CN103341310A - Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas - Google Patents
Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas Download PDFInfo
- Publication number
- CN103341310A CN103341310A CN2013102770660A CN201310277066A CN103341310A CN 103341310 A CN103341310 A CN 103341310A CN 2013102770660 A CN2013102770660 A CN 2013102770660A CN 201310277066 A CN201310277066 A CN 201310277066A CN 103341310 A CN103341310 A CN 103341310A
- Authority
- CN
- China
- Prior art keywords
- mercury
- absorption liquid
- sulfate
- sulfur dioxide
- composite absorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas. The method comprises the following steps of: preparing composite absorption liquid by using mercury sulfate, ferric sulfate and sulfuric acid serving as the main components; efficiently absorbing the zero-valence mercury in the smoke gas by using an absorption tower; converting the zero-valence mercury to sulphurous acid mercury; reacting the ferric sulfate with the sulfur dioxide to generate sulfuric acid by; and decomposing the generated sulphurous acid mercury into elemental mercury and mercury sulfate by virtue of a recycling device. In comparison with the prior art, the method has the advantages that the absorption efficiency of the smoke gas zero-valance mercury can be improved, the use amount of absorbents is reduced and the recycling of the zero-valence mercury is realized. Besides, due to recycling of sulfur dioxide, sulfuric acid can be recycled, the reducing action of the sulfur dioxide on Hg<2+> is reduced, and the overall recovery of the zero-valence is improved. Thus, the method is particularly suitable for discharge control of smoke gas mercury with high sulfur dioxide concentration.
Description
Technical field
The invention belongs to the air pollution control technique of field of environment protection, especially relate to a kind of method of from the non-ferrous metal metallurgy flue gas, removing and reclaim gaseous state nonvalent mercury and sulfur dioxide relieving haperacidity.
Background technology
As everyone knows, mercury is a kind of toxic pollutant, has the characteristics such as biological concentration of persistence, easy animal migration and height.Not only the harm to ecological environment is also very big for it, and health is produced direct or indirect harm.Five sixties of 20th century are broken out " minamata disease " event in Japan, namely are serious mercury disasters.
United Nations Environment Programme (UNEP) classifies mercury as global contaminant.The 5th meeting of the government-to-government talks committee about mercury that hold at Geneva, Switzerland in January, 2013 formed " international control mercury pollution pact ", and international community accelerates gradually to the paces of global mercury pollution control.The mercury emission of China is very big at present, and huge international pressure is bearing just for this reason in the Chinese government.In numerous mercury emissions source, the discharge capacity of mercury accounts for very big proportion in the non-ferrous metal metallurgy flue gas.Tsing-Hua University studies show that: the non-coal-fired atmosphere mercury emission of China was 393t in 2003, and wherein non-ferrous metal metallurgy discharging 330t accounts for about 52% of the total mercury emission in the whole nation.Yet current domestic and international most research all is placed on focus in the mercury emissions control of coal-fired flue-gas, has ignored the research of non-ferrous metal metallurgy industry mercury emissions control to a certain extent.Compare with coal-fired flue-gas, the non-ferrous metal metallurgy flue gas has characteristics such as mercury concentration height, sulfur dioxide concentration height, production cycle fluctuation are big.So be applicable to that the removal of mercury technology of coal-fired flue-gas may not be effectively same in the mercury emissions control of non-ferrous metal metallurgy flue gas.Simultaneously, though mercury is pollutant, also be a kind of scarce resource simultaneously, all be widely used in smelting, instrument manufacturing, chemical industry, medical industry and atomic energy industry etc.Therefore, at the higher characteristics of mercury concentration in the development non-ferrous metal metallurgy industry flue gas, should adopt to be recovered as main removal of mercury technology.Like this, both can effectively control the discharging of mercury in the flue gas, and can realize the recycling to flue gas mercury again.
