CN102188882B - Integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment - Google Patents

Integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment Download PDF

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Publication number
CN102188882B
CN102188882B CN2011100912812A CN201110091281A CN102188882B CN 102188882 B CN102188882 B CN 102188882B CN 2011100912812 A CN2011100912812 A CN 2011100912812A CN 201110091281 A CN201110091281 A CN 201110091281A CN 102188882 B CN102188882 B CN 102188882B
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flue gas
capturing
sour gas
ammonium
absorption
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CN2011100912812A
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Chinese (zh)
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CN102188882A (en
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史绍荣
杜文丹
王艳波
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北京国电清新环保技术股份有限公司
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    • Y02A50/2344
    • Y02A50/2349

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

Flue gas desulfurization and denitrification removing heavy-metal integral method and special equipment

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

Contain sulfur dioxide (SO in the flue gas of the every profession and trade dischargings such as fire coal, fuel oil, combustion gas thermal power plant, metallurgy, chemical industry, solid waste garbage disposal or industrial tail gas 2), nitrogen oxide (mainly comprises NO and NO 2) and the pollutant such as heavy metal (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 desulphurization and denitration Process configuration is at present: after the electricity generation boiler economizer, the front fume high-temperature section of air preheater is established the SCR denitrification apparatus, installs desulfurizer after dedusting additional.Its shortcoming is: one-time investment is large, floor space is large, SR is large, power consumption is high, there is no the demercuration function.There is no at present ripe removing for the heavy metal in flue gas or industrial tail gas.In a word, which kind of technology no matter just present actual conditions adopt, to SO 2All to realize not possessing the function that same set of device integrated efficient removes in the different device of two functions with removing of NOx, more without 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 is 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, realizing that in same set of device, sulfur dioxide, nitrogen oxide and heavy metal being carried out integrated efficient removes.

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 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 is further oxided as 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 former flue gas before entering described absorption plant; In described same set of absorption plant, heavy metal is attracted in 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 flue gas in SO 2Or NOx generates stable complex compound, can adsorb the heavy metal in flue gas.

The described absorbent that removes is ammoniacal liquor, and described ammoniacal liquor is prepared from by liquefied ammonia, ammonia or urea.As long as can satisfy the system held water balance, the concentration of ammoniacal liquor do not had 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 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 enters the described spraying layer of the backward upper process of described absorption plant, the SO in former flue gas 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 described slurries; Described saline solution is isolated described sour gas agent for capturing through Double-effect separator; Isolated sour gas agent for capturing reenters described circulating pump, and the saline solution after separation is processed through evaporation and crystallization system and obtained the finished product sulfuric acid ammonium 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 or/and the clean flue gas of heavy metal be arranged on the demister on described absorption plant top and rinse and discharge after water layer is removed droplet.

realize the special equipment of flue gas desulfurization and denitrification removing heavy-metal integral method of the present invention, comprise the absorption tower for the out of stock removing heavy-metal reaction of desulfurization, with the bottom, absorption tower by inlet pipeline be connected be used for providing remove absorbent for ammonia pump, the sour gas agent for capturing pump that is used for providing the sour gas agent for capturing that is connected by inlet pipeline with the bottom, absorption tower, the former flue that is connected with the middle part, absorption tower, the ozone pipeline that is connected with former flue, the slurries excavationg pump that is connected by discharge line with the bottom, absorption tower, the clean flue that is used for discharging clean flue gas that is connected 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 circulating line, be arranged at the demister in internal upper part zone, absorption tower and rinse water layer, the flushing water pipeline that is used for providing the demist water that is connected with the flushing water layer.Wherein, spraying layer can be set to multilayer.

On the ozone pipeline by from former flue by as far as close to order be disposed with air duct, air separation unit, ozone generator.

Be connected with tank used for storing ammonia by pipeline for ammonia pump.

Sour gas agent for capturing pump is connected with sour gas agent for capturing storage tank by pipeline.

On discharge line after the slurries excavationg pump, be provided with dust separator, Double-effect 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 is connected with the circulating line of circulating pump.

Clean flue is connected with chimney.

Be provided with booster fan on the former flue before the ozone pipeline.

