CN102188882A - Integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment suitable for the method - Google Patents
Integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment suitable for the method Download PDFInfo
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- CN102188882A CN102188882A CN2011100912812A CN201110091281A CN102188882A CN 102188882 A CN102188882 A CN 102188882A CN 2011100912812 A CN2011100912812 A CN 2011100912812A CN 201110091281 A CN201110091281 A CN 201110091281A CN 102188882 A CN102188882 A CN 102188882A
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Abstract
The invention relates to an integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment suitable for the method. The integrated method is characterized in that an acidic gas capture agent adopted by the invention captures SO2 and/or highly charged nitrogen oxides NOx in raw flue gas and thus ammonium sulfate as a by-product and/or ammonium nitrate as a by-product is obtained finally, and the acidic gas capture agent adsorbs heavy metals in the raw flue gas simultaneously, wherein the above processes are carried out in a same absorbing device. The special equipment suitable for the method of the invention comprises an absorbing tower, a raw flue gas input pipeline having an external connection with the absorbing tower body, a purified flue gas output pipeline having an external connection with the absorbing tower body, a system for supplying the acidic gas capture agent and absorbents, a demisting water input pipeline, an absorption liquid cycling system, a slurry discharge system, and a separation and treatment system, wherein the raw flue gas input pipeline is provided with a supercharging system and a forced oxidation system. Through the method of the invention, the integrated purification processes of denitrification, desulfurization and heavy metal removal from flue gas can be completed in a same device and by-products from the integrated purification processes are ammonium sulfate and ammonium nitrate, wherein ammonium sulfate and ammonium nitrate can be utilized as components of fertilizers. Through the method, waste water and waste residue are not produced in the integrated purification processes and the integrated purification processes have the advantages of simple system, low cost, high recovery rate, etc.
Description
Technical field
The invention belongs to the flue gases purification field, be specifically related to flue gas desulfurization and denitrification removing heavy-metal integral method and special equipment.
Background technology
Fire coal, fuel oil, combustion gas thermal power plant, metallurgy, chemical industry, contain sulfur dioxide (SO in every profession and trade discharged flue gas such as useless garbage disposal or the industrial tail gas admittedly
2), nitrogen oxide (mainly comprises NO and NO
2) and heavy metal pollutants such as (Hg, Ag), become the primary pollution source of atmosphere and soil.At present, flue gas or industrial tail gas pollution control technology are more, wherein comparative maturity, representative improvement flue gas SO
2Desulfur technology limestone-gypsum method, ammonia process, two alkaline process etc. are arranged, the denitration technology of administering the flue gas NOx pollutant has SCR (selective catalytic reduction, selective catalytic reduction), SNCR (Selective Non-Catalytic Reduction, non-selective catalytic reduction), low nitrogen burning method etc.
The most common desulfurization, denitrating technique is configured at present: the preceding fume high-temperature section of air preheater is established the SCR denitrification apparatus behind the electricity generation boiler economizer, installs desulfurizer after dedusting additional.Its shortcoming is: one-time investment is big, floor space is big, SR is big, power consumption is high, does not have the demercuration function.Still there be not at present ripe removing for the heavy metal in flue gas or the industrial tail gas.In a word, which kind of technology no matter just present actual conditions adopt, to SO
2With removing of NOx all is to realize not possessing the function that same set of device integrated efficient removes in the different device of two functions, does not more have the technology that in same set of device sulfur dioxide, nitrogen oxide and heavy metal is removed simultaneously.
Summary of the invention
The present invention carries out integrated efficient to sulfur dioxide, nitrogen oxide and heavy metal in the same set of device and removes in order to overcome the deficiencies in the prior art, a kind of flue gas desulfurization and denitrification removing heavy-metal integral method and special equipment to be provided, being implemented in.
The present invention adopts following technical scheme:
Flue gas desulfurization and denitrification removing heavy-metal integral method provided by the invention is characterized in that: utilize a kind of sour gas agent for capturing, in same set of absorption plant to the SO in the former flue gas
2Or/and higher nitrogen oxides (Nox) is caught, generate stable comple; Described complex compound reacts with a kind of absorbent that removes again, displaces described sour gas agent for capturing, and generates the intermediate by-products ammonium sulfite or/and the salting liquid of ammonium nilrite; Described intermediate by-products further is oxidized to accessory substance ammonium sulfate or/and ammonium nitrate; Described former flue gas was oxidized to described higher nitrogen oxides (NOx) by strong oxidizer with the NO in the former flue gas before entering described absorption plant; In described same set of absorption plant, heavy metal is attracted in the described sour gas agent for capturing.NOx of the present invention is nitrogen dioxide (NO
2), nitrogen trioxide (N
2O
3) or/and dinitrogen pentoxide (N
2O
5) etc.