The roasting of non-ferrous metal metallurgy industry ore is generally carried out under hot conditions, so the mercury overwhelming majority in the ore is with nonvalent mercury (Hg
0) form enter in the flue gas.Different with coal-fired flue-gas, at the improvement of high concentration mercury fume, generally adopt several methods such as condensation method, absorption method and absorption process both at home and abroad.Wherein the condensation method removal of mercury is namely concentrated cooling by specific condensing unit with the mercury in the flue gas and since the saturated vapour pressure of mercury sharply the decline meeting from flue gas, condense, thereby reach the purpose of separating with flue gas.But this method removal of mercury efficient is on the low side, and energy consumption is bigger, and is general only as the pre-method for removing hydrargyrum of flue gas.Absorption method mainly utilizes selenium filter or carbon filter that the mercury in the flue gas is adsorbed.Yet the adsorption capacity of selenium filter and carbon filter only is the 10-15% of own wt generally, and therefore general only being fit to handled the lower flue gas of mercury content, and the mercury that is not suitable for the non-ferrous metal metallurgy flue gas is handled.Mostly be absorption process at the many method for removing hydrargyrum of non-ferrous metal metallurgy sector application, wherein more representational is mercury chloride absorption process (Bo Lideng-Nuo Xinke absorption process).The essence of this method is to be absorbent with the mercuric chloride solution, the nonvalent mercury in the flue gas is absorbed, and be translated into the calogreen (calomel) that is insoluble in water, and calogreen can be used as product through post precipitation and reclaims.At present, the mercury chloride absorption process is that the most effective flue gas mercury reclaims one of technology, occupies critical role in field of metallurgy.Yet there are some problems equally in this technology: at first this technological requirement controls the flue gas mercury concentration of absorption tower entrance at 30mg/m
3Below, otherwise absorption efficiency has more significantly decline, causes flue gas mercury emissions concentration over-standard; Secondly, used mercury chloride is toxic articles equally in the absorption liquid, and its absorption liquid concentration is generally about 3g/L, and use amount is bigger, has bigger environmental risk; The 3rd, the outlet mercury concentration of this technology is generally 0.1mg/m
3, can't satisfy more and more stricter mercury emissions standard.Therefore, it is very necessary for emission control and the recycling of realizing non-ferrous metal metallurgy flue gas mercury to develop a kind of new and effective stable absorption techniques.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of efficient, stable and have a method that reclaims gaseous state nonvalent mercury and sulfur dioxide from the non-ferrous metal metallurgy flue gas of anti-sulfur dioxide jamming performance in order to overcome the defective that above-mentioned prior art exists.
Purpose of the present invention can be achieved through the following technical solutions: a kind of method that reclaims gaseous state nonvalent mercury and sulfur dioxide from the non-ferrous metal metallurgy flue gas is characterized in that this method comprises following step:
The first step is mixed with composite absorption liquid with mercuric sulfate, ferric sulfate and sulfuric acid and is stored in the composite absorption liquid liquid pool (1);
Second step, composite absorption liquid in the composite absorption liquid liquid pool (1) is sprayed in the smoke absorption tower (4) by composite absorption liquid circulating slot (2), nonvalent mercury and sulfur dioxide in the non-ferrous metal metallurgy flue gas of input smoke absorption tower (4) are absorbed, wherein the reaction of nonvalent mercury and mercuric sulfate generates mereurous sulfate, sulfur dioxide and ferric sulfate reaction generate sulfuric acid and ferrous sulfate, and the composite absorption liquid after the gas-liquid contact feeds recycling in the composite absorption liquid circulating slot (2);
The 3rd step was lower than after the 25mmol/L by the time the ion concentration of mercury in the composite absorption liquid circulating slot (2) drops to, and part composite absorption liquid is fed mercury decompose in the retracting device (9);
The 4th step, utilize mercury decompose retracting device (9) will absorption liquid in mereurous sulfate resolve into simple substance mercury and mercuric sulfate absorption liquid, wherein can be used as product behind the simple substance mercury process collection purifying and reclaim, and the mercuric sulfate absorption liquid returns recycling mercuric sulfate to consume in the additional flue gas nonvalent mercury absorption process in the composite absorption liquid circulating slot (2);
The 5th step, by the time the sulfate ion concentration in the composite absorption liquid circulating slot (2) greater than 8mol/L after, part composite absorption liquid is fed in the sulfuric acid solution separator (10); Sulfuric acid can be used as product and reclaims after separation, purifying, concentrate, remaining absorption liquid then returns recycling in the composite absorption liquid circulating slot (2).
