CN103331090A - Apparatus and method for removal of zero valent mercury in flue gas through on-site discharge activation oxidation - Google Patents
Apparatus and method for removal of zero valent mercury in flue gas through on-site discharge activation oxidation Download PDFInfo
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- CN103331090A CN103331090A CN2013102770834A CN201310277083A CN103331090A CN 103331090 A CN103331090 A CN 103331090A CN 2013102770834 A CN2013102770834 A CN 2013102770834A CN 201310277083 A CN201310277083 A CN 201310277083A CN 103331090 A CN103331090 A CN 103331090A
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- flue gas
- flue
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Abstract
The invention relates to an apparatus and a method for removal of zero valent mercury in flue gas through on-site discharge activation oxidation. The method utilizes a corona discharge assembly to carry out on-site activation on a mercury-removal agent in a flue, so as to generate a lot of active substances and increase oxidation rate of the mercury-removal agent on the zero valent mercury in the flue gas, thereby rapidly and effectively removing the zero valent mercury in the flue gas. The method is as below: disposing the corona discharge assembly comprising a porous ceramic pipe and electrodes in the flue, and generating a lot of active substances through corona discharge; then sending the active substances into the flue through micropore channels on a wall surface of the ceramic tube by using the pressure difference between the corona discharge assembly and the flue, reacting the active substances with zero valent mercury in the flue gas, so as to converse the zero valent mercury into divalent mercury; and finally removing the divalent mercury by a wet method desulphurization apparatus. The above method can effectively remove zero valent mercury in the flue gas and save the usage amount of the mercury-removal agent.
Description
Technical field
The invention belongs to the flue gas mercury emissions control technology of field of environment protection; mainly be to utilize corona discharge assembly that mercury-removing reagent is carried out with regard to activatable; generate a large amount of active materials; reaction by nonvalent mercury in these active materials and the flue gas is translated into divalence mercury then; by wet desulphurization device divalence mercury is absorbed at last, realize the purpose of fume mercury-removing.
Background technology
Mercury has obtained increasing understanding as a kind of hazardous contaminant.A legally binding international convention about mercury has finally been passed through in the United Nations's government-to-government talks in 2013.International community reaches a new height to mercury pollution discharging and the concern of controlling.In numerous mercury emissions source, the discharge capacity of mercury accounts for very big proportion in the coal-fired flue-gas.And the energy resource structure of China is based on fire coal, and therefore, the mercury emissions in the control coal-fired flue-gas is extremely important.
Mercury oxide (Hg in the coal-fired flue-gas
2+) and particle mercury (Hg
p) can utilize existing Air Pollution Control Board control equipment, as electrostatic precipitator, removals such as flue gas desulfurization device.And nonvalent mercury (Hg
0) because it is volatile, the characteristic that is insoluble in water is not easy effectively to be removed.Therefore, the removal of mercury technology of coal-fired flue-gas main flow is with the Hg in the flue gas
0Be converted into easier removed Hg
2+Or Hg
pThereby, give full play to the mercury removal performance that has the Air Pollution Control Board control equipment now.
The research of China's fume mercury-removing technical elements at present mainly utilizes sorbing materials such as spraying into active carbon in the coal-fired flue-gas with Hg
0Capture or with Hg
0Carry out oxidation, utilize follow-up wet desulphurization device that oxidation state mercury is absorbed then.But, utilize the active carbon spraying technique not only can increase removal of mercury cost, it is mixed with flying dust in dust removal process, influence quality and the comprehensive utilization of flying dust.And utilize catalyst to the Hg in the flue gas
0Carrying out oxidation still is difficult to find can be for a long time efficient and have a catalyst of certain anti-sulfur dioxide influence at present, and its oxidation efficiency to nonvalent mercury of SCR catalyst that denitration is now used is very low, therefore utilize the catalyst oxidation nonvalent mercury need increase extra smoke catalytic unit if desired, increase equipment cost.Therefore, present stage direct oxidation method, namely in flue gas, directly spray into oxidant with Hg
0Be converted into Hg
2+, utilize wet desulphurization device with Hg then
2+The absorption removal is removal of mercury technology the most easily and effectively.As disclosing a kind of method of utilizing the bromine chloride compositional liquor to remove the flue gas nonvalent mercury for Chinese patent CN200810202641.X number, by bromine chloride with the Hg in the flue gas
0Be converted into Hg
2+, then by wet desulphurization device with Hg
2+Absorb and remove.Yet, adopt directly to make usage need a large amount of oxidants, as bromine, iodine etc.Because these oxidants are not component intrinsic in the flue gas, therefore a large amount of use oxidants had both increased the costs of the removal of mercury, had increased the risk of secondary pollution again.And the oxidant found of current research and the reaction rate of nonvalent mercury still have much room for improvement.