Described sour gas agent for capturing is a kind of mixture that takes off aromatic hydrocarbons, sulfoxide, alcoholic extract hydroxyl group, amido, hydramine, saturated hydrocarbons and isoparaffin that contains.This mixture proportion less than water, not volatile, be insoluble in water, can with the SO in the flue gas
2Or NOx generates stable complex compound, can adsorb the heavy metal in the flue gas.
The described absorbent that removes is an ammoniacal liquor, and described ammoniacal liquor is formed by liquefied ammonia, ammonia or urea production.As long as can satisfy the system held water balance, the concentration of ammoniacal liquor there is not specific (special) requirements.
Described strong oxidizer is ozone (O
3) or hydrogen peroxide (H
2O
2).
Described ozone is that purity oxygen or the ionization of air process ozone generator make.Purity oxygen can make through deaerator.
Described former flue gas before by described strong oxidizer oxidation, through boiler induced-draft fan or/and the booster fan supercharging.
Described intermediate by-products ammonium sulfite or/and ammonium nilrite is oxidized to described accessory substance ammonium sulfate the oxygen in the former flue gas that the oxidant of ammonium nitrate utilization is or/and ozone, perhaps for to enter the oxygen of described absorption plant or/and ozone by the oxidation air pipeline.When the oxygen content in the former flue gas is enough to ammonium sulfite or/and ammonium nilrite is oxidized to ammonium sulfate ammonium nitrate, need not to add oxygen or/and ozone by the oxidation air pipeline.
Described sour gas agent for capturing, the described absorbent that removes are mixed into absorption liquid in described absorption plant, described absorption liquid is transported to the spraying layer at middle part, described absorption tower by circulating pump, described former flue gas makes progress through described spraying layer the SO in the former flue gas after entering described absorption plant
2, NOx or/and heavy metal caught by described absorption liquid.
Described absorption liquid also is dissolved with described accessory substance ammonium sulfate or/and ammonium nitrate forms slurries; Or/and ammonium nitrate when reaching finite concentration, described slurries are discharged by the slurries discharger, by dust separator dust separation are gone out, and obtain containing ammonium sulfate or/and the saline solution of ammonium nitrate and sour gas agent for capturing when the ammonium sulfate in the described slurries; Described saline solution is isolated described sour gas agent for capturing through the economic benefits and social benefits separator; Isolated sour gas agent for capturing reenters described circulating pump, and the saline solution after the separation is handled through evaporation and crystallization system and obtained finished product ammonium sulfate or/and ammonium nitrate crystals.
Heavy metal carries out desorption with chemical run up to finite concentration in the sour gas agent for capturing after, and the heavy metal that desorption goes out is concentrated and carried out harmless treatment.
Removed SO through described absorption liquid
2, NOx is or/and the clean flue gas of heavy metal is set at the demister and the flushing water layer on described absorption plant top discharges after removing droplet.
Realize the special equipment of flue gas desulfurization and denitrification removing heavy-metal integral method of the present invention, comprise the absorption tower that is used for the out of stock removing heavy-metal reaction of desulfurization, with the bottom, absorption tower by inlet pipeline link to each other be used to provide remove absorbent for ammonia pump, the sour gas agent for capturing pump that is used to provide the sour gas agent for capturing that links to each other by inlet pipeline with the bottom, absorption tower, the former flue that links to each other with the middle part, absorption tower, the ozone pipeline that links to each other with former flue, the slurries excavationg pump that links to each other by discharge line with the bottom, absorption tower, the clean flue that is used to discharge clean flue gas that links to each other with top, absorption tower, be arranged at the spraying layer of central region in the absorption tower, connect the external circulating line in absorption liquid zone and spraying layer in the absorption tower and be arranged at circulating pump on the circulating line, be arranged at the demister and the flushing water layer in internal upper part zone, absorption tower, the flushing water pipeline that is used to provide the demist water that links to each other with the flushing water layer.Wherein, spraying layer can be set to multilayer.
On the ozone pipeline by from former flue by being disposed with air duct, air separation unit, ozone generator as far as near order.
Link to each other with tank used for storing ammonia by pipeline for ammonia pump.
Sour gas agent for capturing pump links to each other with sour gas agent for capturing storage tank by pipeline.