Described composite absorption liquid key component is mercuric sulfate and sulfuric acid, the mercuric sulfate concentration range is 50-200mmol/L in the composite absorption liquid, the ferric sulfate concentration range is 0.5-1.5mol/L, sulfuric acid concentration ranges is 0.5-2.0mol/L, the temperature of composite absorption liquid remains on 40-60 ℃, to guarantee the dissolving fully of mercuric sulfate.
Described smoke absorption tower (4) is spray column, packed tower or plate column.
Described mercury decomposes retracting device (9) and is mainly photochemical reaction device, mereurous sulfate generates simple substance mercury and mercuric sulfate through photodissociation, wherein simple substance mercury can be used as the product recovery behind collection, purifying, mercuric sulfate then feeds in the composite absorption liquid circulating slot (2) again, to replenish the mercuric sulfate that consumes in the flue gas nonvalent mercury absorption process.
Described sulfuric acid solution separator (10) refers to membrane separation device or extract and separate device.
Studies show that, be absorption liquid with the mercuric sulfate, the mercuric sulfate of low concentration can have higher absorption efficiency to nonvalent mercury, and when allocating a certain proportion of ferric sulfate in the absorption liquid, this absorption liquid not only can absorb sulfur dioxide and make sulfuric acid, and can effectively resist sulfur dioxide to Hg
2+Reduction.The present invention relates to the key reaction equation is:
HgSO
4(l)+Hg
0(g)→Hg
2SO
4(s)
Hg
2SO
4→HgSO
4+Hg
0
Fe
2(SO
4)
3+SO
2+2H
2O→2FeSO
4+2H
2SO
4
2FeSO
4+SO
2+O
2→Fe
2(SO
4)
3
The mereurous sulfate that absorption plant generates is collected through after the coagulative precipitation, decompose generation mercuric sulfate and simple substance mercury by methods such as photodissociation, mercuric sulfate is used for replenishing the mercuric sulfate that flue gas nonvalent mercury absorption process consumes, and simple substance mercury reclaims through can be used as product after collecting, purifying.
And sulfur dioxide can generate ferrous sulfate and sulfuric acid through after the absorption of ferric sulfate.Ferrous sulfate is reused through generating ferric sulfate again with sulfur dioxide and oxygen reaction.
With existing be that " Bo Lideng " technology of main component is compared with mercury chloride, the present invention has following advantages:
1, utilization of the present invention is the composite absorption liquid of key component with mercuric sulfate, ferric sulfate and sulfuric acid, can to nonvalent mercury higher absorption efficiency be arranged under low concentration absorption liquid condition, can guarantee to export the qualified discharge of mercury concentration;
2, the used sulfuric acid of the present invention can be provided by the sulfur dioxide acid making system of enterprises, has both reduced technology operating cost, has reduced the environmental risk of toxic articles again;
3, the present invention uses and contains a certain amount of ferric sulfate in the composite absorption liquid, and ferric sulfate can generate ferrous sulfate and sulfuric acid with the sulfur in smoke reaction, thereby the generation that not only can reduce inferior sulfate radical reduces sulfur dioxide gas to Hg in the absorption liquid
2+Reduction, high concentration sulfur dioxide in the flue gas effectively can be absorbed again and relieving haperacidity, except the nonvalent mercury that is applicable to general sulfur-containing smoke gas removes, be applicable to the non-ferrous metal metallurgy industry flue gas middle and high concentration mercury that contains high concentration sulfur dioxide and removal and the recycling of sulfur dioxide more.
Description of drawings
The equipment schematic diagram that Fig. 1 adopts for the present invention.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further specified.Present embodiment is implemented under with the technical solution of the present invention prerequisite, has provided detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiment.
