CN102205203A - Desulfuration and mercury-removing combined smoke purifying process and system based on magnesium oxide method desulfuration process - Google Patents
Desulfuration and mercury-removing combined smoke purifying process and system based on magnesium oxide method desulfuration process Download PDFInfo
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- CN102205203A CN102205203A CN2011101431383A CN201110143138A CN102205203A CN 102205203 A CN102205203 A CN 102205203A CN 2011101431383 A CN2011101431383 A CN 2011101431383A CN 201110143138 A CN201110143138 A CN 201110143138A CN 102205203 A CN102205203 A CN 102205203A
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Abstract
The invention discloses a desulfuration and mercury-removing combined smoke purifying process and system based on a magnesium oxide method desulfuration process. The desulfuration and mercury-removing combined smoke purifying process comprises the steps of: improving a pre-washing tower in the magnesium oxide method desulfuration process, circularly spraying original smoke by adopting a halogen oxidant solution to realize full oxidization of elementary substance mercury Hg0 in smoke; transforming oxidized gas-phase bivalent mercury ions into liquid-phase bivalent mercury ions through an improved wet-type magnesium oxide method desulfuration process; and transforming the liquid-phase bivalent mercury ions in a wastewater treatment system into a stable mercuric sulfide precipitate through adding a mercury stabilizing agent. The system mainly comprises the pre-washing tower, a desulfuration tower, a cyclone separator, a vacuum belt fulter, a wastewater basin and a sedimentation basin, wherein the pre-washing tower is used for preparing a mercury oxidant and a magnesium oxide solution and oxidizing mercury; the desulfuration tower is used for carrying out desulfuration and mercury removal on smoke; the cyclone separator and the vacuum belt fulter are used for treating side products; and the wastewater basin and the sedimentation basin are respectively used for treating wastewater and the mercuric sulfide precipitate. The process can be used for effectively removing divalent mercury and elementary substance mercury in the smoke on the premise of ensuring the advantages of the magnesium oxide method desulfuration process, and is suitable for reconstructing the traditional magnesium oxide method desulfuration process.
Description
Technical field
The present invention relates to a kind of flue gas purifying technique, refer to a kind of combined desulfurization demercuration flue gas purifying technique and system thereof particularly, belong to field of environment protection based on the magnesium oxide method sulfur removal technology.
Background technology
Coal is a kind of uncleanly energy, can discharge all contaminations in combustion process.At present, the control to the coal-fired flue-gas pollutant mainly concentrates on dust Control, SO
2Control, NOx control aspect.Mercury is a kind of poisonous trace element in the coal, mercury pollution to the mankind and biotic environment cause very harmful, coal-fired mercury pollution has become the universally acknowledged another big pollution problem after coal-fired sulphur pollution.
Mercury in the coal fired power plant flue gas is mainly with simple substance mercury (Hg
0), oxidation state mercury (Hg
2+) and particle mercury (Hg
p) three kinds of forms exist, Hg wherein
0Account for 35～80% of flue gas total mercury content.Usually, simple substance mercury Hg
0Water insoluble, volatility is extremely strong, be difficult to remove, and oxidation state mercury Hg
2+Soluble in water, remove easily.At present, the main method of coal-fired flue gas mercury removal has in demercuration before the burning, the burning three kinds of demercurations and burning back demercuration.Since the burning before and the burning in demercuration limited in one's ability to the removal of mercury, so the burning after demercuration be the major control approach.Mature technique is active carbon spraying technique (ACI) the most at present, to simple substance Hg
0Comparatively desirable removal effect is also arranged, but active carbon consumption height, the operating cost height, and influence the utilization again of flying dust.
