~ 10% (preferably meeting in actual applications: spray acid concentration < 5% in 2%≤two packing tower), the arsenic containing solution that the liquid outlet of two packing towers is discharged all turns back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and flue gas is sent to two-stage electricity demist operation after the purification that the air outlet of secondary packing tower is discharged.
Wherein, the flue-gas temperature of the air outlet of two packing towers is preferably 35 DEG C ~ 45 DEG C, and the gas flow rate in two packing towers is preferably 0.5 ~ 1.5m/s, and the specific liquid rate in two packing towers is preferably 20 ~ 35m
3/ (m
2h).In this two-stage packing tower cleaning section, the diluted acid sprayed in two packing towers can trap As entrained in the rear flue gas of washing
2o
3crystal grain, and enter into solution, form arsenic containing solution, thus can further arsenic remaining in flue gas be trapped in arsenic containing solution, and turn back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber; After this two-stage packing tower cleaning section, the arsenic content in flue gas is very little, and namely only have the arsenic of trace can enter in the electrostatic precipitator of two-stage electricity demist operation, this can be avoided arsenic at electrostatic precipitator intercrystalline.In actual applications, the liquid outlet of two packing towers is preferably regularly discharged arsenic containing solution and turns back to dynamic wave scrubber (such as: the liquid inlet or the circulation groove that turn back to dynamic wave scrubber), as the circulation fluid of dynamic wave scrubber, and the concrete timed interval can be determined according to the demand of reality.
(4) two-stage electricity demist operation: after the purification of discharge secondary packing tower, flue gas carries out two-stage electricity demist process by two electrostatic precipitators successively, the acid solution that the leakage fluid dram of these two electrostatic precipitators is discharged all turns back to two packing towers, as the circulation fluid of two packing towers, and the flue gas after the demist process of two-stage electricity is sent to acid making system of the prior art and carries out conventional relieving haperacidity.
Wherein, the flue-gas temperature of the air outlet of two electrostatic precipitators is preferably all less than 40 DEG C, and the gas flow rate in two electrostatic precipitators is preferably 0.3 ~ 1.0m/s.In this two-stage electricity demist operation, acid mist after two electrostatic precipitators can make purification in flue gas is purified sedimentation, form acid solution, thus the acid mist in flue gas can be removed, make sulphuric acid mist content < 5mg/m in the flue gas after two-stage electricity demist process
3, flue-gas temperature is down to less than 40 DEG C, becomes the qualified relieving haperacidity flue gas meeting existing acid making system requirement.Simultaneously, acid solution can turn back to two packing towers, as the circulation fluid of two packing towers, in actual applications, the leakage fluid dram of two electrostatic precipitators is preferably regularly discharged acid solution and turns back to two packing towers (such as: the liquid inlet or the circulation groove that turn back to two packing towers), as the circulation fluid of two packing towers, and the concrete timed interval can be determined according to the demand of reality.
(5) solution receives arsenic operation: the high arsenic solution of being discharged by the liquid outlet of air cooling tower is sent in desorption tower and carried out desorption process, and the high arsenic solution feeding thickener after desorption process is carried out dense separation, again solid-liquid separation (such as: pressure filter of the prior art can be adopted to carry out solid-liquid separation) is carried out to isolated thickener underflow arsenic minerals slurry, what solid-liquid separation obtained turns back to dynamic wave scrubber containing arsenic filtrate with the dense supernatant liquid obtained that is separated, as the circulation fluid of dynamic wave scrubber, and the solid that solid-liquid separation obtains is As
2o
3, namely realize receiving arsenic.
Wherein, what solid-liquid separation obtained can be divided into two to process branch containing arsenic filtrate with the dense supernatant liquid obtained that is separated: a part turns back to dynamic wave scrubber, and as the circulation fluid of dynamic wave scrubber, and another part is sent to wastewater treatment operation.These two process branches can carry out (such as: major part turns back to dynamic wave scrubber simultaneously, and excess electron excess fraction is sent to wastewater treatment operation), also can separately carry out, second can also be made to process branch just carry out meeting under specified conditions, such as: what solid-liquid separation obtained can be gathered together (such as: converge in filtrate receiver) with the dense supernatant liquid obtained that is separated containing arsenic filtrate, formed containing arsenic mixed solution, when receipts arsenic system, (receiving arsenic system refers to by the air cooling tower in air cooling tower refrigerating work procedure, dynamic wave scrubber in dynamic wave scrubbing operation, the arsenical fume that two electrostatic precipitators in two packing towers in two-stage packing tower cleaning section and two-stage electricity demist operation form jointly receives arsenic system) in circulation fluid superfluous or when should be greater than 8% containing the acid of arsenic mixed solution is dense, just wastewater treatment operation should can be sent to containing arsenic mixed solution, otherwise only should turn back to dynamic wave scrubber containing arsenic mixed solution, as the circulation fluid of dynamic wave scrubber.