Main purpose of the present invention is nonvalent mercury in the general flue gas to be carried out efficient absorption remove; The nonferrous smelting industry flue gas mercury that contains middle and high concentration nonvalent mercury and higher concentration sulfur dioxide is carried out efficient absorption and recycling.In the present invention program's the implementation process, emphasis is target with the efficient absorption that realizes flue gas mercury.
Embodiment 1
Utilize a volume for the glass of 500mL bubbling device processed as main reactor, liquid measure remains on about 250mL in the reactor.(1) preparation composite absorption liquid: take by weighing certain mercuric sulfate and with sulfuric acid it is dissolved, and solution is heated to the 40-60 degree, to guarantee that mercuric sulfate dissolves fully, mercuric sulfate concentration is 50mmol/L in the composite absorption liquid, and sulfuric acid concentration is 0.5mol/L.(2) get the composite absorption liquid 250mL that configures and place bubbling reactor, feeding initial nonvalent mercury concentration in the reactor is 2mg/m
3Simulated flue gas, flue gas flow is controlled at 1L/min, the record flue gas is through the nonvalent mercury concentration of composite absorption liquid, and efficient is removed in the absorption of calculating nonvalent mercury accordingly; Tail gas absorbs with 5% liquor potassic permanganate; The device total output is provided by air pump.After adopting said method, the absorption efficiency of simulated flue gas nonvalent mercury reaches about 99%.(2) under the same composite absorption liquid condition, feed that to contain the nonvalent mercury initial concentration be 2mg/m in the reactor
3With contain 8000mg/m
3The simulated flue gas of sulfur dioxide, mixed flue gas flow-control are at 1L/min, and the mercury concentration of record flue gas after absorption liquid absorbs can calculate and contain under the high concentration sulfur dioxide condition, and the absorption efficiency of nonvalent mercury can be about 50%.(3) add an amount of ferric sulfate in the composite absorption liquid of original preparation, making ferric sulfate concentration is 1.0mol/L, and mercuric sulfate concentration is 50mmol/L, and sulfuric acid concentration is 0.5mol/L; Feed that to contain the nonvalent mercury initial concentration be 2mg/m in the reactor
3With contain 8000mg/m
3The simulated flue gas of sulfur dioxide, the mixed flue gas flow-control is at 1L/min, through behind the absorption reaction, calculate and contain in the flue gas under the high concentration sulfur dioxide condition, the nonvalent mercury absorption efficiency can reach more than 95%, and the anti-sulfur dioxide jamming performance that sulfuric acid that adding in the absorption liquid is an amount of and chlorion can improve composite absorption liquid is described.And the removal efficient of sulfur dioxide has also reached 85%, illustrates that this composite absorption liquid can effectively absorb sulfur dioxide gas.
Embodiment 2
Utilize an internal diameter to be 100mm, the wet scrubbing tower of the lucite material of long 1200mm is absorption reactor thermally.(1) configuration composite absorption liquid: take by weighing certain mercuric sulfate and with sulfuric acid it is dissolved, and solution is heated to the 40-60 degree, to guarantee that mercuric sulfate dissolves fully, mercuric sulfate concentration is 50mmol/L in the composite absorption liquid, and sulfuric acid concentration is 0.5mol/L.(2) containing initial mercury concentration is 2mg/m
3Simulated flue gas enter from wash tower bottoms, enter online mercury vapourmeter through absorption liquid washing back from the top of tower eliminating, the simulated flue gas flow is 3.0m
3/ h; The composite absorption liquid that the prepares flow with 150mL/min is sprayed into from tower top through nozzle, and the Buffer Pool from tower bottom behind the washing flue gas is squeezed into scrubbing tower with the pump circulation, and the liquid-gas ratio in the absorption reactor thermally is 3.0L/m
3(3) tail gas through mercury vapourmeter absorbs with 5% potassium permanganate.After adopting said method, the absorption efficiency of nonvalent mercury can reach more than 90% in the simulated flue gas.(4) the mercuric sulfate concentration in the composite absorption liquid is increased to 100mmol/L, sulfuric acid concentration is 1.0mol/L, sprays in the absorption reactor thermally under same flue gas condition and liquid-gas ratio condition, and the result shows that the absorption efficiency of nonvalent mercury can reach more than 96%.(5) add a certain amount of ferric sulfate in composite absorption liquid, make that mercuric sulfate concentration is 100mmol/L in the composite absorption liquid, ferric sulfate concentration is 1.0mol/L, and sulfuric acid concentration is 1.0mol/L, is 2mg/m with nonvalent mercury content
3With sulfur dioxide concentration be 8000mg/m
3Simulated flue gas with 3.0m
3The flow of/h feeds in the absorption reactor thermally, and the flow of composite absorption liquid with 150mL/min sprayed in the absorption reactor thermally, and the result shows that the absorption efficiency of nonvalent mercury in the flue gas can reach more than 85%, and the sulfur dioxide absorption efficiency reaches about 80%.