The magnesium oxide method desulfur technology has been widely used in coal fired power plant flue gas desulfurization and sintering flue gas desulfurization, and this technology is generally by flue gas system, fresh water (FW) system, desulfurizer slurry preparation and induction system, SO
2Absorption system, accessory substance treatment system, Waste Water Treatment, automatic control and composition such as electric are generally and guarantee the byproduct quality to be provided with pretreater, are used for capturing dirt and Cl in the flue gas
-Deng pollutant, this technology has that desulfurization degree height, operation and investment cost are low, by-product recovery is worth advantages of higher, but this technology can not effectively remove the mercury in the flue gas, especially simple substance Hg
0But utilizing existing wet-type magnesia method desulphurization plant, can strengthen its demercuration performance by reasonable improvement, is a kind of flue gases purification that has potentiality of realizing the combined desulfurization demercuration.
Publication number is to have mentioned the grading desulfurization that is applicable to lime/lime stone-gypsum method in the patent of invention of CN 101310834A, hydrargyrum-removing technology, but at first pass through desulfuration absorbing tower at this technology Central Plains flue gas, enter the secondary desulfurization after the desulfurization, in the demercuration absorption tower, on the one hand because the flue gas after desulfurization temperature is lower, enter the desulfurization of secondary absorption tower, behind the demercuration, flue-gas temperature significantly reduces, fume emission needs heating once more, cause the loss of the energy, on the other hand owing to flue gas behind the mode demercuration that adopts oxidation directly discharges, can cause and carry the severe corrosive drop in the flue gas secretly, all affect greatly to equipment operation and maintenance.Publication number is the Wet-type ammonia process flue gas purifying technique that has proposed the combined desulfurization demercuration in the patent of invention of CN 101157003A, and this process using is to simple substance Hg in the method oxidation flue gas of jet paraffin oxidation agent chlorine in the flue gas
0, consider Cl
2Corrosivity and toxicity, transportation, storage inconvenience, and equipment anticorrosion and leak resistance are required high, application difficult in actual engineering.Publication number is in the patent of invention of CN 101053738A, adopts ultraviolet ray and halogen oxidant to the simple substance mercury Hg in the flue gas
0Carry out oxidation processes, carry out demercuration, but need set up ultraviolet radiation device and oxidizer injector, can the normal operation of electrostatic precipitator in the former flue gas system be impacted, and be awkward control in conjunction with the limestone-gypsum method wet desulphurization.At present, the hydrargyrum-removing technology that does not also have a kind of suitable magnesium oxide method sulfur removal technology.
Summary of the invention
The objective of the invention is, based on the magnesium oxide method sulfur removal technology, the characteristics in conjunction with existing magnesium oxide method desulfurization propose a kind of improved magnesium oxide method sulfur removal technology, this method can effectively remove mercury when guaranteeing desulfuration efficiency, especially adopt halogen oxidant to simple substance Hg
0Carry out deep oxidation and handle,, can reach the high-efficiency mercury removal rate, realize the combined desulfurization demercuration in conjunction with the magnesia desulfurizing tower.A plurality of processing steps are combined as a whole, and synergy is developed a kind of combined desulfurization hydrargyrum-removing technology that is applicable to that grassroot project and transformation project and newly added equipment are few, operation maintenance is simple to operate mutually.
Technical scheme of the present invention is that a kind of combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method sulfur removal technology adopts NaClO
2Solution as oxidant in prewashing column with simple substance Hg in the flue gas
0Carry out abundant oxidation, adopting MgO is that desulfurizing agent removes SO in the flue gas in desulfurizing tower
2, and in byproduct for treatment system and Waste Water Treatment, effectively reclaim desulfurizing byproduct MgSO
3Product and demercuration accessory substance HgS.Its specific embodiment comprises the steps:
In prewashing column, former flue gas is washed in the mode of gas-liquid contact by using aqueous oxidizing agent solution, Hg in the flue gas
0Carry out deep oxidation, be oxidized to Hg soluble in water
2+, part enters in the cleaning solution, enters Waste Water Treatment, and another part enters in the desulfurizing tower with flue gas.
