CN104128081A - Method for removing F and Cl in flue gas by using waste acid - Google Patents
Method for removing F and Cl in flue gas by using waste acid Download PDFInfo
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- CN104128081A CN104128081A CN201410345254.7A CN201410345254A CN104128081A CN 104128081 A CN104128081 A CN 104128081A CN 201410345254 A CN201410345254 A CN 201410345254A CN 104128081 A CN104128081 A CN 104128081A
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Abstract
The invention relates to a method for removing F and Cl in flue gas by using waste acid and belongs to the technical field of flue gas purification. The method comprises the following steps: firstly, spraying and washing the flue gas containing F and Cl by the waste acid, and then conducting alkali absorption to obtain standard flue gas. The invention has the advantage that waste acid is used to wash flue gas containing F and Cl, so that the F and Cl stay in the waste acid rather than entering a tail gas absorption desulfurization system and a zinc hydrometallurgical system; therefore, the method solves the problem of high F in the zinc hydrometallurgical process and saves the production cost for F removal.
Description
Technical field
The invention belongs to flue gases purification field, be specifically related to a kind of method of utilizing dirty acid to remove F in flue gas, Cl.
Background technology
Lead-zinc smelting stove is one of non-ferrous metal metallurgy enterprise environmental issue urgently to be resolved hurrily containing the improvement of F, Cl flue gas, and the improvement method of current domestic employing is roughly divided into dry method and wet method two classes.Dry treatment mainly contains active carbon adsorption, recirculating fluidized bed limestone-based process, spray drying process, Electron Beam Irradiation, impulse electric corona plasma method etc.It is short that dry treatment has flow process, after getting rid of, purify without sewage, dirty acid flue-gas temperature higher, can be by features such as chimney exhausts, but governance efficiency is low, equipment is huge, operating technology requires highly, causes it by wet processing, to be replaced gradually.Typical case's wet method represents that technique has limestone-based process, soda method, propylhomoserin method, magnesium oxide method, ionic adsorption method, zinc oxide method etc., and wet method administers that to have equipment little, operate simple and easy, governance efficiency advantages of higher, but amount of industrial wastewater and the quantity of slag are large, operating cost is high.And lead-zinc smelting stove flue gas is higher containing F, Cl, As, after processing, F, Cl, As Monodispersed, in absorbent solution and slag, directly return to this part liquid containing impurity such as F, Cl, As or slag to zinc smelting system use meeting larger to zinc metallurgy systematic influence.
That uses at present comparative maturity has limestone-based process, soda method, zinc oxide method, an ionic adsorption method.
Zinc oxide method is applicable to the improvement of Lead And Zinc Smelter flue gas, and absorbent can derive from smelting intermediate product zinc oxide dust or zinc-oxide calcine, and recycle in the existing roaster of product zinc sulfite or zinc sulfate Ke Song smeltery or wet method workshop.Because the supply of absorbent and the subsequent treatment of product can be produced and combine with smeltery, technique clean environment firendly and flow process are short, and construction investment and operating cost are all lower.Which existing problems: because zinc sulfite is insoluble in water, and zinc sulfate is soluble in water, if zinc sulfite is oxidized to misoperation in the process control of sulfuric acid, scrubbing tower inwall, nozzle, the easy fouling such as demister in pulp the pond in.Higher containing F, Cl in furnace flue gas, after processing, slag or liquid, all containing F, Cl, return to Zn system and use Zn system harm larger.
There is following problem in limestone-based process: in process control during misoperation, and scrubbing tower inwall, nozzle, the easily fouling such as demister; Higher containing F, Cl in furnace flue gas, after processing, slag or liquid are all containing F, Cl, and gypsum tailings take-away or landfill are all cumbersome.
There is following problem in ionic adsorption method: when pending dust content is more over design load, can cause each heat exchanger to stop up; Ionic liquid desorption and regeneration technique need to consume a large amount of steam; Higher containing F, Cl in furnace flue gas, after processing, slag or liquid, all containing F, Cl, cause secondary pollution.
Above-mentioned multiple lead-zinc smelting stove is only up to standard according to exhaust emissions containing F, Cl smoke gas treatment mode is basis, does not consider to contain the higher problem of F, Cl in furnace flue gas, therefore the rear slag of processing or liquid are all containing F, Cl, causes secondary pollution, and slag or liquid cannot be used.
Therefore the F, the Cl that, effectively remove in flue gas become the technical problem of needing solution badly.
Summary of the invention
The object of this invention is to provide a kind of method of utilizing dirty acid to remove F in flue gas, Cl, the method can effectively remove F in flue gas, Cl.