(6) wastewater treatment operation: what obtain solid-liquid separation carries out sulfuration containing arsenic filtrate sink arsenic process with the dense supernatant liquid obtained that is separated, thus obtains containing solution after arsenic minerals slag and heavy arsenic; Turn back to raw material workshop, smeltery containing arsenic minerals slag, and after heavy arsenic, solution carries out neutralizing treatment, thus obtain gypsum tailings and reuse water.
Wherein, arsenic process is sunk in sulfuration need to containing add sodium sulfide solution and sulfuric acid in arsenic mixed solution, until the pH value of mixed solution entirety is 1 ~ 3, the consumption of sodium sulphite is theoretical value 1 ~ 1.5 times, reacted ore pulp can carry out solid-liquid separation through pressure filter of the prior art, thus obtains containing solution after arsenic minerals slag and heavy arsenic; Raw material workshop, smeltery should can be turned back to containing arsenic minerals slag.After heavy arsenic, solution carries out neutralizing treatment again, and neutralizing treatment need add milk of lime and molysite to solution after heavy arsenic, until the pH value of solution is 7 ~ 9 after heavy arsenic, and the mol ratio of control Fe and As is 7:1 ~ 30:1; Ore pulp after neutralizing treatment can obtain gypsum tailings after filtering and meet the reuse water produced reuse water and require, this reuse water can turn back in other production processes in the smeltery such as to size mixing, therefore the receipts arsenic method of arsenical fume that provides of the embodiment of the present invention is without the need to discharging any waste liquor, safety and environmental protection.
(7) except technique scheme, the receipts arsenic method of this arsenical fume can also comprise: in the liquid circulation that air cooling tower refrigerating work procedure, dynamic wave scrubbing operation, two-stage packing tower cleaning section, two-stage electricity demist operation and solution receipts arsenic operation are formed, when the fluid low circulated, in the air cooling tower in air cooling tower refrigerating work procedure, fill into new water, and/or fill into new water in two electrostatic precipitators in two-stage electricity demist operation; Such as: receive in arsenic operation at solution, what obtain when solid-liquid separation is separated after the supernatant liquid obtained is fed to wastewater treatment operation containing arsenic filtrate with dense, the fluid low of circulation, now need to fill into new water in the air cooling tower in air cooling tower refrigerating work procedure, and/or fill into new water in two electrostatic precipitators in two-stage electricity demist operation.
It should be noted that, the receipts arsenic method of the arsenical fume that the embodiment of the present invention provides, its arsenic rate of recovery can reach 99 more than ﹪, and waste water is less than 0.5mg/L containing arsenic after the process of wastewater treatment operation, meets and produces reuse water requirement.
As fully visible, the receipts arsenic method of arsenical fume that the embodiment of the present invention provides at least possesses following characteristics:
(1) in this receipts arsenic method, dynamic wave scrubber in air cooling tower in air cooling tower refrigerating work procedure and dynamic wave scrubbing operation all have employed mass percentage concentration be the diluted acid of 2 ~ 10% as circulation fluid, and mass percentage concentration can be adopted to be that the diluted acid of 2 ~ 5% is as circulation fluid; Compared with prior art, the acid that this receipts arsenic method adopts dense low (the acid concentration < 5% of 2%≤circulation fluid can be reached), this significantly can alleviate the corrosion of circulation fluid to equipment, reduces the material requirement to equipment, has saved equipment cost.
(2) in this receipts arsenic method, two-stage packing tower cleaning section and two-stage electricity demist operation has been set up after dynamic wave scrubbing operation, namely have employed the flue gas purifying equipment of air cooling tower-dynamic wave scrubber-two-stage packing tower-two-stage electrostatic precipitator combination washing, arsenical fume sequentially passes through aforesaid device successively, this can ensure that arsenic is grown up step by step, aforesaid device can't be made to block, therefore this effectively can solve the halfway problem of low acid dense receipts arsenic in prior art, thus not only ensure that higher receipts arsenic efficiency, and ensure that the flue gas purifying equipment that this combination is washed can run according to the long-term normal table of this receipts arsenic method.