Flue gas enters in the desulfurizing tower after washing, SO in the flue gas
2After the magnesium oxide aqueous solution washing, generate MgSO
3Enter in the loop slurry, remain Hg in the flue gas
2+Through further washing, enter equally in the loop slurry, loop slurry enters accessory substance MgSO through excavationg pump
3Product production system.
Accessory substance MgSO
3The waste water that is produced in the product production system pumps into Waste Water Treatment and unifies to handle.
Pass through in the Waste Water Treatment to add stabilizing agent, with Hg
2+Be converted into demercuration accessory substance HgS, collection and treatment.
Aforesaid deep oxidation Hg
0, in the spray void tower, undertaken by process for contact of gas-liquid.
Aforesaid oxidant is NaClO
2, CaCl
2O
4, KMnO
4In one or more mixed solutions.
Aforesaid aqueous oxidizing agent solution concentration is 1～3%, and pH is 4.5～5.5, with Hg in the flue gas
0Stoichiometric proportion is 1.10～1.20.
In the aforesaid Waste Water Treatment to add stabilizing agent be the mercury stabilizing agent, be selected from organic sulfur and vulcanized sodium.
A kind of combined desulfurization demercuration flue gas purifying technique system of the present invention based on the magnesium oxide method sulfur removal technology, comprise the prewashing column that preparation of mercury oxidation agent and magnesium oxide solution and mercury oxidation are handled, the desulfurizing tower of flue gas desulfurizing and hydrargyrum-removing reaction, cyclone separator and vacuum belt dewaterer that accessory substance is handled, the wastewater disposal basin and the sedimentation basin of wastewater treatment and mercuric sulphide precipitation process.
Aforesaid prewashing column can be and increases or transform original pretreater newly, and tower is for spray void tower, packed tower or add excellent layer of venturi in the spray void tower, and anticorrosion anti-oxidation processing is carried out in inside.
Aforesaid desulfurizing tower is generally selected the spray void tower for use, comprises main parts such as slurries district, spraying layer, demister, is connected with pump, slurries discharge line and pump and import and export flue with the slurries circulating line.
The present invention has following advantage: the present invention adopts halogen oxidant solution that former flue gas is carried out circulated sprinkling by improving the prewashing column in the magnesium oxide method sulfur removal technology, realizes simple substance mercury Hg in the flue gas
0Abundant oxidation, and be converted into liquid phase divalent ion mercury by the gas phase divalent ion mercury of improved wet-type magnesia method sulfur removal technology after with oxidation, by adding the mercury stabilizing agent liquid phase divalent ion mercury in the Waste Water Treatment is converted into stable mercuric sulphide sediment, carries out subsequent treatment after the collection.Institute's technology of carrying realizes that desulfuration demercuration is integrated, and flow process is simple, and floor space is little; Compare with traditional magnesium method sulfur removal technology, newly added equipment is few, can be used for the design of new projects, also can be used for the transformation of old project, influences little to operation, maintenance; Technology that the present invention carries has high desulfurization rate and demercuration rate, by the interpolation of oxidant, can promote desulfurization degree and denitration, desulfurization degree＞98% wherein, and demercuration rate＞90% can also take off part NOx simultaneously; Can realize the recycling of desulfurizing byproduct and demercuration accessory substance.
Description of drawings
Fig. 1 is of the present invention a kind of based on the combined desulfurization demercuration flue gas purifying technique of magnesium oxide method sulfur removal technology and the process chart of system thereof.
Among the figure, 1-booster fan, 2-prewashing column, 3-prewashing column circulating pump, 4-desulfurizing tower, 5-desulfurization slurry circulating pump, 6-chimney, 7-slurries excavationg pump, 8-cyclone separator, 9-vacuum belt dewaterer, the 10-wastewater disposal basin, 11-mercury stabilizing agent is reinforced, 12-waste water excavationg pump, 13-sedimentation basin, 14-MgSO
3Product, 15-aqueous oxidizing agent solution, the 16-MgO aqueous solution, 17-top stream waste water, 18-waste discharge, 19-HgS product, the flushing of 20-demister
The specific embodiment
Below in conjunction with Fig. 1, the invention will be further described.
