CN101053752A - Method for removing mercury in flue gas - Google Patents
Method for removing mercury in flue gas Download PDFInfo
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- CN101053752A CN101053752A CN 200710037415 CN200710037415A CN101053752A CN 101053752 A CN101053752 A CN 101053752A CN 200710037415 CN200710037415 CN 200710037415 CN 200710037415 A CN200710037415 A CN 200710037415A CN 101053752 A CN101053752 A CN 101053752A
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Abstract
The invention relates to a method for depriving hydrargyrum in flue gas, which can be used for depriving hydrargyrum in flue gas in boilerplant and refuse burning station using membrane separation technology, and relates to the technology field of environmental protection and waste gas treatment. The invention deprives hydrargyrum using separation film conformally with Nafion. The flue gas with hydrargyrum enters into corresponding unit of membrane separator, wherein the Hg2+ or Hg is absorbed on the plane of resolution film at one side of separation film and ion exchanges with sulphoacid compound to produce sulfonic acid mercury; sulfonic acid mercury or Hg2+ reaches to the plane of resolution film at the other side of separation film by infiltrating and diffusing, and reacts HCl or H2S feeding by eluent gas loop controller to product solid HgCl2 or HgS which can be discharged from the bottom into the collector for mercury salt; and the mercury salt is eluted and repeatable cycle sent to the membrane separator and membrane reactor. The method of the invention has a simple process, a convenient operation, and a high efficiency when treating the flue gas with mercury, propitious to collection and protection.
Description
Technical field
The present invention relates to a kind of method that removes mercury in the flue gas, utilize membrane separation technique, can be applied to the flue gas demercuration that coal-fired plant and solid refuse burn the station, belong to the environmental protection technical field of waste gas treatment.
Background technology
Mercury is one of heavy metal contaminants of knowing of people, and it is present in atmosphere, water body, soil and the rock stratum (especially coal).Inorganic mercury is subjected to action of microorganisms and changes into organic mercury at occurring in nature, and they can be passed to human body and enrichment in human body along food chain.Activity of human beings is mainly come from continuing to increase of whole world mercury discharge capacity, and at present various artificial big bicycle pump discharge capacities are annual 1900 → 2200 tons.Maximum mercury pollution source is the coal-burning power plant, and China is the maximum in the world coal state that uses, and the average annual sedimentation value of mercury is greater than 70 μ g/m in the atmosphere
3, be one of the most serious zone of the interior atmosphere mercury pollution of global range.
The form of mercury is mainly with gaseous elemental mercury (Hg in the coal-fired flue-gas
0), gaseous state divalent ion mercury (Hg
2+) and particle mercury (Hg
p) three kinds of forms exist.Physics and the chemical property of the mercury of different shape in atmosphere has very big-difference.In boiler combustion process, the mercury major part in the coal is with Hg
0Form enter in the flue gas section H g
0Oxidized in the flue gas cooling procedure, wherein to generate HgCl
2Be main, also have HgO, HgSO in addition
4And Hg (NO
3) 2H
2O etc.The solid phase mercury of particulate form is adsorbed by flying dust easily, is split into when the dust arrester in the lime-ash and removes.The unstable chemcial property of ionic mercury and water-soluble, the shared ratio of this part mercury is higher and be easier to relatively be removed in the mercury total displacement.And that simple substance mercury has higher steam is awkward water-soluble, relatively stable, is difficult to be collected by existing pollution control equipment and directly enters atmosphere.
At present, the main method of flue gas demercuration has absorption method, utilizes WATER-WASHING METHOD, corona discharge plasma technology and the catalytic oxidation method etc. that have desulfurizer now.Absorption method can be divided into fixed bed and absorbent powder again and spray.Fixed bed process mainly adopts active carbon, flying dust, calcium base class material etc. to make adsorbent, and absorbent powder sprays the general active carbon powder that adopts and is ejected in the flue, adsorbs gas phase mercury when mixing with flue gas, then by gas solid separation to reach the purpose of the removal of mercury.Absorption method (especially fixed-bed process) simple to operate, not high to matching requirements, but absorption method becomes end high (adsorbent costs an arm and a leg), causes secondary pollution with the adsorbent of crossing, and can not reach effectively removal to simple substance mercury in the coal-fired flue-gas.Utilize existing some desulfurizer also can reach certain demercuration rate, this method is primarily aimed at ion ground soluble in water, and typical wet desulphurization device can remove 80～90% ionic mercuries.The shortcoming of this technology is to generate mercurous waste water or harmful gypsum, and this is invalid to taking off the simple substance mercuri.In recent years, have report to utilize plasma technology to carry out flue gas demercuration, but because the concentration of flue gas mercury is low, be difficult to be captured, this technology still stays in the experimental stage.Recently, U.S. First Energy and Power Span company cooperative research and development catalytic oxidation method process, and obtained patent.This method is carried out high oxidation by in dielectric barrier discharge to the fluid thing in the flue gas, thereby realizes mercury in the coal-fired flue-gas and SO
2, NO
XRemove simultaneously with finely ground particle substance, but because the energy consumption height is in conceptual phase equally.In addition, the general simultaneous oxidation acidic gas in flue gas of oxidizing process, the product of generation easily causes the corrosion of flue refractory material.