Summary of the invention
Purpose of the present invention is exactly the device and method that nonvalent mercury in the low oxidation removal of the discharge activation on the spot flue gas of a kind of efficient height, cost is provided 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: the device of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas, it is characterized in that, this device comprises corona discharge assembly and mercury-removing reagent storage tank, described corona discharge assembly comprises the mercury-removing reagent jet pipe, capping, main body, discharge electrode, earthing pole, earth connection and high voltage source, described capping is arranged on the main body termination, and be inserted with mercury-removing reagent jet pipe and discharge electrode, described mercury-removing reagent jet pipe connects the mercury-removing reagent storage tank, described discharge electrode connects high voltage source, described earthing pole is wrapped in the outside of body surfaces, and links to each other with ground wire by earth connection.
Described main body is made of the earthenware with numerous microcellular structures, and the wall thickness of earthenware is 0.2-5mm, and the aperture is 10-1000nm.
Described capping and mercury-removing reagent jet pipe are made by insulating materials, insulating materials comprises polytetrafluoroethylene (PTFE), discharge electrode is made by metal material, and the pattern of discharge electrode is smooth round wire, astroid, crepe cord, prickle wire, jaggies, twistedwire or puncture vine silk thread.
The very metal net shaped sleeve of described ground connection is wrapped in the outside on corona discharge assembly surface, and the hole of wire netting is 0.1-2mm.
Described corona discharge assembly is positioned over behind the dust arrester and the flue section before the wet desulphurization device.
A kind of described device method of nonvalent mercury in the discharge activation oxidation removal flue gas on the spot that adopts is characterized in that this method may further comprise the steps:
The first step is positioned over corona discharge assembly in the flue;
In second step, mercury-removing reagent gas is sprayed into the corona discharge assembly by mercury-removing reagent jet pipe 2 from the mercury-removing reagent storage tank;
The 3rd step, utilize high voltage source in corona discharge assembly, to apply 5-20kV voltage, in corona discharge assembly, produce ionized field by the discharge electrode corona discharge, thus with regard to the activatable mercury-removing reagent and generate many active materials;
In the 4th step, the active material of Sheng Chenging enters in the flue gas by the micro channel of corona discharge assembly wall and the space of earthing pole under the suction function of flue on the spot, generates divalence mercury with the nonvalent mercury reaction;
In the 5th step, utilize follow-up wet desulphurization device that the divalence mercury in the flue gas is removed.
The mercury-removing reagent that stores in the described mercury-removing reagent storage tank is mainly one or more mixtures of hydrogen chloride, hydrogen bromide or hydrogen iodide gas, and the concentration range of mercury-removing reagent in flue gas is between the 0.1ppm-20ppm.
Described corona discharge assembly inboard is than the high 0-3000Pa of the pressure in the flue.
Described flue gas temperature is in the 100-300 ℃ of scope.
Compare with existing absorption process demercuration technology, the present invention has following advantages:
1, the present invention utilize the ionization reaction device in flue gas with regard to the activatable mercury-removing reagent, generate a large amount of active materials, and utilize these active materials rapidly with the nonvalent mercury efficient oxidation in the flue gas;
2, the mercury-removing reagent consumption of the present invention's use is considerably less, and cost is lower;
3, the present invention is used in combination with the flue gas desulfur device of using always, both can realize the effective control to the flue gas mercury emissions, does not increase equipment cost again.
Description of drawings
The device 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.
As shown in Figure 1, the present invention is the device of nonvalent mercury in the discharge activation oxidation removal flue gas on the spot, this device comprises corona discharge assembly, mercury-removing reagent storage tank 1, described corona discharge assembly comprises mercury-removing reagent jet pipe 2, capping 3, main body 7, discharge electrode 8, earthing pole 4, earth connection 6 and high voltage source 9, described capping 3 is arranged on main body 7 terminations, and be inserted with mercury-removing reagent jet pipe 2 and discharge electrode 8, described mercury-removing reagent jet pipe 2 connects mercury-removing reagent storage tank 1, described discharge electrode 8 connects high voltage source 9, described earthing pole 4 is wrapped in the outside on main body 7 surfaces, and links to each other with ground wire by earth connection 6.