Also be connected with in the bottom, absorption tower be used to the oxidation air system that oxygen or ozone are provided, this system is comprised of air duct and the upper oxidation fan that arranges thereof.When the oxygen content in flue gas is enough to ammonium sulfite/ammonium nilrite is oxidized to ammonium sulfate/ammonium nitrate, can not establish this road oxidation air system.

Be connected with bypass flue on the former flue before booster fan, the port of export of bypass flue is connected with clean flue.

Advantage of the present invention and beneficial effect are as follows:

(1) realize flue gas desulfurization and denitrification removing heavy-metal integrated purifying function in a covering device, 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 approximately 30%; Take up an area 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) the sour gas agent for capturing is out separable after using, and returns in tower by circulating pump to recycle;

(4) clean nitrogen oxides in effluent content is reduced to below 50mg, and content of sulfur dioxide is reduced to below 50mg.

In a word, the present invention have system simple, be easy to realize, cost is low, rate of recovery high.

Description of drawings

Fig. 1 is process chart of the present invention

in figure: the former flue of 1-, the 2-booster fan, the 3-absorption tower, the 4-demister, the clean flue of 5-, the 6-chimney, the 7-bypass flue, 8-flushing water pipeline, the 9-air duct, the 10-air separation unit, the 11-ozone generator, 12-ozone pipeline, the 13-air duct, the 14-oxidation fan, the 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, the 20-dust separator, the 21-Double-effect 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-rinses 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, utilize equipment shown in Figure 1 to carry out the integral method of flue gas desulfurization and denitrification removing heavy-metal as follows: 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, be the high price nitrogen oxide (NOx) such as nitrogen dioxide with the oxidation of nitric oxide in former flue gas, former flue gas enters absorption tower 3 from former flue 1 import afterwards.The former flue gas that enters behind absorption tower 3 upwards flows through spraying layer 27, the SO in flue gas 2, NOx and heavy metal absorbed by the lower absorption liquid washing reaction that contains a certain proportion of sour gas agent for capturing, absorbent of spraying layer 27 sprays, the clean flue gas after removing is through demister 4 and rinse and discharged by chimney 6 through clean flue 5 after water layer 28 is removed droplet.The flushing water pipeline 8 that is connected with flushing water layer 28 is used for providing mist eliminator flushing water.

The absorption tower 3 that removes absorption plant as flue gas washing is spray column.The interior absorption liquid in absorption tower 3 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 is 3 interior necessary certain liquid levels that keep on the absorption tower, 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 flue gas 2, NOx is converted into ammonium sulfite, ammonium nilrite, be dissolved in absorption liquid, be ammonium sulfate, nitrous acid by oxidation step subsequently.

The addition of sour gas agent for capturing is directly proportional to sulfur dioxide in flue gas content, is initially adding fashionablely, and sour gas agent for capturing and moisture add by the volume ratio of 1/1-5.The concentration that removes absorbent ammoniacal liquor that adds is substantially unrestricted, and concentration commonly used all can be used at the ammoniacal liquor of 1-25%.Control the ammoniacal liquor addition according to the pH value in the absorption tower and denitrification efficiency.

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, then obtains ozone through ozone generator 11 ionization.Ozone also available air directly ionization obtains through ozone generator 11, but the ozone concentration that obtains with the air direct ionization is lower, power consumption is higher.Ozone is uniformly distributed in 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 the high price nitrogen oxide such as nitrogen dioxide.The addition of ozone, relevant with the content of nitric oxide in flue gas and nitrogen dioxide.The coefficient of excess of ozone is 1.03-2, and coefficient of excess is larger 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 (not indicating in figure) that the oxidation fan 14 on air duct 13 forms.Air is entered by air duct 13, delivers in absorption tower 3 by oxidation fan 14, establishes aeration tube in absorption tower 3, is beneficial to oxidation air uniform.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 entrance 2And NOx content is relevant.The oxidation air system also can be used to the 3 interior ozone supplies to the absorption tower.When the oxygen in flue gas or ozone content when larger, 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 pass through dust separator 20 with the dust separation in slurries out, slurries after separation are sent to and carry out in Double-effect separator 21 separating of sour gas agent for capturing and saline solution, isolated sour gas agent for capturing returns to 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 process, 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 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, after running up to finite concentration, carries out desorption with chemical, and the heavy metal that desorption goes out is concentrated and carried out harmless treatment.