Embodiment 3
The equipment that adopts as shown in Figure 1, comprise composite absorption liquid liquid pool 1, composite absorption liquid circulating slot 2, smoke absorption tower 4, pump 8, mercury decomposes retracting device 9, sulfuric acid solution separator 10, smoke absorption tower 4 is spray column, bottom one side is provided with smoke absorption tower entrance 3, the non-ferrous metal metallurgy flue gas is from smoke absorption tower entrance 3 input smoke absorption towers 4, the top is provided with absorption liquid nozzle 7, tail gas demister 5 and smoke absorption tower outlet 6, wherein composite absorption liquid circulating slot 2 one ends connect composite absorption liquid liquid pool 1, the other end connects pump 8 and absorption liquid nozzle 7 successively by pipeline, by pump 8 composite absorption liquid is imported absorption liquid nozzle 7, spray in the smoke absorption tower 4, mercury decomposes retracting device 9 and connects pump 8 outlets by branch road, and connection composite absorption liquid circulating slot 2, sulfuric acid solution separator 10 connects pump 8 outlets by branch road, and is communicated with composite absorption liquid circulating slot 2.
Adopt the said equipment from the non-ferrous metal metallurgy flue gas, to reclaim the method for gaseous state nonvalent mercury and sulfur dioxide, comprise following step:
The first step is mixed with composite absorption liquid with mercuric sulfate, ferric sulfate and sulfuric acid and is stored in the composite absorption liquid liquid pool 1; Described composite absorption liquid key component is mercuric sulfate and sulfuric acid, mercuric sulfate concentration is 200mmol/L in the composite absorption liquid, and ferric sulfate concentration is 1.5mol/L, and sulfuric acid concentration is 2.0mol/L, the temperature of composite absorption liquid remains on 40-60 ℃, to guarantee the dissolving fully of mercuric sulfate.
Second step, composite absorption liquid in the composite absorption liquid liquid pool 1 is sprayed in the smoke absorption tower 4 by composite absorption liquid circulating slot 2, nonvalent mercury and sulfur dioxide in the non-ferrous metal metallurgy flue gas of input smoke absorption tower 4 are absorbed, wherein the reaction of nonvalent mercury and mercuric sulfate generates mereurous sulfate, sulfur dioxide and ferric sulfate reaction generate sulfuric acid and ferrous sulfate, and the composite absorption liquid after the gas-liquid contact feeds recycling in the composite absorption liquid circulating slot 2; Smoke absorption tower 4 is spray column.
The 3rd step was lower than after the 25mmol/L by the time the ion concentration of mercury in the composite absorption liquid circulating slot 2 drops to, and part composite absorption liquid is fed mercury decompose in the retracting device 9; Mercury decomposes retracting device 9 and is mainly photochemical reaction device, mereurous sulfate generates simple substance mercury and mercuric sulfate through photodissociation, wherein simple substance mercury can be used as the product recovery behind collection, purifying, mercuric sulfate then feeds in the composite absorption liquid circulating slot 2 again, to replenish the mercuric sulfate that consumes in the flue gas nonvalent mercury absorption process.