(3) in this receipts arsenic method, the high arsenic solution that air cooling tower is discharged is removing SO by desorption tower
2after gas, be fed into thickener and carry out crystallisation by cooling-dense separation, and isolated thickener underflow arsenic minerals slurry carries out solid-liquid separation; In this course, except solid-liquid separation obtains the As of recovery
2o
3outside solid, remaining liquid (can comprise supernatant liquid that dense separation obtains and solid-liquid separation obtain containing arsenic filtrate) major part all turns back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, this effectively reduces wastewater treatment and discharge.
(4) in this receipts arsenic method, when the liquid produced in solution receipts arsenic operation is more, except major part turns back to dynamic wave scrubber, unnecessary liquid can enter wastewater treatment operation, carry out sulfuration successively and sink arsenic and neutralizing treatment, thus obtain containing arsenic minerals slag, gypsum tailings and reuse water; Smelting arsenic operation should can be turned back to containing arsenic minerals slag, as smelting arsenic raw material, and reuse water meets the requirement of production reuse water, can turn back in other production processes in the factory such as to size mixing, therefore this Efficient Cycle that can realize waste liquid utilizes, without the need to outer row, safety and environmental protection, effectively reduces the pollution to environment.
(5) by volume percentages, this receipts arsenic method can to As
2o
3content be 0.1 ~ 1.0%, SO
2content be 5 ~ 10% arsenical fume process, therefore this receipts arsenic method has very strong adaptability to the content of arsenic in flue gas, can be applicable to the multiple purification containing arsenic flue gas during smelting.
(6) this receipts arsenic method is a kind of wet arsenic method, effectively can avoid the generation containing arsenic powder dirt, and operating environment is relatively friendly.
In order to the technique effect more clearly showing technical scheme provided by the present invention and produce, also by reference to the accompanying drawings the receipts arsenic method of the arsenical fume that the embodiment of the present invention provides is described in detail with a few specific embodiment below.
Embodiment 1
As shown in Figure 1, Xinjiang solution of gold smelting plant adopts the pretreatment process of two-stage roasting to process certain arsenic-containing gold concentrate, and the baking flue gas that roasting produces is after gathering dust through cyclone dust collection, electricity, the receipts arsenic method that have employed the arsenical fume that the invention described above embodiment provides carries out wet arsenic.Wherein, the electricity temperature of baking flue gas that outlet discharges of gathering dust is 330 ~ 350 DEG C, and exhaust gas volumn is 17072Nm
3/ h; By volume percentages, in this baking flue gas, As
2o
3content is 0.21%, SO
2content be 6.99%.
Particularly, according to the technical parameter described in following table 1, and the receipts arsenic method of the arsenical fume adopting the invention described above embodiment to provide makes baking flue gas carry out gas cleaning by air cooling tower-dynamic wave scrubber-two-stage packing tower-two-stage electrostatic precipitator successively.Electricity gathers dust and exports the dustiness 0.2 ~ 0.5g/m of the baking flue gas of discharging
3, after passing through air cooling tower-dynamic wave scrubber-two-stage packing tower successively, the collection rate of arsenic reaches more than 99%, is substantially all collected; After this, flue gas enters two-stage electrostatic precipitator and removes remaining acid mist, after two-stage electricity demist operation, and the sulphuric acid mist content <5mg/m in flue gas
3, and flue-gas temperature is down to less than 40 DEG C, meets the requirement of existing acid making system, can pass into existing acid making system and carry out conventional relieving haperacidity.