Summary of the invention
A kind of method that removes mercury in the flue gas of the present invention is characterized in that utilizing class Nafion diffusion barrier to carry out flue gas demercuration; The process of its flue gas demercuration is as follows:
It is membrane reactor that mercury fume at first enters class Nafion membrane separator by flowmeter, valve, gaseous ion mercury and simple substance mercury at first are adsorbed on the adsorbed film laminar surface of membrane separator in the mercury fume, the sulfoacid compound that exists in the ionic mercury of absorption and the device works, also the sulfonic acid generation ion-exchange reactions on the diffusion barrier in mercury ion that promptly adsorbs and the device forms sulfonic acid ground at separation membrane surface; Simple substance mercury then is oxidized to ionic state, subsequently regeneration sulfonic acid mercury; The mercury ion of absorption arrives desorb face by the infiltration diffusion through the diffusion barrier aspect; Separator desorb face one side has wash-out gas cycle controller that wash-out gas HCl or H are provided
2S gas enters desorb face one side in membrane separator or the membrane reactor by pipeline, valve; At desorb face, the wash-out gas of feeding and mercury ion generate HgCl
2Or the HgS solid, this mercury salt is discharged from membrane separator or membrane reactor bottom, enters in the mercury salt gatherer; And wash-out gas follows collection controller repetitive cycling by wash-out gas and delivers in membrane separator or the membrane reactor;
The reaction equation of the ionic mercury of separator membrane surface absorption and sulfonic acid generation ion-exchange reactions formation sulfonic acid mercury is as follows:
Hg
2++2HSO
3-R→Hg(SO
3-R)
2+2H
+；
Simple substance mercury is oxidized to ionic state, and the reaction equation of regeneration sulfonic acid mercury is as follows:
Hg+2HSO
3-R→Hg(SO
3-R)
2+H
2。
A kind of class Nafion membrane separator that removes the method for mercury in the flue gas of the present invention is the system and device of membrane reactor, and it includes membrane separator is membrane reactor, flowmeter, mercury salt gatherer, wash-out gas cycle controller, triple valve, pipeline etc.; It is characterized in that membrane separator or membrane reactor centre position are provided with a Nafion film or modification Nafion film, the two side faces one of this film is desorb face for the absorption aspect is one; Be provided with the flowmeter that mercury fume enters and measures on the right side of membrane separator or membrane reactor, be connected with absorption aspect one side bottom through triple valve and film from device or membrane reactor by pipeline; Be provided with a wash-out gas cycle controller in the left side of membrane separator or membrane reactor, it is connected by pipeline desorb face one side roof part of membrane separator or membrane reactor on triple valve; There is pipeline to be connected in the bottom at this place, to collect wash-out gas and the reacted mercury salt product of mercury with the mercury salt gatherer; It in the left side of membrane separator or membrane reactor the periodic duty system of the wash-out gas formed by wash-out gas cycle controller, triple valve, mercury salt gatherer, pipeline; The right upper portion of membrane separator or membrane reactor also is provided with Hg, Hg
++Analytical equipment and gas analyzing apparatus, the one end is connected with absorption cell, as other part treatment of waste gas.
Advantage of the present invention and effect are as follows:
Propose a kind of method for removing hydrargyrum of mercury fume, utilized class Nafion diffusion barrier, and adopted wash-out gas and mercury ion that is adsorbed or mercury reaction to generate purer mercury salt, collected the back and handle easily, can be used as industrial chemicals.Technology of the present invention is simple, and is easy to operate, and the efficient of demercuration is higher in flue gas, can be used for the demercuration that coal-fired plant and solid refuse burn the field, and a kind of new method is provided concerning environmental protection.
Description of drawings
Fig. 1 is the rough schematic of the membrane separator system and device of flue gas demercuration of the present invention.