A kind of combined desulfurization demercuration flue gas purifying technique process based on the magnesium oxide method sulfur removal technology of the present invention is as follows:
1, adopt NaClO
2As oxidant, be mixed with mass concentration and be 3% the aqueous solution, according to simple substance Hg
0Measure concentration, with oxidant and simple substance Hg
0The NaClO of stoichiometric proportion 1.10～1.20
2After the aqueous solution pumps in the prewashing column, adopt the mode of void tower circulated sprinkling the coal-fired flue-gas of being introduced to be carried out drip washing, simple substance mercury Hg in the flue gas
0With NaClO
2Oxidation reaction takes place, and generates divalent ion mercury Hg soluble in water rapidly
2+The generation chemical reaction is as follows:
Key reaction:
2Hg+4NaClO
2+2H
2O→2HgCl
2+4NaOH+3O
2↑
Side reaction:
2SO
2+NaClO
2+2H
2O→2H
2SO
4+NaCl
4NO+3NaClO
2+2H
2O→4HNO
3+3NaCl
2NaOH+H
2SO
4→Na
2SO
4+2H
2O
NaOH+HNO
3→NaNO
3+H
2O
2, flue gas enters and carries out desulfurization in the desulfurizing tower after the oxidant washing, in sweetening process, and the dimercurion Hg in the flue gas that is not washed in the prewashing column
2+The further drip washing of quilt is in desulfurization slurry.Main chemical reactions is as follows:
MgO+H
2O→Mg(OH)
2
Mg(OH)
2+SO
2→MgSO
3
3, NaClO
2Enter Waste Water Treatment behind the solution washing flue gas, control pH value of solution value scope is 4.5～5.5, adds flocculation aid and mercury stabilizing agent HgS (or organic S) in wastewater treatment process, with liquid phase divalent ion mercury Hg
2+Be converted into stable HgS precipitation, realize that the Hg resource reclaims.Wherein, chemical equation is as follows:
Hg
2++S
2-→4HgS↓
4, the MgSO that generates
3Slurries enter accessory substance MgSO
3Behind the product production system, to desulfurizing byproduct MgSO
3Carry out rotational flow separation, wherein the top flows to Waste Water Treatment in the step 3, and underflow enters vacuum belt dewaterer and dewaters
Handle, obtain MgSO
3Product is realized recycling.
Combined desulfurization demercuration flue gas purifying technique system based on the magnesium oxide method sulfur removal technology of the present invention, comprise the prewashing column 2 that preparation of mercury oxidation agent and magnesium oxide solution and mercury oxidation are handled, the desulfurizing tower 4 of flue gas desulfurizing and hydrargyrum-removing reaction, cyclone separator 8 and vacuum belt dewaterer 9 that accessory substance is handled, the wastewater disposal basin 10 of wastewater treatment and mercuric sulphide precipitation process and sedimentation basin 13.Its prewashing column spray void tower, in establish venturi rod layer, anticorrosion anti-oxidation processing is carried out in inside.Its desulfurizing tower comprises main parts such as slurries district, spraying layer, demister for the spray void tower, is connected with pump, slurries discharge line and pump and import and export flue with the slurries circulating line.
Its using method is: former coal-fired flue-gas is introduced in the prewashing column 2 through booster fan 1, prepares mass concentration and be 3% NaClO
2Solution 15 adds in the prewashing column 2, by prewashing column circulating pump 3 the aqueous oxidizing agent solution circulated sprinkling is fully contacted with flue gas, with simple substance Hg in the flue gas
0Be oxidized to divalent ion mercury Hg
2+, most divalent ion mercury Hg
2+Be washed in the aqueous solution, enter into wastewater disposal basin 10 afterwards, add Na by mercury stabilizing agent reinforced 11
2S (or organic sulfur) after fully stirring, is drained in the sedimentation basin 13 with waste water excavationg pump 12.