The 4th step, utilize mercury decompose retracting device 9 will absorption liquid in mereurous sulfate resolve into simple substance mercury and mercuric sulfate absorption liquid, wherein can be used as product behind the simple substance mercury process collection purifying and reclaim, and the mercuric sulfate absorption liquid returns recycling mercuric sulfate to consume in the additional flue gas nonvalent mercury absorption process in the composite absorption liquid circulating slot 2;
The 5th step, by the time the sulfate ion concentration in the composite absorption liquid circulating slot 2 greater than 8mol/L after, part composite absorption liquid is fed in the sulfuric acid solution separator 10; Sulfuric acid can be used as product and reclaims after separation, purifying, concentrate, remaining absorption liquid then returns recycling in the composite absorption liquid circulating slot 2; Described sulfuric acid solution separator 10 refers to membrane separation device or extract and separate device.
Embodiment 4
From the non-ferrous metal metallurgy flue gas, reclaim the method for gaseous state nonvalent mercury and sulfur dioxide, comprise following step:
The first step is mixed with composite absorption liquid with mercuric sulfate, ferric sulfate and sulfuric acid and is stored in the composite absorption liquid liquid pool; Described composite absorption liquid key component is mercuric sulfate and sulfuric acid, the mercuric sulfate concentration range is 50mmol/L in the composite absorption liquid, and the ferric sulfate concentration range is 0.5mol/L, and sulfuric acid concentration ranges is 0.5mol/L, the temperature of composite absorption liquid remains on 40-60 ℃, to guarantee the dissolving fully of mercuric sulfate.
Second step, composite absorption liquid in the composite absorption liquid liquid pool is sprayed in the smoke absorption tower by composite absorption liquid circulating slot, nonvalent mercury and sulfur dioxide in the non-ferrous metal metallurgy flue gas of input smoke absorption tower are absorbed, wherein the reaction of nonvalent mercury and mercuric sulfate generates mereurous sulfate, sulfur dioxide and ferric sulfate reaction generate sulfuric acid and ferrous sulfate, and the composite absorption liquid after the gas-liquid contact feeds in the composite absorption liquid circulating slot and reuses; The smoke absorption tower is packed tower.
The 3rd step was lower than after the 25mmol/L by the time the ion concentration of mercury in the composite absorption liquid circulating slot drops to, and part composite absorption liquid is fed mercury decompose in the retracting device; Mercury decomposes retracting device and is mainly photochemical reaction device, mereurous sulfate generates simple substance mercury and mercuric sulfate through photodissociation, wherein simple substance mercury can be used as the product recovery behind collection, purifying, mercuric sulfate then feeds in the composite absorption liquid circulating slot again, to replenish the mercuric sulfate that consumes in the flue gas nonvalent mercury absorption process.
The 4th step, utilize mercury decompose retracting device will absorption liquid in mereurous sulfate resolve into simple substance mercury and mercuric sulfate absorption liquid, wherein can be used as product behind the simple substance mercury process collection purifying and reclaim, and the mercuric sulfate absorption liquid returns recycling mercuric sulfate to consume in the additional flue gas nonvalent mercury absorption process in the composite absorption liquid circulating slot;
The 5th step, by the time the sulfate ion concentration in the composite absorption liquid circulating slot greater than 8mol/L after, part composite absorption liquid is fed in the sulfuric acid solution separator; Sulfuric acid can be used as product and reclaims after separation, purifying, concentrate, remaining absorption liquid then returns in the composite absorption liquid circulating slot and reuses; Described sulfuric acid solution separator refers to membrane separation device or extract and separate device.