Described main body 7 is made of the earthenware with numerous microcellular structures, and the wall thickness of earthenware is 0.2-5mm, and the aperture is 10-1000nm.
Described capping 3 and mercury-removing reagent jet pipe 2 are made by insulating materials, insulating materials comprises polytetrafluoroethylene (PTFE), discharge electrode 8 is made by metal material, and the pattern of discharge electrode 8 is smooth round wire, astroid, crepe cord, prickle wire, jaggies, twistedwire or puncture vine silk thread.
Described earthing pole 4 is metal net shaped sleeve, is wrapped in the outside on corona discharge assembly 7 surfaces, and the hole of wire netting is 0.1-2mm.
Described corona discharge assembly is positioned over behind the dust arrester and the flue section before the wet desulphurization device.
Adopt the said apparatus method of nonvalent mercury in the discharge activation oxidation removal flue gas on the spot, may further comprise the steps:
The first step is positioned over corona discharge assembly in the flue 5; Flue 5 flue-gas temperatures are in the 100-300 ℃ of scope;
In second step, mercury-removing reagent gas is sprayed into the corona discharge assembly by mercury-removing reagent jet pipe 2 from mercury-removing reagent storage tank 1; The concentration range of mercury-removing reagent in flue gas is between the 0.1ppm-20ppm.
The 3rd step, utilize high voltage source 9 in corona discharge assembly, to apply 5-20kV voltage, in corona discharge assembly, produce ionized field by discharge electrode 8 corona discharges, thus with regard to the activatable mercury-removing reagent and generate many active materials; The corona discharge assembly inboard is than the high 0-3000Pa of the pressure in the flue 5;
In the 4th step, the active material of Sheng Chenging enters in the flue gas by the micro channel of corona discharge assembly wall and the space of earthing pole 4 under the suction function of flue on the spot, generates divalence mercury with the nonvalent mercury reaction;
In the 5th step, utilize follow-up wet desulphurization device that the divalence mercury in the flue gas is removed.
Embodiment 1
Present embodiment adopts the stainless steel device of a square as analog flue, and the length size of flue is 2000mm, 400mm and 400mm respectively.In the flue upstream air heating apparatus is housed, utilizes air-introduced machine with situ configuration thermal simulation flue gas ([NO]=200ppm, [Hg
0]=20 μ g/m
3, [SO
2]=1000ppm, all the other are 150 ℃ hot-air of electric furnace heating) with 100m
3The flow of/h feeds flue continuously.Be horizontally disposed with a row totally five corona discharge assemblies at the side of flue position of center line, the diameter of corona discharge assembly is 100mm, and the distance between each corona discharge assembly center of circle is 400mm.The corona discharge assembly main body adopts earthenware, and ceramic vessel wall thickness is 0.5mm, and discharge electrode structure is the single needle shape, the very stainless filter screen shape of ground connection sleeve, be wrapped in the main body outer surface of corona discharge assembly, supply voltage 0-20kV, charged electric current are the 0-20 microampere.Mercury-removing reagent adopts gas chlorination hydrogen, and spraying into concentration is 10ppmv.At first do not open high voltage source, feed the hydrogen chloride front and back by detecting, the nonvalent mercury concentration in the tail gas, the removal efficient that can calculate nonvalent mercury is about about 10%; When with voltage-regulation during to 8.0kV, the removal efficient of nonvalent mercury has reached about 50%; Further with voltage-regulation to 10kV, the removal efficient of nonvalent mercury has reached about 70%.
Embodiment 2
Device and method is identical with example 1, just changes mercury-removing reagent into the gas hydrogen bromide, spray into hydrogen bromide in the flue gas after, the concentration in simulated flue gas is 2ppmv.When not applying voltage, the removal efficient of nonvalent mercury is 40% in the flue gas; Progressively voltage is transferred to 8.0kV, the removal efficient of nonvalent mercury has reached about 75%; Further with voltage-regulation to 9.0kV, the removal efficient of nonvalent mercury has reached about 90%.
Claims (9)
1. device of nonvalent mercury in the discharge activation oxidation removal flue gas on the spot, it is characterized in that, this device comprises corona discharge assembly and mercury-removing reagent storage tank (1), described corona discharge assembly comprises mercury-removing reagent jet pipe (2), capping (3), main body (7), discharge electrode (8), earthing pole (4), earth connection (6) and high voltage source (9), described capping (3) is arranged on main body (7) termination, and be inserted with mercury-removing reagent jet pipe (2) and discharge electrode (8), described mercury-removing reagent jet pipe (2) connects mercury-removing reagent storage tank (1), described discharge electrode (8) connects high voltage source (9), described earthing pole (4) is wrapped in the outside on main body (7) surface, and links to each other with ground wire by earth connection (6).