Divalent ion mercury Hg in the waste water
2+Be stabilized the stable HgS of generation of agent sediment 19 and carry out subsequent treatment after the enrichment in sedimentation basin 13, sedimentation basin 13 top stream waste discharges 18 enter and carry out advanced treating in other waste water disposal facility.
Flue gas enters into desulfurizing tower 4 after the aqueous oxidizing agent solution washing, and desulfurization agent aqueous solution carries out the desulfurization washing through desulfurization slurry circulating pump 5 circulated sprinklings to flue gas, and desulfurization degree reaches more than 98%, simultaneously remainder divalent ion mercury Hg
2+Also be washed in the slurries, flue gas is cleaned the back by demisters in the desulfurizing tower 4, enters chimney 6 dischargings after removing most water droplets.
Absorb saturated desulfurization slurry and enter cyclone separator 8 through slurries excavationg pump 7, top stream waste water 17 enters into above-mentioned waste water system and handles, and the underflow slurries dewater by vacuum belt dewaterer 9, obtain desulfuration byproduct MgSO
314.
Implementation result 1:
Flue gas flow is 3000Nm
3/ h, SO
2Concentration 3000mg/Nm
3, NOx concentration 500mg/Nm
3, Hg concentration is 18 μ g/Nm
3Hg in oxidant and the flue gas
0Stoichiometric proportion is 1.10, and pH value of solution is 5.5.Under these conditions, desulfurization degree can reach 98%, and the demercuration rate can reach 90%, and the denitration rate can reach 10%.
Implementation result 2:
Flue gas flow is 3000Nm
3/ h, SO
2Concentration 3000mg/Nm
3, NOx concentration 500mg/Nm
3, Hg concentration is 18 μ g/Nm
3Hg in oxidant and the flue gas
0Stoichiometric proportion is 1.15, and pH value of solution is 5.0.Under these conditions, desulfurization degree can reach 98.5%, and the demercuration rate can reach 92%, and the denitration rate can reach 10.6%.
Implementation result 3:
Flue gas flow is 3000Nm
3/ h, SO
2Concentration 3000mg/Nm
3, NOx concentration 500mg/Nm
3, Hg concentration is 18 μ g/Nm
3Hg in oxidant and the flue gas
0Stoichiometric proportion is 1.20, and pH value of solution is 4.5.Under these conditions, desulfurization degree can reach 98.6%, and the demercuration rate can reach 93.1%, and the denitration rate can reach 10.9%.
Claims (6)
1. the combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method sulfur removal technology comprises the flue gas pre-wash, and desulfurizing byproduct and demercuration accessory substance are reclaimed in flue gas desulfurization, and its concrete processing step feature is:
In prewashing column, former flue gas is washed in the mode of gas-liquid contact by using aqueous oxidizing agent solution, Hg in the flue gas
0Carry out deep oxidation, be oxidized to Hg soluble in water
2+, part enters in the cleaning solution, enters Waste Water Treatment, and another part enters in the desulfurizing tower with flue gas;
Flue gas enters in the desulfurizing tower after washing, SO in the flue gas
2After the magnesium oxide aqueous solution washing, generate MgSO
3Enter in the loop slurry, remain Hg in the flue gas
2+Through further washing, enter equally in the loop slurry, loop slurry enters accessory substance MgSO through excavationg pump
3Product production system;
Accessory substance MgSO
3The waste water that is produced in the product production system pumps into Waste Water Treatment and unifies to handle;
Pass through in the Waste Water Treatment to add stabilizing agent with Hg
2+Be converted into HgS, collection and treatment.
2. the combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method desulfurization as claimed in claim 1 is characterized in that described deep oxidation Hg
0, in the spray void tower, undertaken by process for contact of gas-liquid.