Claims (5)
1. method that reclaims gaseous state nonvalent mercury and sulfur dioxide from the non-ferrous metal metallurgy flue gas is characterized in that this method comprises following step:
The first step is mixed with composite absorption liquid with mercuric sulfate, ferric sulfate and sulfuric acid and is stored in the composite absorption liquid liquid pool (1);
Second step, composite absorption liquid in the composite absorption liquid liquid pool (1) is sprayed in the smoke absorption tower (4) by composite absorption liquid circulating slot (2), nonvalent mercury and sulfur dioxide in the non-ferrous metal metallurgy flue gas of input smoke absorption tower (4) are absorbed, wherein the reaction of nonvalent mercury and mercuric sulfate generates mereurous sulfate, sulfur dioxide and ferric sulfate reaction generate sulfuric acid and ferrous sulfate, and the composite absorption liquid after the gas-liquid contact feeds recycling in the composite absorption liquid circulating slot (2);
The 3rd step was lower than after the 25mmol/L by the time the ion concentration of mercury in the composite absorption liquid circulating slot (2) drops to, and part composite absorption liquid is fed mercury decompose in the retracting device (9);
The 4th step, utilize mercury to decompose retracting device (9) mereurous sulfate in the absorption liquid is resolved into simple substance mercury and mercuric sulfate absorption liquid, wherein can be used as product behind the simple substance mercury process collection purifying and reclaim, and the mercuric sulfate absorption liquid returns recycling mercuric sulfate to consume in the additional flue gas nonvalent mercury absorption process in the composite absorption liquid circulating slot (2);
The 5th step, by the time the sulfate ion concentration in the composite absorption liquid circulating slot (2) greater than 8mol/L after, part composite absorption liquid is fed in the sulfuric acid solution separator (10); Sulfuric acid can be used as product and reclaims after separation, purifying, concentrate, remaining absorption liquid then returns recycling in the composite absorption liquid circulating slot (2).
2. a kind of method that from the non-ferrous metal metallurgy flue gas, reclaims gaseous state nonvalent mercury and sulfur dioxide according to claim 1, it is characterized in that, described composite absorption liquid key component is mercuric sulfate, ferric sulfate and sulfuric acid, the mercuric sulfate concentration range is 50-200mmol/L in the composite absorption liquid, the ferric sulfate concentration range is 0.5-1.5mol/L, sulfuric acid concentration ranges is 0.5-2.0mol/L, and the temperature of composite absorption liquid remains on 40-60 ℃, to guarantee the dissolving fully of mercuric sulfate.
3. a kind of method that reclaims gaseous state nonvalent mercury and sulfur dioxide from the non-ferrous metal metallurgy flue gas according to claim 1 is characterized in that described smoke absorption tower (4) is spray column, packed tower or plate column.
4. a kind of method that from the non-ferrous metal metallurgy flue gas, reclaims gaseous state nonvalent mercury and sulfur dioxide according to claim 1, it is characterized in that, described mercury decomposes retracting device (9) and is mainly photochemical reaction device, mereurous sulfate generates simple substance mercury and mercuric sulfate through photodissociation, wherein simple substance mercury can be used as the product recovery behind collection, purifying, mercuric sulfate then feeds in the composite absorption liquid circulating slot (2) again, to replenish the mercuric sulfate that consumes in the flue gas nonvalent mercury absorption process.