Claims (7)

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 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 is further oxided as accessory substance ammonium sulfate or/and ammonium nitrate; Described former flue gas is oxidized to described NOx by strong oxidizer with the NO in former flue gas before entering described absorption plant; In described same set of absorption plant, heavy metal is attracted in described sour gas agent for capturing;
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;
The described absorbent that removes is ammoniacal liquor, and described ammoniacal liquor is prepared from by liquefied ammonia, ammonia or urea.
2. the method for claim 1, is characterized in that, described strong oxidizer is ozone or hydrogen peroxide.
3. the method for claim 1, it is characterized in that, the oxidant of ammonium nitrate utilization is that oxygen in 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.
4. 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 enters the described spraying layer of the backward upper process of described absorption plant, the SO in former flue gas 2, NOx or/and heavy metal caught by described absorption liquid.
5. method as claimed in claim 4, 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 described slurries; Described saline solution is isolated described sour gas agent for capturing through Double-effect separator; Isolated sour gas agent for capturing reenters described circulating pump, and the saline solution after separation is processed through evaporation and crystallization system and obtained the finished product sulfuric acid ammonium or/and ammonium nitrate crystals.
6. 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.
7. realize the special equipment of method as claimed in claim 1 for one kind, it is characterized in that, comprise the absorption tower (3) for the out of stock removing heavy-metal reaction of desulfurization, with bottom, absorption tower (3) by inlet pipeline be connected be used for providing remove absorbent for ammonia pump (16), the sour gas agent for capturing pump (18) that is used for providing the sour gas agent for capturing that is connected by inlet pipeline with bottom, absorption tower (3), the former flue (1) that is connected with absorption tower (3) middle part, the ozone pipeline (12) that is connected with former flue (1), the slurries excavationg pump (19) that is connected by discharge line with bottom, absorption tower (3), the clean flue (5) that is used for discharging clean flue gas that is connected 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 circulating line, be arranged at the demister (4) in internal upper part zone, absorption tower (3) and rinse water layer (28), the flushing water pipeline (8) that is used for providing the demist water that is connected with flushing water layer (28),
Ozone pipeline (12) upper by from former flue by as far as close to order be disposed with air duct (9), air separation unit (10), ozone generator (11); Be connected with tank used for storing ammonia (15) by pipeline for ammonia pump (16); Sour gas agent for capturing pump (18) is connected with sour gas agent for capturing storage tank (17) by pipeline.
CN2011100912812A 2011-04-12 2011-04-12 Integrated method for simultaneously realizing denitrification, desulfurization and heavy metal removal from flue gas, and special equipment CN102188882B (en)

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CN102358621A (en) * 2011-10-17 2012-02-22 大连理工大学 Method for ammonium sulfite or ammonium nitrite oxidation by ozone
CN103212284A (en) * 2013-03-15 2013-07-24 孙琦 Method and device for combined removal of nitric oxide and sulfide in flue gas
CN103480251B (en) * 2013-09-29 2015-07-01 中悦浦利莱环保科技有限公司 System and method for performing desulfurization, denitration and demercuration to flue gas simultaneously
CN104043325B (en) * 2014-05-30 2016-08-24 江苏大学 The flue gas purifying method of a kind of ozone activation persulfate and device
CN104857834B (en) * 2015-06-05 2017-03-08 北京中晶环境科技股份有限公司 Equipment for denitrifying flue gas based on ozone and method
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

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CN100496675C (en) * 2007-04-30 2009-06-10 武汉凯迪电力环保有限公司 Simultaneous desulfurization and denitration wet ammonia flue gas cleaning technology and system thereof
CN101327397B (en) * 2008-07-03 2011-03-23 大连理工大学 Method for simultaneously removing SO2 and NO in flue gas by biological reduction and complexing absorption
CN101530729B (en) * 2009-03-09 2011-06-29 华东理工大学 Multifunctional absorption tower for controlling NO and SO2 in waste gas simultaneously
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