3. the combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method desulfurization as claimed in claim 1 is characterized in that described oxidant is NaClO
2, CaCl
2O
4, KMnO
4In one or more mixed solutions.
4. the combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method desulfurization as claimed in claim 1 is characterized in that described aqueous oxidizing agent solution concentration is 1～3%, and pH is 4.5～5.5, with Hg in the flue gas
0Stoichiometric proportion is 1.10～1.20.
5. the combined desulfurization demercuration flue gas purifying technique based on the magnesium oxide method desulfurization as claimed in claim 1 is characterized in that adding stabilizing agent in the Waste Water Treatment is the mercury stabilizing agent, is selected from organic sulfur and vulcanized sodium.
6. adopt the combined desulfurization demercuration flue gas purifying technique system based on the magnesium oxide method desulfurization of technology according to claim 1, comprise the prewashing column that preparation of mercury oxidation agent and magnesium oxide solution and mercury oxidation are handled, the desulfurizing tower of flue gas desulfurizing and hydrargyrum-removing reaction, cyclone separator and vacuum belt dewaterer that accessory substance is handled, the wastewater disposal basin of wastewater treatment and mercuric sulphide precipitation process and sedimentation basin, it is characterized in that, prewashing column is the spray void tower, in establish venturi rod layer, anticorrosion anti-oxidation processing is carried out in inside: desulfurizing tower is the spray void tower, establish the slurries district in the main body, spraying layer, demister is with slurries circulating line and pump, the slurries discharge line is connected with pump and import and export flue.
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| CN102380306A (en) * | 2011-10-18 | 2012-03-21 | 中钢集团天澄环保科技股份有限公司 | Flue gas desulfurization tower adopting sodium-alkaline method |
| CN103232061A (en) * | 2013-05-13 | 2013-08-07 | 中国环境科学研究院 | Device and method for recovering mercury from solid precipitate by ammonia process desulfurization |
| CN104801176A (en) * | 2015-05-08 | 2015-07-29 | 中国环境科学研究院 | Method for removing mercury in flue gas by carrying out high-temperature oxidation on chlorine-containing waste |
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| CN103232061A (en) * | 2013-05-13 | 2013-08-07 | 中国环境科学研究院 | Device and method for recovering mercury from solid precipitate by ammonia process desulfurization |
| CN104801176A (en) * | 2015-05-08 | 2015-07-29 | 中国环境科学研究院 | Method for removing mercury in flue gas by carrying out high-temperature oxidation on chlorine-containing waste |
| CN105999938B (en) * | 2016-05-10 | 2019-08-20 | 湖州荣大环境科技有限公司 | A kind of flue gas processing device of heat-recoverable |
| CN105854580B (en) * | 2016-05-10 | 2019-06-18 | 东莞市鹏驰净化科技有限公司 | A kind of flue gas processing device |
| CN105879547A (en) * | 2016-05-10 | 2016-08-24 | 湖州荣大环境科技有限公司 | Ultraviolet flue gas treating device |
| CN105999938A (en) * | 2016-05-10 | 2016-10-12 | 湖州荣大环境科技有限公司 | Flue gas treatment device capable of recycling heat |
| CN105879548A (en) * | 2016-05-10 | 2016-08-24 | 湖州荣大环境科技有限公司 | Flue gas treatment device of forming machine |
| CN105854580A (en) * | 2016-05-10 | 2016-08-17 | 湖州荣大环境科技有限公司 | Smoke treatment device |
| CN105879547B (en) * | 2016-05-10 | 2018-12-14 | 湖州荣大环境科技有限公司 | A kind of ultraviolet light flue gas processing device |
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| CN112755758A (en) * | 2021-02-25 | 2021-05-07 | 大唐环境产业集团股份有限公司 | By spraying NaClO2Flue gas treatment system for mercury removal by solution gas phase oxidation |
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Application publication date: 20111005 |