The specific embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Referring to Fig. 1, remove in the present embodiment that the method for mercury is to utilize class Nafion membrane separator in the flue gas, also be that membrane reactor is main system and device.It is membrane reactor, flowmeter, mercury salt gatherer, wash-out gas cycle controller, triple valve, pipeline etc. that this system and device includes membrane separator; Membrane separator or membrane reactor centre position are provided with the Nafion diffusion barrier, and the two side faces one of this film is the absorption aspect, and another is a desorb face; Be provided with the flowmeter that mercurous cigarette enters and measures on the right side of membrane separator or membrane reactor, be connected through the bottom of triple valve with absorption aspect one side of membrane separator or membrane reactor by pipeline; Be provided with a wash-out gas cycle controller in the left side of membrane separator, it is connected through the top of triple valve with desorb face one side of membrane separator or membrane reactor by pipeline; There is pipeline to be connected in the bottom at this place, to collect wash-out gas and the reacted mercury salt product of mercury with following set mercury salt gatherer; In the left side of membrane separator or membrane reactor for take off the periodic duty system that follows the wash-out gas that living controller, triple valve, mercury salt gatherer, pipeline form by gas washing; The right upper portion of membrane separator or membrane reactor also is provided with Hg, Hg
++Analytical equipment and gas analyzing apparatus, the one end is connected with absorption cell by pipeline, as other part treatment of waste gas.
The method of operating of flue gas demercuration and the course of work thereof are as described below in the present embodiment:
Mercurous flue gas process flowmeter is with the control flue gas flow, by pipeline, three-phase valve, entering membrane separator from the bottom is membrane reactor, and enters the adsorbed film aspect on Nafion diffusion barrier right side, and mercury ion and mercury in the flue gas are attracted on this adsorbed film aspect; Be contained with sulfoacid compound in membrane separator or the membrane reactor in advance, the sulfonic acid generation ion-exchange reactions on the diffusion barrier in the mercury ion of absorption or mercury simple substance and the device forms sulfonic acid mercury on the film surface; Sulfonic acid mercury or its mercury ion arrive the desorb face in the left side of diffusion barrier through the adsorbed film aspect by the infiltration diffusion; Have the wash-out ion to react on desorb face in desorb face one side, generate the HgS solid sediment, this mercury salt can be discharged from the bottom of membrane separator or membrane reactor, and enters in the mercury salt gatherer that is provided with below.Wash-out gas is then delivered in membrane separator or the membrane reactor by wash-out gas cycle controller repetitive cycling.
Part waste gas can be shunted by pipeline through Hg, Hg
++Analytical equipment and gas analyzing apparatus enter absorption cell and make aid in treatment.
Claims (2)
1. a method that removes mercury in the flue gas is characterized in that utilizing class Nafion diffusion barrier to carry out flue gas demercuration; The process of its flue gas demercuration is as follows:
It is membrane reactor that mercury fume at first enters class Nafion membrane separator by flowmeter, valve, gaseous ion mercury and simple substance mercury at first are adsorbed on the adsorbed film laminar surface of membrane separator in the mercury fume, the sulfoacid compound that exists in the ionic mercury of absorption and the device works, also the sulfonic acid generation ion-exchange reactions on the diffusion barrier in mercury ion that promptly adsorbs and the device forms sulfonic acid ground at separation membrane surface; Simple substance mercury then is oxidized to ionic state, subsequently regeneration sulfonic acid mercury; The mercury ion of absorption arrives desorb face by the infiltration diffusion through the diffusion barrier aspect; Separator desorb face one side has wash-out gas cycle controller that wash-out gas HCl or H are provided
2S gas enters desorb face one side in membrane separator or the membrane reactor by pipeline, valve; At desorb face, the wash-out gas of feeding and mercury ion generate HgCl
2Or the HgS solid, this mercury salt is discharged from membrane separator or membrane reactor bottom, enters in the mercury salt gatherer; And wash-out gas follows collection controller repetitive cycling by wash-out gas and delivers in membrane separator or the membrane reactor;
The reaction equation of the ionic mercury of separator membrane surface absorption and sulfonic acid generation ion-exchange reactions formation sulfonic acid mercury is as follows:
Hg
2++2HSO
3-R→Hg(SO
3-R)
2+2H
+；
Simple substance mercury is oxidized to ionic state, and the reaction equation of regeneration sulfonic acid mercury is as follows:
Hg+2HSO
3-R→Hg(SO
3-R)
2+H
2。