The technical solution used in the present invention is a kind of method of utilizing dirty acid to remove F in flue gas, Cl, and the method comprises the following steps: first utilize H
+the dirt acid of concentration≤4mol/L is carried out spray washing to the flue gas that contains F, Cl, and then absorbs by alkali, obtains flue gas up to standard.
H in dirty acid
+when concentration is greater than 4mol/L, flue gas is washed, can cause volatilizing HF, HCl in dirty acid, enter into flue gas, cause F, Cl to enter in a large number zinc wet process, thereby affect the serviceability of equipment and the quality of following process product.
Preferably, in described dirty acid, do not contain volatile material.When described volatile material refers to 90 ℃ of temperature >, can be from H
+the material volatilizing in the dirt acid of concentration≤4mol/L.
Inventor finds, if while containing volatile substances in dirty acid, can pollute pipeline
Preferably, temperature≤90 ℃ of described dirty acid.
Inventor is through verification experimental verification, in the amount of the flue gas that contains F, Cl described in dirty acid elution every cubic metre described, is less than 4000Nm
3time, can not make full use of dirty acid, and increase later stage energy consumption when F, Cl in the dirty acid of stripping; Amount at the flue gas that contains F, Cl described in dirty acid elution every cubic metre described is greater than 6000Nm
3time, can not well F contained in flue gas, Cl be remained in dirty acid, cause clean result bad.Preferably, for guaranteeing effectively flue gas to be washed, when described spray washing, by the sour spray washing 4000Nm of dirt every cubic metre described
3～6000Nm
3the amount of the flue gas of the described F of containing, Cl is carried out.
Preferably, the temperature in described when washing is 50 ℃～120 ℃.
Preferably, described alkali is solution or the ore pulp of metal hydroxides or metal oxide.Particularly preferred, metal hydroxides comprises NaOH, Ca (OH)
2, Mg (OH)
2or Zn (OH)
2; Metal oxide comprises ZnO or CaO.
Preferably, the absorption liquid of gained after spray washing is carried out in described dirty acid to the flue gas that contains F, Cl, and F, Cl with containing in dry relieving haperacidity tail gas stripping absorption liquid, obtain high concentrated acid.
Preferably, the temperature of described relieving haperacidity tail gas is 60 ℃～70 ℃.
Preferably, the water content≤20mg/Nm of described relieving haperacidity tail gas
3.
Preferably, when described stripping, adopt the mode of reverse contact stripping to carry out.
Preferably, during described reverse contact stripping, the speed≤5m/s of relieving haperacidity tail gas.
In the present invention, dirty acid used, is the olefin(e) acid that contains various impurity producing in metallurgy or Chemical Manufacture flow process.
Beneficial effect of the present invention is:
(1) flue gas that utilizes dirty acid elution to contain F, Cl, is retained in dirty acid F, Cl in flue gas, no longer enters tail gas absorbing system and zinc smelting system, has solved the high problem of F in zinc metallurgical process, has saved the production cost except F.
(2) flue gas that utilizes dirty acid elution to contain F, Cl, high owing to waiting to need the flue-gas temperature of washing, can effectively concentrate dirty acid, while having solved existing concentrated dirty acid, there is the problem of high energy consumption, reduced production cost.
(3) utilizing dirty acid to absorb after F, the Cl in flue gas, dirty acid can all be recycled.Wherein, dirty acid can be that 60 ℃～70 ℃ and water content relieving haperacidity tail gas seldom concentrate dirty acid by temperature, dirt acid after concentrated can be all for hydrometallurgy system, as acid decomposition, the leaching of indium, the leaching of copper etc. of tail gas absorption slag, while also having avoided sour with PROCESS FOR TREATMENT dirt in traditional utilization, produce the problem of harmful slag simultaneously.
The specific embodiment
For making those skilled in the art understand in detail production technology of the present invention and technique effect, with concrete production instance, further introduce application of the present invention and technique effect below.
Embodiment 1:
A kind of method of utilizing dirty acid to remove F in flue gas, Cl, the method comprises the following steps: first utilizing temperature is that spray washing is carried out in the dirt acid of 90 ℃ under the condition of 80 ℃ to the flue gas that contains F, Cl, and then absorb by sodium hydroxide solution, obtain flue gas up to standard; Wherein, when described spray washing, by the sour spray washing 5000Nm of dirt every cubic metre described
3the amount of described flue gas is carried out; H in dirty acid
+concentration is 4mol/L, and does not contain volatile material.