On the discharge line after the slurries excavationg pump, be provided with dust separator, economic benefits and social benefits separator, multi-effect evaporation system, chemical fertilizer drying system, chemical fertilizer pipe outlet; The top of dust separator is connected with sour gas agent for capturing pipeline, and the port of export of sour gas agent for capturing pipeline links to each other with the circulating line of circulating pump.
Clean flue links to each other with chimney.
Former flue before the ozone pipeline is provided with booster fan.
Also be connected with the oxidation air system that is used to provide oxygen or ozone in the bottom, absorption tower, this system is made up of the oxidation fan of air duct and upward setting thereof.When the oxygen content in the flue gas is enough to that ammonium sulfite/ammonium nilrite is oxidized to ammonium sulfate/ammonium nitrate, can not establish this road oxidation air system.
Be connected with the bypass flue on the former flue before the booster fan, the port of export of bypass flue links to each other with clean flue.
Advantage of the present invention and beneficial effect are as follows:
(1) in a covering device, realize the integrated purification function of flue gas desulfurization and denitrification removing heavy-metal, and its SR is only suitable with existing limestone-gypsum method; Relatively the SCR denitration adds the wet method desulfurization and unites and arrange and reduced about 30%; Take up an area of also only suitable with the limestone-gypsum subtraction unit;
(2) accessory substance is ammonium sulfate and ammonium nitrate, does not produce waste water, waste residue;
(3) sour gas agent for capturing separable come out after using returns in the tower by circulating pump and to recycle;
(4) amount of nitrogen oxides is reduced to below the 50mg in the clean flue gas, and content of sulfur dioxide is reduced to below the 50mg.
In a word, the present invention have system simple, be easy to realize, characteristics such as cost is low, rate of recovery height.
Description of drawings
Fig. 1 is a process chart of the present invention
Among the figure: the former flue of 1-, 2-booster fan, 3-absorption tower, the 4-demister, the clean flue of 5-, 6-chimney, 7-bypass flue, 8-flushing water pipeline, 9-air duct, the 10-air separation unit, 11-ozone generator, 12-ozone pipeline, the 13-air duct, 14-oxidation fan, 15-tank used for storing ammonia, 16-is for ammonia pump, 17-sour gas agent for capturing storage tank, 18-sour gas agent for capturing pump, 19-slurries excavationg pump, 20-dust separator, 21-economic benefits and social benefits separator, the 22-multi-effect evaporation system, 23-chemical fertilizer drying system, 24-chemical fertilizer pipe outlet, 25-sour gas agent for capturing pipeline, the 26-circulating pump, the 27-spraying layer, 28-washes water layer.
The specific embodiment
Below in conjunction with drawings and Examples the method for the invention and special equipment are done a detailed description, but not as limitation of the present invention.
Fig. 1 is the structural representation of special equipment of the present invention, it is as follows to utilize equipment shown in Figure 1 to carry out the integral method of flue gas desulfurization and denitrification removing heavy-metal: former flue gas is through booster fan 2 superchargings, enter former flue 1, before entering absorption tower 3, add a certain amount of ozone from ozone pipeline 12 to former flue 1, with the oxidation of nitric oxide in the former flue gas is high price nitrogen oxide (NOx) such as nitrogen dioxide, and former afterwards flue gas enters absorption tower 3 from former flue 1 import.The former flue gas that enters behind the absorption tower 3 upwards flows through spraying layer 27, the SO in the flue gas
2, NOx and heavy metal absorbed by the spraying layer 27 sprays absorption liquid washing reaction that contains a certain proportion of sour gas agent for capturing, absorbent down, the clean flue gas after removing is discharged by chimney 6 through clean flue 5 after removing droplet through demister 4 and flushing water layer 28.The flushing water pipeline 8 that links to each other with flushing water layer 28 is used to provide the demister flushing water.
The absorption tower 3 that removes absorption plant as flue gas washing is spray column.In the absorption tower 3 absorption liquids be sour gas agent for capturing, moisture arranged, remove absorbent ammoniacal liquor, the mix emulsion fluid of reaction intermediate by-products ammonium sulfite and ammonium nilrite and byproduct of reaction ammonium sulfate and ammonium nitrate etc.Absorption liquid must keep certain liquid level in absorption tower 3, to guarantee the absorption reaction time.The sour gas agent for capturing joins absorption liquid by sour gas agent for capturing pump 18, certain density ammoniacal liquor is supplied with by tank used for storing ammonia 15, join absorption liquid after for ammonia pump 16 meterings, both all should add absorption liquid below liquid level, escape to prevent sour gas agent for capturing and ammoniacal liquor.Absorption liquid is transported to spraying layer 27 by circulating pump 26, the SO in nozzle atomization washing, purifying flue gas
2, NOx and heavy metal.Wherein, the SO in the flue gas
2, NOx is converted into ammonium sulfite, ammonium nilrite, be dissolved in the absorption liquid, be ammonium sulfate, nitrous acid by oxidation step subsequently.