2. a kind of class Nafion membrane separator that removes the method for mercury in the flue gas of claim is the system and device of membrane reactor, and it includes membrane separator is membrane reactor, flowmeter, mercury salt gatherer, wash-out gas cycle controller, triple valve, pipeline etc.; It is characterized in that membrane separator or membrane reactor centre position are provided with a Nafion film or modification Nafion film, the two side faces one of this film is desorb face for the absorption aspect is one; Be provided with the flowmeter that mercury fume enters and measures on the right side of membrane separator or membrane reactor, be connected with absorption aspect one side bottom through triple valve and film from device or membrane reactor by pipeline; Be provided with a wash-out gas cycle controller in the left side of membrane separator or membrane reactor, it is connected by pipeline desorb face one side roof part of membrane separator or membrane reactor on triple valve; There is pipeline to be connected in the bottom at this place, to collect wash-out gas and the reacted mercury salt product of mercury with the mercury salt gatherer; It in the left side of membrane separator or membrane reactor the periodic duty system of the wash-out gas formed by wash-out gas cycle controller, triple valve, mercury salt gatherer, pipeline; The right upper portion of membrane separator or membrane reactor also is provided with Hg, Hg
++Analytical equipment and gas analyzing apparatus, the one end is connected with absorption cell, as other part treatment of waste gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710037415 CN101053752A (en) | 2007-02-09 | 2007-02-09 | Method for removing mercury in flue gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710037415 CN101053752A (en) | 2007-02-09 | 2007-02-09 | Method for removing mercury in flue gas |
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|---|---|
| CN101053752A true CN101053752A (en) | 2007-10-17 |
Family
ID=38793909
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8409535B2 (en) | 2010-11-03 | 2013-04-02 | Calpine Corporation | System and method for removing a contaminant from a gas stream |
| US8641890B2 (en) | 2012-03-22 | 2014-02-04 | Saudi Arabian Oil Company | Method for removing mercury from a gaseous or liquid stream |
| CN103550989A (en) * | 2013-10-16 | 2014-02-05 | 贵州大龙银星汞业有限责任公司 | Comprehensive treatment method of tail gas in mercury chloride production process |
| CN104511227A (en) * | 2014-11-17 | 2015-04-15 | 江苏大学 | Fluidized bed mercury removal method and device based on straw ash |
| CN104722188A (en) * | 2015-03-02 | 2015-06-24 | 江苏汇维特新材料科技有限公司 | Mercury vapor absorbing device and mercury vapor absorbing method |
| CN105983297A (en) * | 2015-02-09 | 2016-10-05 | 华北电力大学 | Coal-fired power plant fly ash adsorbent integral modification and injection mercury-removing system |
| CN105999993A (en) * | 2016-07-05 | 2016-10-12 | 中国环境科学研究院 | Flue gas demercuration device and method for recycling flue gas mercury through adsorption-desorption self-coupling |
| CN107485981A (en) * | 2017-09-05 | 2017-12-19 | 北京科技大学 | A kind of equipment for denitrifying flue gas and method |
| CN115448423A (en) * | 2022-08-26 | 2022-12-09 | 大连东道尔膜技术有限公司 | Electrocatalysis waste water hardness removing device |
-
2007
- 2007-02-09 CN CN 200710037415 patent/CN101053752A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8409535B2 (en) | 2010-11-03 | 2013-04-02 | Calpine Corporation | System and method for removing a contaminant from a gas stream |
| US8641890B2 (en) | 2012-03-22 | 2014-02-04 | Saudi Arabian Oil Company | Method for removing mercury from a gaseous or liquid stream |
| CN103550989B (en) * | 2013-10-16 | 2015-10-28 | 贵州大龙银星汞业有限责任公司 | The integrated conduct method of tail gas in a kind of mercury chloride production process |
| CN103550989A (en) * | 2013-10-16 | 2014-02-05 | 贵州大龙银星汞业有限责任公司 | Comprehensive treatment method of tail gas in mercury chloride production process |
| CN104511227A (en) * | 2014-11-17 | 2015-04-15 | 江苏大学 | Fluidized bed mercury removal method and device based on straw ash |
| CN105983297A (en) * | 2015-02-09 | 2016-10-05 | 华北电力大学 | Coal-fired power plant fly ash adsorbent integral modification and injection mercury-removing system |
| CN105983297B (en) * | 2015-02-09 | 2019-06-18 | 华北电力大学 | A kind of coal fired power plant flying dust adsorbent integration is modified and sprays demercuration system |
| CN104722188A (en) * | 2015-03-02 | 2015-06-24 | 江苏汇维特新材料科技有限公司 | Mercury vapor absorbing device and mercury vapor absorbing method |
| CN105999993A (en) * | 2016-07-05 | 2016-10-12 | 中国环境科学研究院 | Flue gas demercuration device and method for recycling flue gas mercury through adsorption-desorption self-coupling |
| CN105999993B (en) * | 2016-07-05 | 2018-09-11 | 中国环境科学研究院 | The method of flue gas mercury removal device and adsorption-desorption self coupling method recovered flue gas mercury |
| CN107485981A (en) * | 2017-09-05 | 2017-12-19 | 北京科技大学 | A kind of equipment for denitrifying flue gas and method |
| CN107485981B (en) * | 2017-09-05 | 2020-05-12 | 北京科技大学 | Flue gas denitration device and method |
| CN115448423A (en) * | 2022-08-26 | 2022-12-09 | 大连东道尔膜技术有限公司 | Electrocatalysis waste water hardness removing device |
| CN115448423B (en) * | 2022-08-26 | 2023-12-22 | 大连东道尔膜技术有限公司 | Electrocatalytic waste water hardness removal device |
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