Table 1:
Further, the high arsenic solution that air cooling tower is discharged removes SO through desorption tower
2after, be fed into thickener and carry out crystallisation by cooling-dense separation, and isolated thickener underflow arsenic minerals slurry feeding pressure filter carries out solid-liquid separation, thus obtain the As of recovery
2o
3solid phase prod, and being gathered together containing arsenic filtrate that the supernatant liquid that dense separation obtains and solid-liquid separation obtain is formed containing arsenic mixed solution; All should turn back to dynamic wave scrubber containing arsenic mixed solution major part, as the circulation fluid of dynamic wave scrubber, excess electron excess fraction is fed into wastewater treatment operation.In wastewater treatment operation, carry out sulfuration to this sink arsenic containing adding sodium sulfide solution and sulfuric acid in arsenic mixed solution, until the pH value of mixed solution entirety is 1.5 ~ 2, reacted ore pulp can carry out solid-liquid separation through pressure filter of the prior art, thus obtains containing solution after arsenic minerals slag and heavy arsenic; Raw material workshop, smeltery should can be turned back to containing arsenic minerals slag, and solution carries out neutralizing treatment again after this heavy arsenic, neutralizing treatment need add milk of lime and molysite in solution after heavy arsenic, until the pH value of solution is 7 ~ 9 after heavy arsenic, and the mol ratio of Fe and As is 20:1, blast air and carry out aeration, the ore pulp after neutralizing treatment can obtain gypsum tailings and reuse water after filtering; This reuse water meets produces reuse water requirement, in other production processes that can turn back to sizes mixing waits in smeltery, therefore this can realize waste liquid Efficient Cycle utilization, without the need to outer row, safety and environmental protection, effectively reduce the pollution to environment.
As fully visible, the embodiment of the present invention is not only sour dense low, can effectively avoid peracid etching apparatus and blocking pipe, and receipts arsenic efficiency is high, operating process simple, safety and environmental protection, significantly can improve the rate of recovery of arsenic in flue gas.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1. a receipts arsenic method for arsenical fume, is characterized in that, comprise following operation:
Air cooling tower refrigerating work procedure: arsenical fume is passed in air cooling tower and carries out cooling process, in air cooling tower, spray acid concentration is 2 ~ 10% (by mass percentage), the high arsenic solution that the liquid outlet of air cooling tower is discharged is sent to solution receipts arsenic operation, and after the cooling that the air outlet of air cooling tower is discharged, flue gas sends into dynamic wave scrubbing operation;
Dynamic wave scrubbing operation: after the cooling of discharge air cooling tower, flue gas is sent in dynamic wave scrubber and carries out dynamic wave scrubbing process, in dynamic wave scrubber, spray acid concentration is 2 ~ 10% (by mass percentage), the arsenic containing solution that the liquid outlet of dynamic wave scrubber is discharged turns back to air cooling tower, as the circulation fluid of air cooling tower, and after the washing that the air outlet of dynamic wave scrubber is discharged, flue gas sends into two-stage packing tower cleaning section;
Two-stage packing tower cleaning section: after the washing of discharge dynamic wave scrubber, flue gas carries out two-step purification process by one-level packing tower and secondary packing tower successively, in two packing towers, spray acid concentration is 2 ~ 10% (by mass percentage), the arsenic containing solution that the liquid outlet of two packing towers is discharged all turns back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and after the purification that the air outlet of secondary packing tower is discharged, flue gas sends into two-stage electricity demist operation;
Two-stage electricity demist operation: after the purification of discharge secondary packing tower, flue gas carries out two-stage electricity demist process by two electrostatic precipitators successively, the acid solution that the leakage fluid dram of these two electrostatic precipitators is discharged all turns back to two packing towers, as the circulation fluid of two packing towers, and the flue gas feeding acid making system after two-stage electricity demist process carries out conventional relieving haperacidity;
Solution receives arsenic operation: the high arsenic solution of being discharged by the liquid outlet of air cooling tower is sent in desorption tower and carried out desorption process, and the high arsenic solution feeding thickener after desorption process is carried out dense separation, again solid-liquid separation is carried out to isolated thickener underflow arsenic minerals slurry, what solid-liquid separation obtained turns back to dynamic wave scrubber containing arsenic filtrate with the dense supernatant liquid obtained that is separated, as the circulation fluid of dynamic wave scrubber, and the solid that solid-liquid separation obtains is As
2o
3, namely realize receiving arsenic.
2. receipts arsenic method according to claim 1, it is characterized in that, receive in arsenic operation at solution, what solid-liquid separation obtained is divided into two to process branch containing arsenic filtrate with the dense supernatant liquid obtained that is separated: a part turns back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and another part is sent to wastewater treatment operation;
Wastewater treatment operation: what obtain solid-liquid separation carries out sulfuration containing arsenic filtrate sink arsenic process with the dense supernatant liquid obtained that is separated, thus obtains containing solution after arsenic minerals slag and heavy arsenic; Be smelting arsenic raw material containing the reuse of arsenic minerals slag, and after heavy arsenic, solution carries out neutralizing treatment, thus obtain gypsum tailings and reuse water.