The addition of sour gas agent for capturing is directly proportional with sulfur dioxide in flue gas content, is initially adding fashionablely, and the volume ratio that sour gas agent for capturing and moisture are pressed 1/1-5 adds.The concentration that removes absorbent ammoniacal liquor that adds is unrestricted substantially, and concentration commonly used all can be used at the ammoniacal liquor of 1-25%.According to pH value in the absorption tower and denitrification efficiency control ammoniacal liquor addition.
In special equipment of the present invention, air enters air separation unit 10 through air duct 9 and makes high-concentration oxygen or purity oxygen, obtains ozone through ozone generator 11 ionization again.Ozone also available air directly obtains through ozone generator 11 ionization, but the ozone concentration that obtains with the air direct ionization is lower, and power consumption is higher.Ozone is uniformly distributed in the former flue by flue gas-ozone uniform device (applying for a patent separately), and the oxidation of nitric oxide that is used for former flue gas is high price nitrogen oxide such as nitrogen dioxide.The addition of ozone, relevant with the content of nitric oxide in the flue gas and nitrogen dioxide.The coefficient of excess of ozone is 1.03-2, and coefficient of excess is bigger to the removal of nitrogen oxide effectiveness affects.
In special equipment of the present invention, also be provided with by air duct 13 and be arranged on the oxidation air system that the oxidation fan 14 on the air duct 13 forms (indicating among the figure).Air is entered by air duct 13, delivers in the absorption tower 3 by oxidation fan 14, establishes aeration tube in the absorption tower 3, and it is uniform to be beneficial to oxidation air.Oxidation air is in order to be sulfite oxidation ammonium sulfate, and ammonium nilrite is oxidized to ammonium nitrate.The coefficient of excess of oxidation air amount is 1-3, the SO of its addition and inlet
2And NOx content is relevant.The oxidation air system also can be used to ozone supply in absorption tower 3.When the oxygen in the flue gas or ozone content are big, the oxidation air system can be set.
Ammonium sulfate in slurries, after ammonium nitrate reaches certain concentration, discharge through slurries excavationg pump 19, at first the dust separation in the slurries is come out through dust separator 20, slurries after the separation are sent to and carry out in the economic benefits and social benefits separator 21 separating of sour gas agent for capturing and saline solution, isolated sour gas agent for capturing returns absorption tower 3 by circulating pump 26 and recycles, simultaneously, contain ammonium sulfate, the chemical fertilizer treatment process that is sent to the saline solution of ammonium nitrate continues to handle, obtain byproduct of ammonium sulfate through multi-effect evaporation system 22 and chemical fertilizer drying system 23, ammonium nitrate fertilizer, the gained chemical fertilizer is discharged by chemical fertilizer pipe outlet 24.
Heavy metal in the flue gas is caught and is enriched in the sour gas agent for capturing by the oily matter in the sour gas agent for capturing, run up to finite concentration after, carry out desorption with chemical, the heavy metal that desorption goes out is concentrated and to be carried out harmless treatment.
Claims (9)
1. flue gas desulfurization and denitrification removing heavy-metal integral method is characterized in that: utilize a kind of sour gas agent for capturing, in same set of absorption plant to the SO in the former flue gas
2Or/and NOx catches, generate stable comple; Described complex compound reacts with a kind of absorbent that removes again, displaces described sour gas agent for capturing, and generates the intermediate by-products ammonium sulfite or/and the salting liquid of ammonium nilrite; Described sour gas agent for capturing is recycled; Described intermediate by-products further is oxidized to accessory substance ammonium sulfate or/and ammonium nitrate; Described former flue gas is oxidized to described NOx by strong oxidizer with the NO in the former flue gas before entering described absorption plant; In described same set of absorption plant, heavy metal is attracted in the described sour gas agent for capturing.
2. the method for claim 1 is characterized in that, described sour gas agent for capturing is a kind of mixture that takes off aromatic hydrocarbons, sulfoxide, alcoholic extract hydroxyl group, amido, hydramine, saturated hydrocarbons and isoparaffin that contains.