The absorption liquid of gained after spray washing is carried out in dirty acid to the flue gas that contains F, Cl, by water content, be 20mg/Nm
3, temperature is that the relieving haperacidity tail gas of 65 ℃ adopts F, the Cl containing in the mode stripping absorption liquid of reverse contact stripping, the stripping speed of relieving haperacidity tail gas is 5m/s, obtains high concentrated acid.
The flue gas that contains F, Cl that stripping goes out adopts the sheet aqueous slkali that pH is 9.0 to absorb.Wherein according to circumstances, regularly discharge NaF, NaCl.
Embodiment 2:
A kind of method of utilizing dirty acid to remove F in flue gas, Cl, the method comprises the following steps: first utilizing temperature is that spray washing is carried out in the dirt acid of 70 ℃ under the condition of 50 ℃ to the flue gas that contains F, Cl, and then absorb by sodium hydroxide solution, obtain flue gas up to standard; Wherein, when described spray washing, by the sour spray washing 4000Nm of dirt every cubic metre described
3the amount of described flue gas is carried out; H in dirty acid
+concentration is 1mol/L, and does not contain volatile material.
The absorption liquid of gained after spray washing is carried out in dirty acid to the flue gas that contains F, Cl, by water content, be 15mg/Nm
3, temperature is that the relieving haperacidity tail gas of 70 ℃ adopts F, the Cl containing in the mode stripping absorption liquid of reverse contact stripping, the stripping speed of relieving haperacidity tail gas is 5m/s, obtains high concentrated acid.
The flue gas that contains F, Cl that stripping goes out adopts the sheet aqueous slkali that pH is 10.0 to absorb.Wherein according to circumstances, regularly discharge NaF, NaCl.
Embodiment 3:
A kind of method of utilizing dirty acid to remove F in flue gas, Cl, the method comprises the following steps: first utilizing temperature is that spray washing is carried out in the dirt acid of 50 ℃ under the condition of 120 ℃ to the flue gas that contains F, Cl, and then absorb by sodium hydroxide solution, obtain flue gas up to standard; Wherein, when described spray washing, by the sour spray washing 6000Nm of dirt every cubic metre described
3the amount of described flue gas is carried out; H in dirty acid
+concentration is 2mol/L, and does not contain volatile material.
The absorption liquid of gained after spray washing is carried out in dirty acid to the flue gas that contains F, Cl, by water content, be 6mg/Nm
3, temperature is that the relieving haperacidity tail gas of 60 ℃ adopts F, the Cl containing in the mode stripping absorption liquid of reverse contact stripping, the stripping speed of relieving haperacidity tail gas is 5m/s, obtains high concentrated acid.
The flue gas that contains F, Cl that stripping goes out adopts the sheet aqueous slkali that pH is 9.5 to absorb.Wherein according to circumstances, regularly discharge NaF, NaCl.
Comparative example 1-3:
H in the dirt acid of F in flue gas, Cl will be removed
+concentration is for replacing with 4.2mol/L, 4.5mol/L and 5mol/L, and all the other are implemented according to the mode of embodiment 1 completely, obtain comparative example 1-3.
For verifying technique effect of the present invention, spy makes following contrast test:
| Embodiment | F content | Cl content | As content |
| Remove the flue gas of front embodiment 1 | 50mg/Nm 3 | 70mg/Nm 3 | 1mg/Nm 3 |
| Remove the flue gas of rear embodiment 1 | 1.3mg/Nm 3 | 0.4mg/Nm 3 | Do not detect |
| Remove the flue gas of front embodiment 2 | 56mg/Nm 3 | 67mg/Nm 3 | 1.6mg/Nm 3 |
| Remove the flue gas of rear embodiment 2 | 1.1mg/Nm 3 | 0.8mg/Nm 3 | Do not detect |
| Remove the flue gas of front embodiment 3 | 63mg/Nm 3 | 86mg/Nm 3 | 1.2mg/Nm 3 |
| Remove the flue gas of rear embodiment 3 | 1.1mg/Nm 3 | 0.5mg/Nm 3 | Do not detect |
| Remove the flue gas of front comparative example 1 | 52mg/Nm 3 | 74mg/Nm 3 | 1.1mg/Nm 3 |
| Remove the flue gas of rear comparative example 1 | 51.3mg/Nm 3 | 56mg/Nm 3 | Do not detect |
| Remove the flue gas of front comparative example 2 | 56mg/Nm 3 | 79mg/Nm 3 | 1.2mg/Nm 3 |
| Remove the flue gas of rear comparative example 2 | 67mg/Nm 3 | 78mg/Nm 3 | 0.6mg/Nm 3 |
| Remove the flue gas of front comparative example 3 | 48mg/Nm 3 | 84mg/Nm 3 | 1.4mg/Nm 3 |
| Remove the flue gas of rear comparative example 3 | 75mg/Nm 3 | 99mg/Nm 3 | 1.1mg/Nm 3 |
As can be seen from the above table, H in dirty acid
+concentration is on removing the impact of F in flue gas, Cl, As, H in dirty acid
+when concentration is greater than 4mol/L, dirty acid not only can not adsorbed F in flue gas, Cl, As, also can make in dirty acid original F, Cl thereupon by stripping out yet, causes removing F in rear flue gas, Cl content apparently higher than before removing; The removal efficiency of As is also obviously reduced.In the present invention, utilize H
+the dirt acid of concentration≤4mol/L is carried out spray washing to the flue gas that contains F, Cl, can remove well F, Cl, As in flue gas, has obtained unexpected technique effect.