2. the device of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 1 is characterized in that described main body (7) is made of the earthenware with numerous microcellular structures, and the wall thickness of earthenware is 0.2-5mm, and the aperture is 10-1000nm.
3. the device of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 1, it is characterized in that, described capping (3) and mercury-removing reagent jet pipe (2) are made by insulating materials, insulating materials comprises polytetrafluoroethylene (PTFE), discharge electrode (8) is made by conductive metallic material, and the pattern of discharge electrode (8) is smooth round wire, astroid, crepe cord, prickle wire, jaggies, twistedwire or puncture vine silk thread.
4. the device of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 1, it is characterized in that, described earthing pole (4) is metal net shaped sleeve, is wrapped in the outside on corona discharge assembly (7) surface, and the hole of wire netting is 0.1-2mm.
5. the device of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 1 is characterized in that, described corona discharge assembly is positioned over behind the dust arrester and the flue section before the wet desulphurization device.
6. one kind is adopted the described device of claim 1 method of nonvalent mercury in the discharge activation oxidation removal flue gas on the spot, it is characterized in that this method may further comprise the steps:
The first step is positioned over corona discharge assembly in the flue (5);
In second step, mercury-removing reagent gas is sprayed into the corona discharge assembly by mercury-removing reagent jet pipe (2) from mercury-removing reagent storage tank (1);
The 3rd step, utilize high voltage source (9) in corona discharge assembly, to apply 5-20kV voltage, in corona discharge assembly, produce ionized field by discharge electrode (8) corona discharge, thus with regard to the activatable mercury-removing reagent and generate many active materials;
In the 4th step, the active material of Sheng Chenging enters in the flue gas by the micro channel of corona discharge assembly wall and the space of earthing pole (4) under the suction function of flue on the spot, generates divalence mercury with the nonvalent mercury reaction;
In the 5th step, utilize follow-up wet desulphurization device that the divalence mercury in the flue gas is removed.
7. the method for nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 6, it is characterized in that, the mercury-removing reagent that stores in the described mercury-removing reagent storage tank (1) is mainly one or more mixtures of hydrogen chloride, hydrogen bromide or hydrogen iodide gas, and the concentration range of mercury-removing reagent in flue gas is between the 0.1ppm-20ppm.
8. the method for nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 6 is characterized in that described corona discharge assembly inboard is than the high 0-3000Pa of pressure in the flue (5).
9. the method for nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas according to claim 1 is characterized in that described flue (5) flue-gas temperature is in the 100-300 ℃ of scope.
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|---|---|---|---|
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|---|---|---|---|
| CN201310277083.4A CN103331090B (en) | 2013-07-03 | 2013-07-03 | The device and method of nonvalent mercury in a kind of oxidation removal of discharge activation on the spot flue gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106268223A (en) * | 2016-09-22 | 2017-01-04 | 山东理工大学 | A kind of method of low-temperature plasma synergistic catalyst of transition metal oxide oxidation mercury in flue gas |
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| CN102580493A (en) * | 2012-02-27 | 2012-07-18 | 浙江大学 | Flue gas demercuration system and method based on discharge and activation of halogen materials |
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2013
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Patent Citations (5)
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| CN2535112Y (en) * | 2002-04-01 | 2003-02-12 | 广东杰特科技发展有限公司 | Horizontal line-box type streamer-discahrge flue gas desulfurizing wet reactor |
| US20050214181A1 (en) * | 2004-03-26 | 2005-09-29 | Canon Kabushiki Kaisha | Dielectric, gas treatment apparatus using the same, and plasma generator |
| CN101590370A (en) * | 2009-06-11 | 2009-12-02 | 上海交通大学 | The method of catalytically oxidizing elemental mercury by oxidant controlledly released by porous ceramic membrane |
| CN102580493A (en) * | 2012-02-27 | 2012-07-18 | 浙江大学 | Flue gas demercuration system and method based on discharge and activation of halogen materials |
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Cited By (1)
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| CN106268223A (en) * | 2016-09-22 | 2017-01-04 | 山东理工大学 | A kind of method of low-temperature plasma synergistic catalyst of transition metal oxide oxidation mercury in flue gas |
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