3. the method for claim 1 is characterized in that, the described absorbent that removes is an ammoniacal liquor, and described ammoniacal liquor is formed by liquefied ammonia, ammonia or urea production.
4. the method for claim 1 is characterized in that, described strong oxidizer is ozone or hydrogen peroxide.
5. the method for claim 1, it is characterized in that, the oxidant of ammonium nitrate utilization is that oxygen in the former flue gas is or/and ozone, perhaps for to enter the oxygen of described absorption plant or/and ozone by the oxidation air pipeline to described intermediate by-products ammonium sulfite or/and ammonium nilrite is oxidized to described accessory substance ammonium sulfate.
6. the method for claim 1, it is characterized in that, described sour gas agent for capturing, the described absorbent that removes are mixed into absorption liquid in described absorption plant, described absorption liquid is transported to the spraying layer at middle part, described absorption tower by circulating pump, described former flue gas makes progress through described spraying layer the SO in the former flue gas after entering described absorption plant
2, NOx or/and heavy metal caught by described absorption liquid.
7. method as claimed in claim 6 is characterized in that, described absorption liquid also is dissolved with described accessory substance ammonium sulfate or/and ammonium nitrate forms slurries; Or/and ammonium nitrate when reaching finite concentration, described slurries are discharged by the slurries discharger, by dust separator dust separation are gone out, and obtain containing ammonium sulfate or/and the saline solution of ammonium nitrate when the ammonium sulfate in the described slurries; Described saline solution is isolated described sour gas agent for capturing through the economic benefits and social benefits separator; Isolated sour gas agent for capturing reenters described circulating pump, and the saline solution after the separation is handled through evaporation and crystallization system and obtained finished product ammonium sulfate or/and ammonium nitrate crystals.
8. the method for claim 1 is characterized in that, described heavy metal carries out desorption with chemical run up to finite concentration in described sour gas agent for capturing after, and the heavy metal that desorption goes out is concentrated and carried out harmless treatment.
9. realize the special equipment of method according to claim 1 for one kind, it is characterized in that, comprise the absorption tower (3) that is used for the out of stock removing heavy-metal reaction of desulfurization, with bottom, absorption tower (3) by inlet pipeline link to each other be used to provide remove absorbent for ammonia pump (16), the sour gas agent for capturing pump (18) that is used to provide the sour gas agent for capturing that links to each other by inlet pipeline with bottom, absorption tower (3), the former flue (1) that links to each other with absorption tower (3) middle part, the ozone pipeline (12) that links to each other with former flue (1), the slurries excavationg pump (19) that links to each other by discharge line with bottom, absorption tower (3), the clean flue (5) that is used to discharge clean flue gas that links to each other with top, absorption tower (3), be arranged at the spraying layer (27) of the interior central region in absorption tower (3), connect the external circulating line of interior absorption liquid zone, absorption tower (3) and spraying layer (27) and be arranged at circulating pump (26) on the circulating line, be arranged at the demister (4) and the flushing water layer (28) in internal upper part zone, absorption tower (3), the flushing water pipeline (8) that is used to provide the demist water that links to each other with flushing water layer (28).
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| CN105148698A (en) * | 2015-08-21 | 2015-12-16 | 南京白云化工环境监测有限公司 | Boiler flue gas desulfurization and denitrification system |
| CN105709574A (en) * | 2016-01-27 | 2016-06-29 | 西安航天源动力工程有限公司 | Efficient stokerfeed boiler ozonation desulfurization and denitrification integrated process system |
| CN107131517A (en) * | 2016-02-26 | 2017-09-05 | 杭州中兵环保股份有限公司 | A kind of ozone oxidation lifts the device and method of SNCR denitration efficiency |
| CN105833686A (en) * | 2016-03-23 | 2016-08-10 | 凯天环保科技股份有限公司 | Fume nitrogen and sulfur resource utilization method and device thereof |
| CN106823731A (en) * | 2017-03-24 | 2017-06-13 | 西安热工研究院有限公司 | A kind of system and method for coal-fired flue-gas simultaneous SO_2 and NO removal |
| CN111974187A (en) * | 2020-08-20 | 2020-11-24 | 长春净月潭供热有限公司 | Flue gas desulfurization method using magnesium oxide as desulfurizer |
| CN112547065A (en) * | 2020-11-18 | 2021-03-26 | 中国恩菲工程技术有限公司 | Catalyst and method for removing metal elements in flue gas |
| CN112547065B (en) * | 2020-11-18 | 2023-07-21 | 中国恩菲工程技术有限公司 | Catalyst and method for removing metal elements in flue gas |
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