Finally it should be noted that, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to above-described embodiment, those skilled in the art are to be understood that, still can modify or be equal to replacement the present invention, and not departing from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in claim scope of the present invention.
Claims (10)
1. utilize dirty acid to remove a method of F in flue gas, Cl, it is characterized in that, the method comprises the following steps: first utilize H
+the dirt acid of concentration≤4mol/L is carried out spray washing to the flue gas that contains F, Cl, and then absorbs by alkali, obtains flue gas up to standard.
2. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 1, is characterized in that, in described dirty acid, does not contain volatile material.
3. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 1, is characterized in that, temperature≤90 ℃ of described dirty acid.
4. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 1, is characterized in that, when described spray washing, by the sour spray washing 4000Nm of dirt every cubic metre described
3～6000Nm
3the amount of the flue gas of the described F of containing, Cl is carried out; Temperature during described washing is 50 ℃～120 ℃.
5. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 1, is characterized in that, described alkali is the solution of metal hydroxides or metal oxide.
6. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 1, it is characterized in that, the absorption liquid of gained after spray washing is carried out in described dirty acid to the flue gas that contains F, Cl, F, Cl with containing in dry relieving haperacidity tail gas stripping absorption liquid, obtain high concentrated acid.
7. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 6, is characterized in that, the temperature of described relieving haperacidity tail gas is 60 ℃～70 ℃.
8. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 6, is characterized in that the water content≤20mg/Nm of described relieving haperacidity tail gas
3.
9. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 6, is characterized in that, when described stripping, adopts the mode of reverse contact stripping to carry out.
10. a kind of method of utilizing dirty acid to remove F in flue gas, Cl according to claim 9, is characterized in that, during described reverse contact stripping, and the speed≤5m/s of relieving haperacidity tail gas.
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| CN201410345254.7A CN104128081B (en) | 2014-07-18 | 2014-07-18 | A kind of utilize the method for F, Cl in waste acid removing flue gas |
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| CN201410345254.7A CN104128081B (en) | 2014-07-18 | 2014-07-18 | A kind of utilize the method for F, Cl in waste acid removing flue gas |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386654A (en) * | 2014-11-17 | 2015-03-04 | 云南华联锌铟股份有限公司 | Method for treating acidic wastewater of sulfide ore roasted flue gas acid manufacture system |
| CN104787927A (en) * | 2015-04-16 | 2015-07-22 | 株洲冶炼集团股份有限公司 | Novel method for purifying and repeatedly using lead and zinc smelting flue gas washing contaminated acid wastewater |
| CN105126558A (en) * | 2015-07-28 | 2015-12-09 | 中国恩菲工程技术有限公司 | Waste acid treatment method |
| CN105731704A (en) * | 2016-01-18 | 2016-07-06 | 云南世邦环保科技发展有限公司 | Treatment method for removing fluorine and chlorine ions in acidic wastewater |
| CN108014627A (en) * | 2017-12-21 | 2018-05-11 | 双盾环境科技有限公司 | A kind of flue gas fluoride removal chlorine, zinc oxide desulfurization combined treatment process |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104386654A (en) * | 2014-11-17 | 2015-03-04 | 云南华联锌铟股份有限公司 | Method for treating acidic wastewater of sulfide ore roasted flue gas acid manufacture system |
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| CN105731704B (en) * | 2016-01-18 | 2019-01-01 | 云南世邦环保科技发展有限公司 | Fluorine removal, the processing method of chloride ion are gone in a kind of waste acid |
| CN108014627A (en) * | 2017-12-21 | 2018-05-11 | 双盾环境科技有限公司 | A kind of flue gas fluoride removal chlorine, zinc oxide desulfurization combined treatment process |
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