5. a kind of method that reclaims gaseous state nonvalent mercury and sulfur dioxide from the non-ferrous metal metallurgy flue gas according to claim 1 is characterized in that described sulfuric acid solution separator (10) refers to membrane separation device or extract and separate device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310277066.0A CN103341310B (en) | 2013-07-03 | 2013-07-03 | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310277066.0A CN103341310B (en) | 2013-07-03 | 2013-07-03 | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103341310A true CN103341310A (en) | 2013-10-09 |
| CN103341310B CN103341310B (en) | 2015-07-08 |
Family
ID=49276163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310277066.0A Active CN103341310B (en) | 2013-07-03 | 2013-07-03 | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103341310B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669366A (en) * | 2016-12-29 | 2017-05-17 | 郴州丰越环保科技有限公司 | Clean efficient demercuration method for oxygen-enriched side-blown smelting gas |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110133186A (en) * | 2019-04-18 | 2019-08-16 | 贵州开磷集团矿肥有限责任公司 | A kind of diammonium phosphate exhaust washer pH measuring device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040219083A1 (en) * | 2003-05-01 | 2004-11-04 | Keith Schofield | Method and apparatus for mitigating mercury emissions in exhaust gases |
| CN101590362A (en) * | 2009-06-12 | 2009-12-02 | 浙江大学 | A kind of flue gas mercury absorption liquid with simultaneous oxidation and fixation |
| CN102688677A (en) * | 2012-06-12 | 2012-09-26 | 上海交通大学 | Method for enhancing total mercury recovery rate of metallurgical fume by reducing bivalent mercury |
| CN103143252A (en) * | 2013-02-22 | 2013-06-12 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
-
2013
- 2013-07-03 CN CN201310277066.0A patent/CN103341310B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040219083A1 (en) * | 2003-05-01 | 2004-11-04 | Keith Schofield | Method and apparatus for mitigating mercury emissions in exhaust gases |
| CN101590362A (en) * | 2009-06-12 | 2009-12-02 | 浙江大学 | A kind of flue gas mercury absorption liquid with simultaneous oxidation and fixation |
| CN102688677A (en) * | 2012-06-12 | 2012-09-26 | 上海交通大学 | Method for enhancing total mercury recovery rate of metallurgical fume by reducing bivalent mercury |
| CN103143252A (en) * | 2013-02-22 | 2013-06-12 | 广东电网公司电力科学研究院 | Additive capable of simultaneous desulphurization and demercuration and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669366A (en) * | 2016-12-29 | 2017-05-17 | 郴州丰越环保科技有限公司 | Clean efficient demercuration method for oxygen-enriched side-blown smelting gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103341310B (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105238933B (en) | It is a kind of from the method containing removing and reclaiming element mercury in sulfur dioxide flue gas | |
| US9895661B2 (en) | Process and device for desulphurization and denitration of flue gas | |
| US20190023585A1 (en) | Method and apparatus for the recovery and deep treatment of polluted acid | |
| CN105384195B (en) | Method for recovering rhenium from molybdenum smelting waste acid | |
| CN106430244B (en) | A method of it is recycled from ammonia nitrogen waste water and purifies ammonia | |
| CN107774082B (en) | Method and device for flue gas desulfurization | |
| CN102491477B (en) | Method for removing mercury from high concentration acid | |
| CN103421566B (en) | A kind of natural gas deviates from sulfur recovery technology and device | |
| CN102949926B (en) | Method for recycling sulfur dioxide (SO2) and heavy metal in metallurgical gas | |
| CN104368232A (en) | Sulfuric acid tail gas recovery device | |
| CN108889110B (en) | Method for removing mercury from flue gas | |
| CN106669360B (en) | A kind of flue gas desulfurization and the method and apparatus for producing sulfuric acid | |
| CN103432877A (en) | Integrated method for wet-process dust removal, desulfurization, denitrification demercuration, dearsenification of complexing ferroporphyrin smoke based on supergravity | |
| CN103011084A (en) | Method for extracting iodine from dehydrate wet method diluted phosphoric acid reaction iodic waste gas | |
| CN102120658B (en) | Treatment and recycling method of ammonia nitrogen in electrolytic manganese production end wastewater | |
| CN104772029B (en) | Coupled double-region type high-efficiency flue gas mercury recovery device and application thereof | |
| CN206188534U (en) | Phenol ammonia wastewater deamination and ammonia purification system | |
| CN103331094B (en) | Method for purifying non ferrous metal smelting flue gas and realizing synchronized multiple resource utilization | |
| CN103341310B (en) | Method for recycling gas-state zero-valence mercury and sulfur dioxide from non-ferrous metal metallurgy smoke gas | |
| CN106268241B (en) | Copper making ring collection fume desulphurization method and device | |
| CN102179134A (en) | Ammonia water recovery device | |
| CN110124510A (en) | A method of utilizing oxygen-enriched side-blowing smelting lead extracting sulfuric acid | |
| CN102688677B (en) | Method for enhancing total mercury recovery rate of metallurgical fume by reducing bivalent mercury | |
| CN104740986A (en) | Hydrolysis treatment process for organosilicon slurry residue | |
| CN205528524U (en) | Utilize phenol sodium salt to prepare device of crude carbolic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |