CN104803416B - Arsenic collecting method for arsenic-containing flue gas - Google Patents
Arsenic collecting method for arsenic-containing flue gas Download PDFInfo
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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; returning the arsenic-containing solution discharged from each process to the previous process as a circulating liquid of the previous process, and feeding the high-arsenic solution discharged from the cooling process of the air cooling tower 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 not only has low acid concentration, can effectively avoid high acid from corroding equipment and blocking pipelines, but also can collectThe method has the advantages of high arsenic efficiency, simple operation process, safety and environmental protection, and can greatly improve the recovery rate of arsenic in the flue gas.
Description
Technical field
The present invention relates to environment-protecting clean production technical field, more particularly to a kind of arsenical fume receipts arsenic method.
Background technology
At present, the method for being reclaimed to the arsenic in flue gas during smelting mainly has dry bag-type to receive arsenic technique and wet arsenic work
Skill.The dry bag-type that generally uses of the country receives arsenic technique, this technical maturity reliability, but in process of production workman contacted with arsenic compared with
Many, this can not only cause damage to the healthy of workman, and the airborne dust for producing can cause sizable harm to environment.It is wet
Method receipts arsenic technique avoids the disadvantages mentioned above existing for dry bag-type receipts arsenic technique, is a kind of clean manufacturing work of safety and environmental protection
Skill.
In recent years, domestic wet arsenic technique mainly has following two：The first is Publication No. CN101734718A
The wet arsenic technique that is illustrated of Chinese patent, it is lowered the temperature flue gas during smelting with the sulfuric acid scrubbing of 50~60%wt, then will
As2O3Wet method is collected, but the technique uses acid elution high, high to equipment material requirement, and many equipment need import, equipment cost
It is higher, and As in peracid2O3Solubility is low, a large amount of As2O3Crystallization can out block pipeline and nozzle, cause the production can not be just
Often carry out；It is for second three-level washing wet arsenic technique that the Chinese patent of Publication No. CN202099361U is illustrated, it
What is used is sour dense relatively low, but the technique is excessively simple, and receipts arsenic is not thorough, causes most of arsenic to be crystallized on tube wall and electrode,
Needs often stop and clear up electric demisting, while also part arsenic can enter the conversion system destruction catalyst of relieving haperacidity.
The content of the invention
For above-mentioned weak point of the prior art, and combine As2O3The slow-footed characteristic of crystal growth, the present invention is carried
A kind of receipts arsenic method of arsenical fume has been supplied, it is not only sour dense low, peracid etching apparatus can be prevented effectively from and pipeline is blocked, and
Receipts arsenic efficiency high, operating process are simple, safety and environmental protection, can greatly improve the rate of recovery of arsenic in flue gas.
The purpose of the present invention is achieved through the following technical solutions：
A kind of receipts arsenic method of arsenical fume, including following operation：
Air cooling tower refrigerating work procedure：Arsenical fume is passed into air cooling tower carries out cooling treatment, and spray acid is dense in air cooling tower
It is 2~10% (by mass percentage) to spend, and the arsenic solution high of the liquid outlet discharge of air cooling tower is sent to solution and receives arsenic operation, and
Flue gas feeding dynamic wave scrubbing operation after the cooling of the gas outlet discharge of air cooling tower；
Dynamic wave scrubbing operation：Flue gas is sent in dynamic wave scrubber and carries out dynamic wave after the cooling that air cooling tower is discharged
Carrying out washing treatment, it is 2~10% (by mass percentage) that acid concentration is sprayed in dynamic wave scrubber, and dynamic wave scrubber goes out liquid
The arsenic containing solution of mouth discharge returns to air cooling tower, as the circulation fluid of air cooling tower, and what the gas outlet of dynamic wave scrubber was discharged
Flue gas feeding two-stage packed tower cleaning procedure after washing；
Two-stage packed tower cleaning procedure：By dynamic wave scrubber discharge washing after flue gas pass sequentially through one-level packed tower and
Two grades of packed towers carry out two-step purification treatment, acid concentration is sprayed in two packed towers and is 2~10% (by mass percentage),
The arsenic containing solution of two liquid outlet discharges of packed tower returns to dynamic wave scrubber, used as the circulation of dynamic wave scrubber
Liquid, and flue gas feeding two-stage electricity demisting operation after two grades of purifications of the gas outlet discharge of packed tower；
Two-stage electricity demisting operation：Flue gas after two grades of purifications of packed tower discharge is passed sequentially through into two electrostatic precipitators carries out two
The electric demisting treatment of level, the acid solution of the leakage fluid dram discharge of the two electrostatic precipitators returns to two packed towers, is filled out as two
Expect the circulation fluid of tower, and the flue gas feeding acid making system after two-stage electricity demisting treatment carries out conventional relieving haperacidity；
Solution receives arsenic operation：Desorption treatment is carried out in the arsenic solution high feeding desorption tower that the liquid outlet of air cooling tower is discharged,
And the arsenic solution high feeding concentrator after desorption is processed carries out dense separation, then thickener underflow arsenic minerals to isolating starch into
Row separation of solid and liquid, the filtrate containing arsenic that separation of solid and liquid is obtained returns to dynamic wave scrubbing with dense isolated supernatant liquid
Device, used as the circulation fluid of dynamic wave scrubber, and the solid that separation of solid and liquid is obtained is As2O3, that is, realize receiving arsenic.
Preferably, in solution receives arsenic operation, the filtrate containing arsenic that separation of solid and liquid is obtained is clear with dense isolated upper strata
Clear liquid is divided into two treatment branches：A part returns to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and it is another
Part is sent to wastewater treatment operation；
Wastewater treatment operation：The filtrate containing arsenic obtained to separation of solid and liquid carries out sulphur with dense isolated supernatant liquid
Change heavy arsenic treatment, so as to solution after obtaining slag containing arsenic minerals and heavy arsenic；The reuse of slag containing arsenic minerals is smelting arsenic raw material, and solution enters after heavy arsenic
Row neutralisation treatment, so as to obtain gypsum tailings and recycle-water.
Preferably, in solution receives arsenic operation, the filtrate containing arsenic that separation of solid and liquid is obtained is clear with dense isolated upper strata
Clear liquid is gathered together, and forms mixed liquor containing arsenic；Circulation fluid is superfluous or this contains the sour dense of arsenic mixed liquor and is more than in arsenic system is received
When 8%, this contains arsenic mixed liquor can be sent to wastewater treatment operation, and otherwise this contains arsenic mixed liquor can only return to dynamic wave scrubber,
As the circulation fluid of dynamic wave scrubber.
Preferably, in wastewater treatment operation, the heavy arsenic treatment of vulcanization need to added in mixed liquor containing arsenic sodium sulfide solution and
Sulfuric acid, until the overall pH value of mixed liquor is 1~3；Neutralisation treatment need to in solution after heavy arsenic add milk of lime and molysite, 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 into the arsenical fume in air cooling tower is 250~400 DEG C, and
And by volume percentage, in the arsenical fume, As2O3Content be 0.1~1.0%, and SO2Content be 5~10%.
Preferably, in air cooling tower refrigerating work procedure, the flue-gas temperature of the gas outlet of air cooling tower for 70 DEG C~110 DEG C, air cooling
Gas flow rate in tower is 0.5~2m/s, and the sprinkle density in air cooling tower is 10~30m3/(m2·h)。
Preferably, in dynamic wave scrubbing operation, the flue-gas temperature of the gas 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 sprinkle density in dynamic wave scrubber is 100~300m3/(m2·
h)。
Preferably, in two-stage packed tower cleaning procedure, the flue-gas temperature of two gas outlets of packed tower be 35 DEG C~
45 DEG C, the gas flow rate in two packed towers is 0.5~1.5m/s, and the sprinkle density in two packed towers is 20~
35m3/(m2·h)。
Preferably, in two-stage electricity demisting operation, the flue-gas temperature of two gas outlets of electrostatic precipitator is respectively less than 40 DEG C, two
Gas flow rate in individual electrostatic precipitator is 0.3~1.0m/s.
Preferably, in air cooling tower refrigerating work procedure, dynamic wave scrubbing operation, two-stage packed tower cleaning procedure, two-stage electricity demisting
Operation and solution are received in the liquid circulation that arsenic operation is constituted, when the fluid low of circulation, in air cooling tower refrigerating work procedure
Air cooling tower in fill into new water, and/or to filling into new water in two electrostatic precipitators in two-stage electricity demisting operation.
As seen from the above technical solution provided by the invention, the receipts arsenic of the arsenical fume that the embodiment of the present invention is provided
Method makes arsenical fume sequentially pass through air cooling tower refrigerating work procedure, dynamic wave scrubbing operation, two-stage packed tower cleaning procedure, two-stage
Dynamic wave scrubbing in the treatment of electric demisting operation, and air cooling tower and dynamic wave scrubbing operation in air cooling tower refrigerating work procedure
Device employs the low sour dense circulation fluid that mass percentage concentration is 2~10%, therefore the receipts arsenic method can not only significantly mitigate
Corrosion of the circulation fluid to equipment, reduces to the requirement of the material of equipment, and ensure that arsenic is grown up step by step, will not make equipment or
Pipeline is blocked, and efficiently solves the dense receipts halfway problem of arsenic of low acid in the prior art.The arsenic solution high of air cooling tower discharge
SO is removed by desorption tower2After gas, feeding concentrator carries out crystallisation by cooling-dense separation, and the thickener underflow isolated
Arsenic minerals slurry carries out separation of solid and liquid again, so as to the As for being reclaimed2O3Solid product.By dense isolated supernatant liquid
The filtrate containing arsenic obtained with separation of solid and liquid is gathered together and to form mixed liquor containing arsenic；This contains arsenic mixed liquor and is largely returned to power
Ripple washer, used as the circulation fluid of dynamic wave scrubber, this effectively reduces wastewater treatment with discharge；And excess electron excess fraction is fed into
Wastewater treatment operation carries out vulcanizing heavy arsenic and neutralisation treatment, and so as to generate slag containing arsenic minerals, gypsum tailings and backwater, this contains arsenic minerals
Slag can return to smeltery raw material workshop dispensing and use, and backwater meets production recycle-water requirement, may return to size mixing and waits smelting
In other production processes in factory, thus this can realize waste liquid Efficient Cycle utilize, without outer row, safety and environmental protection, effectively
Reduce the pollution to environment.As can be seen here, the embodiment of the present invention is not only sour dense low, can be prevented effectively from peracid etching apparatus and
Block pipeline, and receive that arsenic efficiency high, operating process be simple, safety and environmental protection, the rate of recovery of arsenic in flue gas can be greatly improved.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will use needed for embodiment description
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of creative work row is not paid, it can also be obtained according to these accompanying drawings
His accompanying drawing.
The schematic flow sheet of the receipts arsenic method of the arsenical fume that Fig. 1 is provided by the embodiment of the present invention.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Inventive embodiment, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
The receipts arsenic method of the arsenical fume for being provided the embodiment of the present invention below is described in detail.
As shown in figure 1, a kind of receipts arsenic method of arsenical fume, can include following operation：
(1) air cooling tower refrigerating work procedure：Arsenical fume is passed into air cooling tower (i.e. air cooling compressor) carries out cooling treatment,
By mass percentage, acid concentration is sprayed in air cooling tower for 2~10% (preferably meet in actual applications：In 2%≤air cooling tower
Spray acid concentration ＜ 5%), the arsenic solution high of the liquid outlet discharge of air cooling tower is sent to solution and receives arsenic operation, and air cooling tower goes out
Flue gas is sent to dynamic wave scrubbing operation after the cooling of gas port discharge.
Wherein, the temperature into the arsenical fume in air cooling tower is preferably 250~400 DEG C, and by volume percentage,
In the arsenical fume, As2O3Content be preferably 0.1~1.0%, and SO2Content be preferably 5~10%.Air cooling tower goes out
The flue-gas temperature of gas port is preferably 70 DEG C~110 DEG C, and the gas flow rate in air cooling tower is preferably 0.5~2m/s, in air cooling tower
Sprinkle density is preferably 10~30m3/(m2·h).In the air cooling tower refrigerating work procedure, when arsenical fume cools to less than 120 DEG C
When, the As in arsenical fume2O3It is transformed into the As of solid-state form by gaseous state2O3Crystal grain, and by the diluted acid of circulated sprinkling in air cooling tower
Trapping is entered into solution, forms arsenic solution high, in the most of arsenic in arsenical fume trapped into arsenic solution high,
Solution receipts arsenic operation need to only be carried out to arsenic solution high again can just be realized reclaiming arsenic.
(2) dynamic wave scrubbing operation：Flue gas enters action in being sent to dynamic wave scrubber after the cooling that air cooling tower is discharged
Reeb carrying out washing treatment, it is 2~10% (in actual applications most that acid concentration is sprayed by mass percentage, in dynamic wave scrubber
It is good to meet：Acid concentration ＜ 5% is sprayed in 2%≤dynamic wave scrubber), the arsenic containing solution of the liquid outlet discharge of dynamic wave scrubber
Air cooling tower is returned to, used as the circulation fluid of air cooling tower, and flue gas is sent to after the washing of the gas outlet of dynamic wave scrubber discharge
Two-stage packed tower cleaning procedure.
Wherein, the flue-gas temperature of the gas outlet of dynamic wave scrubber is preferably 50 DEG C~85 DEG C, in dynamic wave scrubber
Gas flow rate is preferably 10~20m/s, and the sprinkle density in dynamic wave scrubber is preferably 100~300m3/(m2·h).At this
In dynamic wave scrubbing operation, the diluted acid sprayed in dynamic wave scrubber can efficiently trap entrained in flue gas after cooling down
As2O3Crystal grain, and enter into solution, arsenic containing solution is formed, such that it is able to the arsenic in flue gas further is trapped into arsenic containing solution
In, and air cooling tower is returned to, as the circulation fluid of air cooling tower.In actual applications, the liquid outlet of dynamic wave scrubber is preferably
Periodically discharge arsenic containing solution and return to air cooling tower (for example：Return to the liquid inlet or circulating slot of air cooling tower), as air cooling tower
Circulation fluid, and specific time interval can determine according to actual demand.
(3) two-stage packed tower cleaning procedure：Flue gas passes sequentially through one-level filler after the washing that dynamic wave scrubber is discharged
Tower and two grades of packed towers carry out two-step purification treatment, spray by mass percentage, in two packed towers acid concentration be 2~
10% (preferably meets in actual applications：Acid concentration ＜ 5% is sprayed in 2%≤two packed tower), two packed towers go out liquid
The arsenic containing solution of mouthful discharge returns to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and two grades of packed towers
Flue gas is sent to two-stage electricity demisting operation after the purification of gas outlet discharge.
Wherein, two flue-gas temperatures of the gas outlet of packed tower are preferably 35 DEG C~45 DEG C, the gas in two packed towers
Rate of flow of fluid is preferably 0.5~1.5m/s, and the sprinkle density in two packed towers is preferably 20~35m3/(m2·h).At this
In two-stage packed tower cleaning procedure, the diluted acid sprayed in two packed towers can trap As entrained in flue gas after washing2O3
Crystal grain, and enter into solution, arsenic containing solution is formed, such that it is able to arsenic remaining in flue gas further is trapped into arsenic containing solution
In, and dynamic wave scrubber is returned to, as the circulation fluid of dynamic wave scrubber；By after the two-stage packed tower cleaning procedure,
Arsenic content in flue gas is very little, i.e., only micro arsenic can enter in the electrostatic precipitator of two-stage electricity demisting operation, this
Arsenic can be avoided to be crystallized in electrostatic precipitator.In actual applications, the liquid outlet of two packed towers is preferably periodically discharge containing arsenic
Solution simultaneously returns to dynamic wave scrubber (for example：Return to the liquid inlet or circulating slot of dynamic wave scrubber), as dynamic wave
The circulation fluid of washer, and specific time interval can determine according to actual demand.
(4) two-stage electricity demisting operation：Flue gas after two grades of purifications of packed tower discharge is passed sequentially through into two electrostatic precipitators to enter
Row two-stage electricity demisting treatment, the acid solution that the leakage fluid dram of the two electrostatic precipitators is discharged returns to two packed towers, as
Two circulation fluids of packed tower, and the flue gas after two-stage electricity demisting treatment is sent to acid making system of the prior art and carries out routine
Relieving haperacidity.
Wherein, two flue-gas temperatures of the gas outlet of electrostatic precipitator are preferably respectively less than 40 DEG C, the gas in two electrostatic precipitators
Rate of flow of fluid is preferably 0.3~1.0m/s.In two-stage electricity demisting operation, two electrostatic precipitators can make after purification in flue gas
Acid mist be purified sedimentation, form acid solution, such that it is able to remove the acid mist in flue gas, make the cigarette after two-stage electricity demisting treatment
Sulphuric acid mist content ＜ 5mg/m in gas3, flue-gas temperature is down to less than 40 DEG C, as the qualified relieving haperacidity for meeting existing acid making system requirement
Flue gas.Meanwhile, acid solution may return to two packed towers, used as two circulation fluids of packed tower, in actual applications, two
The leakage fluid dram of electrostatic precipitator is preferably periodically to discharge acid solution and return to two packed towers (for example：Return to two packed towers
Liquid inlet or circulating slot), as two circulation fluids of packed tower, and specific time interval can according to actual demand come
It is determined that.
(5) solution receives arsenic operation：Carried out at desorption in the arsenic solution high feeding desorption tower that the liquid outlet of air cooling tower is discharged
Reason, and arsenic solution high feeding concentrator after desorption is processed carries out dense separation, then the thickener underflow arsenic minerals to isolating
Slurry carries out separation of solid and liquid (for example：Separation of solid and liquid can be carried out using filter press of the prior art), what separation of solid and liquid was obtained contains
Arsenic filtrate returns to dynamic wave scrubber with dense isolated supernatant liquid, as the circulation fluid of dynamic wave scrubber,
And the solid that separation of solid and liquid is obtained is As2O3, that is, realize receiving arsenic.
Wherein, the filtrate containing arsenic that separation of solid and liquid is obtained can be divided into two treatment with dense isolated supernatant liquid
Branch：A part returns to dynamic wave scrubber, and used as the circulation fluid of dynamic wave scrubber, and another part is sent at waste water
Science and engineering sequence.The two treatment branches can be carried out (for example simultaneously：Dynamic wave scrubber is largely returned to, and excess electron excess fraction send
Enter to wastewater treatment operation), it is also possible to separately carry out, second treatment branch can also be made just to enter in the case where specified conditions are met
OK, for example：The filtrate containing arsenic that separation of solid and liquid is obtained can be gathered together (for example with dense isolated supernatant liquid：
In converging in filtrate receiver), mixed liquor containing arsenic is formed, when arsenic system is received, (receipts arsenic system refers to by the sky in air cooling tower refrigerating work procedure
Two packed towers in dynamic wave scrubber, two-stage packed tower cleaning procedure and two-stage in cold tower, dynamic wave scrubbing operation
Arsenical fume that two electrostatic precipitators in electric demisting operation are collectively constituted receives arsenic system) in circulation fluid it is superfluous or this contains arsenic and mixes
The sour dense when being more than 8% of liquid is closed, this contains arsenic mixed liquor can just be sent to wastewater treatment operation, and otherwise this contains arsenic mixed liquor and only returns
To dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber.
(6) wastewater treatment operation：The filtrate containing arsenic obtained to separation of solid and liquid is entered with dense isolated supernatant liquid
The heavy arsenic treatment of row vulcanization, so as to solution after obtaining slag containing arsenic minerals and heavy arsenic；Slag containing arsenic minerals returns to smeltery raw material workshop, and sinks
Solution carries out neutralisation treatment after arsenic, so as to obtain gypsum tailings and recycle-water.
Wherein, vulcanizing heavy arsenic treatment need to be to sodium sulfide solution and sulfuric acid be added, until mixed liquor entirety in mixed liquor containing arsenic
PH value be 1~3, the consumption of vulcanized sodium is 1~1.5 times of theoretical value, and reacted ore pulp can be through press filtration of the prior art
Machine carries out separation of solid and liquid, so as to solution after obtaining slag containing arsenic minerals and heavy arsenic；This contains arsenic minerals slag and can return to smeltery raw material workshop.
Solution carries out neutralisation treatment again after heavy arsenic, and neutralisation treatment need to add milk of lime and molysite to solution after heavy arsenic, until molten after heavy arsenic
The pH value of liquid is 7~9, and it is 7 to control the mol ratio of Fe and As:1~30:1；Ore pulp after neutralisation treatment after filtering can be with
Obtain gypsum tailings and meet the recycle-water of production recycle-water requirement, its in the smeltery such as the recycle-water may return to size mixing
In his production process, therefore the receipts arsenic method of arsenical fume that the embodiment of the present invention is provided is without discharging any waste liquor, safety and environmental protection.
(7) in addition to above-mentioned technical proposal, the receipts arsenic method of the arsenical fume can also include：In air cooling tower bosher
Sequence, dynamic wave scrubbing operation, two-stage packed tower cleaning procedure, two-stage electricity demisting operation and solution receive the liquid that arsenic operation is constituted
In body circulation, when the fluid low of circulation, to filling into new water in the air cooling tower in air cooling tower refrigerating work procedure, and/or to
New water is filled into two electrostatic precipitators in two-stage electricity demisting operation；For example：In solution receives arsenic operation, when separation of solid and liquid is obtained
Filtrate containing arsenic be fed to wastewater treatment operation with dense isolated supernatant liquid after, the fluid low of circulation, this
When need to filling into new water in the air cooling tower in air cooling tower refrigerating work procedure, and/or to two in two-stage electricity demisting operation
New water is filled into electrostatic precipitator.
It should be noted that the receipts arsenic method of the arsenical fume that the embodiment of the present invention is provided, its arsenic rate of recovery can reach
99 more than ﹪ are reached, waste water is less than 0.5mg/L after being processed through wastewater treatment operation containing arsenic, meets production recycle-water requirement.
As fully visible, the receipts arsenic method of the arsenical fume that the embodiment of the present invention is provided at least possesses following characteristics：
(1) in the receipts arsenic method, the power in air cooling tower and dynamic wave scrubbing operation in air cooling tower refrigerating work procedure
Ripple washer employs diluted acid that mass percentage concentration is 2~10% as circulation fluid, and can be dense using quality percentage
The diluted acid for 2~5% is spent as circulation fluid；Compared with prior art, what the receipts arsenic method was used sour dense low (can reach
The acid concentration ＜ 5% of 2%≤circulation fluid), this can significantly mitigate corrosion of the circulation fluid to equipment, reduce the material to equipment
It is required that, save equipment cost.
(2) in the receipts arsenic method, two-stage packed tower cleaning procedure and two-stage electricity are additionally arranged after dynamic wave scrubbing operation
Demisting operation, that is, the flue gas for employing air cooling tower-dynamic wave scrubber-two-stage packed tower-two-stage electrostatic precipitator combination washing is net
Change equipment, arsenical fume is to sequentially pass through the said equipment successively, and this ensure that arsenic is grown up step by step, can't make the said equipment
Block, thus this can effectively solve the problem that low acid in the prior art it is dense receive the halfway problem of arsenic so that not only ensure that compared with
Receipts arsenic efficiency high, and ensure that the flue gas purifying equipment of combination washing can be according to the receipts long-term normal table of arsenic method
Ground operation.
(3) in the receipts arsenic method, the arsenic solution high of air cooling tower discharge is removing SO by desorption tower2After gas, feeding
Concentrator carries out crystallisation by cooling-dense separation, and the thickener underflow arsenic minerals slurry isolated has carried out separation of solid and liquid；At this
During one, except the As that separation of solid and liquid is reclaimed2O3Outside solid, remaining liquid (can include dense isolated
The filtrate containing arsenic that supernatant liquid and separation of solid and liquid are obtained) major part return to dynamic wave scrubber, washed as dynamic wave
The circulation fluid of device is washed, this effectively reduces wastewater treatment with discharge.
(4) in the receipts arsenic method, when the liquid that solution receives generation in arsenic operation is more, except being largely returned to move
Outside the washer of Reeb, unnecessary liquid can enter wastewater treatment operation, carry out vulcanizing heavy arsenic and neutralisation treatment successively, so that
To slag containing arsenic minerals, gypsum tailings and recycle-water；This contains arsenic minerals slag and may return to smelting arsenic operation, used as smelting arsenic raw material, and reuse
Water meets production recycle-water requirement, and in other production processes in the factory such as may return to size mixing, therefore this can realize giving up
The Efficient Cycle of liquid utilizes, without outer row, safety and environmental protection, effectively reduce the pollution to environment.
(5) by volume percentage, the receipts arsenic method can be to As2O3Content for 0.1~1.0%, SO2Content be 5
~10% arsenical fume is processed, therefore the receipts arsenic method has very strong adaptability, Neng Goushi to the content of arsenic in flue gas
For various purifications containing arsenic flue gas during smelting.
(6) the receipts arsenic method is a kind of wet arsenic method, can be prevented effectively from the generation containing arsenic powder dirt, and operation ring
Border is relatively friendly.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with several
The receipts arsenic method of specific embodiment and the arsenical fume provided the embodiment of the present invention with reference to accompanying drawing is described in detail.
Embodiment 1
As shown in figure 1, Xinjiang solution of gold smelting plant is carried out using the preprocess method of two-stage roasting to certain arsenic-containing gold concentrate
Treatment, and the baking flue gas for producing are calcined after being gathered dust by cyclone dust collection, electricity, employ the embodiments of the present invention and provided
The receipts arsenic method of arsenical fume carry out wet arsenic.Wherein, electricity gather dust the baking flue gas of outlet discharge temperature for 330~
350 DEG C, exhaust gas volumn is 17072Nm3/h；By volume percentage, in the baking flue gas, As2O3Content is 0.21%, SO2's
Content is 6.99%.
Specifically, according to the technical parameter described in table 1 below, and the cigarette containing arsenic provided using the embodiments of the present invention
The receipts arsenic method of gas makes baking flue gas pass sequentially through air cooling tower-dynamic wave scrubber-two-stage packed tower-two-stage electrostatic precipitator to be carried out
Gas cleaning.Electricity gathers dust and exports the 0.2~0.5g/m of dustiness of the baking flue gas discharged3, passing sequentially through air cooling tower-dynamic wave
After washer-two-stage packed tower, the collection rate of arsenic has reached more than 99%, is all collected substantially；Hereafter, flue gas enters two-stage
Electrostatic precipitator removes remaining acid mist, after two-stage electricity demisting operation, the sulphuric acid mist content in flue gas<5mg/m3, and flue-gas temperature drops
To less than 40 DEG C, the requirement of existing acid making system is met, can be passed through existing acid making system carries out conventional relieving haperacidity.
Table 1：
Further, the stripped tower removing SO of arsenic solution high that air cooling tower is discharged2Afterwards, concentrator is fed into be cooled down
Crystallization-dense separation, and the thickener underflow arsenic minerals slurry isolated sends into filter press and carries out separation of solid and liquid, so as to obtain time
The As of receipts2O3Solid product, and the filtrate containing arsenic that dense isolated supernatant liquid and separation of solid and liquid are obtained converges in one
Rise and form mixed liquor containing arsenic；This contains arsenic mixed liquor major part and returns to dynamic wave scrubber, used as following for dynamic wave scrubber
Ring liquid, excess electron excess fraction is fed into wastewater treatment operation.In wastewater treatment operation, to being added in the mixed liquor containing arsenic, vulcanized sodium is molten
Liquid and sulfuric acid carry out vulcanizing heavy arsenic, until the overall pH value of mixed liquor is 1.5~2, reacted ore pulp can be through prior art
In filter press carry out separation of solid and liquid, so as to solution after obtaining slag containing arsenic minerals and heavy arsenic；This contains arsenic minerals slag and can return to smeltery
Raw material workshop, and solution carries out neutralisation treatment again after the heavy arsenic, neutralisation treatment need to be to addition milk of lime and iron in solution after heavy arsenic
Salt, 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 be aerated, neutralize
Ore pulp after treatment can obtain gypsum tailings and recycle-water after filtering；The recycle-water meets production recycle-water requirement, can return
In returning to other production processes in the smeltery such as size mixing, thus this can realize waste liquid Efficient Cycle utilize, without outer row,
Safety and environmental protection, effectively reduces the pollution to environment.
As fully visible, the embodiment of the present invention is not only sour dense low, can be prevented effectively from peracid etching apparatus and block pipeline, and
And receive that arsenic efficiency high, operating process be simple, safety and environmental protection, the rate of recovery of arsenic in flue gas can be greatly improved.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (10)
1. a kind of receipts arsenic method of arsenical fume, it is characterised in that including following operation：
Air cooling tower refrigerating work procedure：Arsenical fume is passed into air cooling tower carries out cooling treatment, by mass percentage, air cooling tower
Middle spray acid concentration is 2~10%, and the arsenic solution high of the liquid outlet of air cooling tower discharge is sent to solution and receives arsenic operation, and air cooling tower
Gas outlet discharge cooling after flue gas feeding dynamic wave scrubbing operation；
Dynamic wave scrubbing operation：Flue gas is sent in dynamic wave scrubber and carries out dynamic wave scrubbing after the cooling that air cooling tower is discharged
Treatment, it is 2~10% that acid concentration is sprayed by mass percentage, in dynamic wave scrubber, and the liquid outlet of dynamic wave scrubber is arranged
The arsenic containing solution for going out returns to air cooling tower, used as the circulation fluid of air cooling tower, and the washing of the gas outlet of dynamic wave scrubber discharge
Flue gas sends into two-stage packed tower cleaning procedure afterwards；
Two-stage packed tower cleaning procedure：Flue gas passes sequentially through one-level packed tower and two grades after the washing that dynamic wave scrubber is discharged
Packed tower carries out two-step purification treatment, and spraying acid concentration by mass percentage, in two packed towers is 2~10%, two
The arsenic containing solution of the liquid outlet discharge of packed tower returns to dynamic wave scrubber, as the circulation fluid of dynamic wave scrubber, and
Flue gas feeding two-stage electricity demisting operation after two grades of purifications of the gas outlet discharge of packed tower；
Two-stage electricity demisting operation：Flue gas after two grades of purifications of packed tower discharge is passed sequentially through into two electrostatic precipitators carries out two-stage electricity
Demisting treatment, the acid solution of the leakage fluid dram discharge of the two electrostatic precipitators returns to two packed towers, used as two packed towers
Circulation fluid, and two-stage electricity demisting treatment after flue gas feeding acid making system carry out conventional relieving haperacidity；
Solution receives arsenic operation：Desorption treatment is carried out in the arsenic solution high feeding desorption tower that the liquid outlet of air cooling tower is discharged, and will
Arsenic solution high feeding concentrator after desorption treatment carries out dense separation, then thickener underflow arsenic minerals slurry to isolating is consolidated
Liquid is separated, and the filtrate containing arsenic that separation of solid and liquid is obtained returns to dynamic wave scrubber with dense isolated supernatant liquid, is made
It is the circulation fluid of dynamic wave scrubber, and the solid that separation of solid and liquid is obtained is As2O3, that is, realize receiving arsenic.
2. it is according to claim 1 to receive arsenic method, it is characterised in that in solution receives arsenic operation, what separation of solid and liquid was obtained
Filtrate containing arsenic is divided into two treatment branches with dense isolated supernatant liquid：A part returns to dynamic wave scrubber,
Used as the circulation fluid of dynamic wave scrubber, and another part is sent to wastewater treatment operation；
Wastewater treatment operation：It is heavy that the filtrate containing arsenic obtained to separation of solid and liquid carries out vulcanization with dense isolated supernatant liquid
Arsenic treatment, so as to solution after obtaining slag containing arsenic minerals and heavy arsenic；The reuse of slag containing arsenic minerals is smelting arsenic raw material, and during solution is carried out after heavy arsenic
And treatment, so as to obtain gypsum tailings and recycle-water.
3. it is according to claim 2 to receive arsenic method, it is characterised in that in solution receives arsenic operation, what separation of solid and liquid was obtained
Filtrate containing arsenic is gathered together with dense isolated supernatant liquid, forms mixed liquor containing arsenic；Circulated in arsenic system is received
Liquid is superfluous or this is when containing arsenic mixed liquor sour dense and being more than 8%, and this contains arsenic mixed liquor can be sent to wastewater treatment operation, and otherwise this contains arsenic
Mixed liquor can only return to dynamic wave scrubber, used as the circulation fluid of dynamic wave scrubber.
4. according to claim 3 to receive arsenic method, it is characterised in that in wastewater treatment operation, the heavy arsenic treatment of vulcanization is needed
To sodium sulfide solution and sulfuric acid is added in mixed liquor containing arsenic, until the overall pH value of mixed liquor is 1~3；Neutralisation treatment need to be to heavy
Milk of lime and molysite are added after arsenic in solution, 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. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in air cooling tower refrigerating work procedure, to enter
The temperature for entering the arsenical fume in air cooling tower is 250~400 DEG C, and by volume percentage, in the arsenical fume, As2O3
Content be 0.1~1.0%, and SO2Content be 5~10%.
6. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in air cooling tower refrigerating work procedure, it is empty
The flue-gas temperature of the gas outlet of cold tower is 70 DEG C~110 DEG C, and the gas flow rate in air cooling tower is 0.5~2m/s, in air cooling tower
Sprinkle density is 10~30m3/(m2·h)。
7. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in dynamic wave scrubbing operation, move
The flue-gas temperature of the gas outlet of Reeb washer is 50 DEG C~85 DEG C, and the gas flow rate in dynamic wave scrubber is 10~20m/s,
Sprinkle density in dynamic wave scrubber is 100~300m3/(m2·h)。
8. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in two-stage packed tower cleaning procedure
In, the flue-gas temperature of two gas outlets of packed tower is 35 DEG C~45 DEG C, and the gas flow rate in two packed towers is 0.5~
1.5m/s, the sprinkle density in two packed towers is 20~35m3/(m2·h)。
9. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in two-stage electricity demisting operation, two
The flue-gas temperature of the gas outlet of individual electrostatic precipitator is respectively less than 40 DEG C, and the gas flow rate in two electrostatic precipitators is 0.3~1.0m/
s。
10. it is according to any one of claim 1 to 4 to receive arsenic method, it is characterised in that in air cooling tower refrigerating work procedure, to move
The liquid that Reeb washing procedure, two-stage packed tower cleaning procedure, two-stage electricity demisting operation and solution receipts arsenic operation are constituted is followed
In ring, when the fluid low of circulation, to filling into new water in the air cooling tower in air cooling tower refrigerating work procedure, and/or to two-stage
New water is filled into two electrostatic precipitators in electric demisting operation.
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| CN1994531A (en) * | 2006-12-06 | 2007-07-11 | 山东国大黄金股份有限公司 | Process for purifying arsenic-containing mineral burned fume |
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