3. receipts arsenic method according to claim 2, is characterized in that, receives in arsenic operation at solution, and what solid-liquid separation obtained is gathered together with the dense supernatant liquid obtained that is separated containing arsenic filtrate, is formed containing arsenic mixed solution; When receiving that circulation fluid in arsenic system is superfluous maybe should be greater than 8% containing the acid of arsenic mixed solution is dense, should can deliver to wastewater treatment operation containing arsenic mixed solution, otherwise only should can turn back to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber containing arsenic mixed solution.
4. receipts arsenic method according to claim 3, is characterized in that, in wastewater treatment operation, arsenic process is sunk in sulfuration need to containing add sodium sulfide solution and sulfuric acid, until the pH value of mixed solution entirety is 1 ~ 3 in arsenic mixed solution; Neutralizing treatment need add milk of lime and molysite in solution after heavy arsenic, until the pH value of solution is 7 ~ 9 after heavy arsenic, and the mol ratio of Fe and As is 7:1 ~ 30:1.
5. receipts arsenic method according to any one of claim 1 to 4, is characterized in that, in air cooling tower refrigerating work procedure, the temperature entering the arsenical fume in air cooling tower is 250 ~ 400 DEG C, and by volume percentages, in this arsenical fume, As
2o
3content be 0.1 ~ 1.0%, and SO
2content be 5 ~ 10%.
6. receipts arsenic method according to any one of claim 1 to 4, it is characterized in that, in air cooling tower refrigerating work procedure, the flue-gas temperature of the air outlet of air cooling tower is 70 DEG C ~ 110 DEG C, gas flow rate in air cooling tower is 0.5 ~ 2m/s, and the specific liquid rate in air cooling tower is 10 ~ 30m
3/ (m
2h).
7. receipts arsenic method according to any one of claim 1 to 4, it is characterized in that, in dynamic wave scrubbing operation, the flue-gas temperature of the air outlet of dynamic wave scrubber is 50 DEG C ~ 85 DEG C, gas flow rate in dynamic wave scrubber is 10 ~ 20m/s, and the specific liquid rate in dynamic wave scrubber is 100 ~ 300m
3/ (m
2h).
8. receipts arsenic method according to any one of claim 1 to 4, it is characterized in that, in two-stage packing tower cleaning section, the flue-gas temperature of the air outlet of two packing towers is 35 DEG C ~ 45 DEG C, gas flow rate in two packing towers is 0.5 ~ 1.5m/s, and the specific liquid rate in two packing towers is 20 ~ 35m
3/ (m
2h).
9. receipts arsenic method according to any one of claim 1 to 4, is characterized in that, in two-stage electricity demist operation, the flue-gas temperature of the air outlet of two electrostatic precipitators is all less than 40 DEG C, and the gas flow rate in two electrostatic precipitators is 0.3 ~ 1.0m/s.
10. receipts arsenic method according to any one of claim 1 to 4, it is characterized in that, in the liquid circulation that air cooling tower refrigerating work procedure, dynamic wave scrubbing operation, two-stage packing tower cleaning section, two-stage electricity demist operation and solution receipts arsenic operation are formed, when the fluid low circulated, in the air cooling tower in air cooling tower refrigerating work procedure, fill into new water, and/or fill into new water in two electrostatic precipitators in two-stage electricity demist operation.
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| CN108970308A (en) * | 2018-07-04 | 2018-12-11 | 北京矿冶科技集团有限公司 | A kind of high-temp chlorination flue gas processing method containing gold |
| CN110433630A (en) * | 2019-08-15 | 2019-11-12 | 株洲冶炼集团科技开发有限责任公司 | A kind of lead-zinc smelting mercury in flue gas deep purifying and mercury recovery process |
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| CN105617843A (en) * | 2016-02-14 | 2016-06-01 | 楚雄滇中有色金属有限责任公司 | Contaminated acid treatment water recycling method |
| CN108970308A (en) * | 2018-07-04 | 2018-12-11 | 北京矿冶科技集团有限公司 | A kind of high-temp chlorination flue gas processing method containing gold |
| CN108970308B (en) * | 2018-07-04 | 2020-11-20 | 北京矿冶科技集团有限公司 | High-temperature chlorination gold-containing flue gas treatment method |
| CN110433630A (en) * | 2019-08-15 | 2019-11-12 | 株洲冶炼集团科技开发有限责任公司 | A kind of lead-zinc smelting mercury in flue gas deep purifying and mercury recovery process |
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