CN101306308B - Method for synchronously treating the combined pollution exhaust gas containing nitric oxide and sulfur dioxide - Google Patents

Method for synchronously treating the combined pollution exhaust gas containing nitric oxide and sulfur dioxide Download PDF

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CN101306308B
CN101306308B CN2008100329390A CN200810032939A CN101306308B CN 101306308 B CN101306308 B CN 101306308B CN 2008100329390 A CN2008100329390 A CN 2008100329390A CN 200810032939 A CN200810032939 A CN 200810032939A CN 101306308 B CN101306308 B CN 101306308B
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龙湘犁
陶力三
李伟
袁渭康
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East China University of Science and Technology
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Abstract

The invention relates to a method for simultaneous treatment of mixed pollutant exhaust gas containing NOx and SO2. Absorption liquid of ferrous salt, ethylenediaminetetraacetic acid disodium and a desulphurization agent and waste gas containing SO2 and NO are introduced into a conventional reactor to carry out the reaction, thereby realizing the simultaneous absorption of NO and SO2. The absorption liquid after the reaction can be introduced in a liquid-solid reactor which takes activated carbon as a catalyst for regeneration. The method is a low-cost wet desulphurization and denitrification technique with market competitiveness.

Description

A kind of improvement simultaneously contains NO xAnd SO 2The method of mixed pollutants waste gas
Technical field
The present invention relates to a kind of improvement simultaneously and contain NO XAnd SO 2The method of mixed pollutants waste gas especially relates to NO and SO in the power-plant flue gas 2The time removal methods.
Background technology
The pollution of acid rain and the harm that causes thereof have become one of environmental problem of paying close attention to countries in the world.SO 2And NO xBeing two kinds of dusty gas that discharge capacity is maximum, harmfulness is maximum, also is the main matter that forms acid rain.With the coal country of main energy sources, the SO that coal combustion produces 2(1000～4000ppm) and NO x(300～800ppm), be that industrial waste gas pollutes the main root of (acid rain harm).
NO xBe the general designation of nitrogen oxide, comprise N 2O, NO, N 2O 3, NO 2, N 2O 5Deng.NO xHarmfulness be that not only it is an acid rain property gas, and NO is the same with fluorochlorohydrocarbon can significantly damage the ozone layer NO and N 2O also is greenhouse gases simultaneously, and NO ability and hydrocarbon react in the sun and cause photochemical pollution.
NO in the atmosphere more than 95% XBe NO, NO 2Only account for very small amount, the NO in the flue gas XAlso NO more than 90%.Because the NO respond is relatively poor, is insoluble in water again, therefore, it removes also just quite difficult technically.Developed multiple method of denitration through years of researches.What at present, industrial employing was more is catalytic reduction method.Like patent USP:4,221,768, Swedish Patent 8404840-4, USP:4,101; 238, US:4,048,112 disclosed method; But a large amount of reducing agent of this method reaction needs consumption, and the nitrogen in the flue gas can not recycle, and causes the valuable wasting of resources.
Japan Patent JP1659565 (1976), JP63100918A2 (1988) remove NO when proposing XAnd SO 2Oxidant that method adopts, like chloric acid, potassium permanganate, hydrogen peroxide solution, ozone etc., liquid phase oxidation NO XDeng because cost height etc. is former thereby fail to promote and come.The yellow phosphorus method that California, USA university Berkeley laboratory proposes (is seen document Nature, 1990,343 (11): 151-153), can remove the NO in the flue gas simultaneously XAnd SO 2, but belong to the method for abandoning entirely.This method will consume a large amount of phosphor resources, and its toxicity is big, and operation is had relatively high expectations.
The early 1970s people propose to adopt Fe (II)-EDTA (EDTA representes disodium ethylene diamine tetraacetate) to remove NO in the waste gas, and the reaction equation of Fe (II)-EDTA and NO is following:
Fe(II)-EDTA+NO_Fe(II)-EDTA(NO) (1)
In nearly three ten years afterwards, many scholars have carried out comparatively systematic research to this reaction, but do not see the industrialization report at present yet; Main cause is that (document sees reference: Bull.ofthe Chem.Soc.of Jpn., 1968,41:2234-2239.Ind.Eng.Chem.Res. because Fe (II)-EDTA is prone to be oxidized to Fe (III)-EDTA; 1987,26:1468-1472.Inorg.Chem., 1990; 29:1705-1711.Ind.Eng.Chem.Res., 1993,32:2580-2594.); And Fe (III)-EDTA can not complexing NO, and absorption efficiency is descended rapidly.People propose to regenerate with the living things catalysis reducing process, and (Fe (II) sees reference document: UnitedStates Patent US5891408.Biotechnol.Prog., 2003,19:1323-1328.J Chem Technol Biotechnol; 2004,79:835-841.Biotechnology and Bio engineering, 2005; 90:433-441.Environ Sci Technol, 2005,39:2616-2623.J of Chem Technol and Biotechnol; 2006; 81:306-311.), but this method just is in the exploratory stage at present, in the waste gas pollution control and treatment process, obtain large-scale application and also have many problems to need to solve.
Summary of the invention
The objective of the invention is to propose a kind of improvement simultaneously and contain NO XAnd SO 2The method of mixed pollutants waste gas.
The technical issues that need to address of the present invention provide and a kind ofly remove NO and SO in the waste gas with Fe (II)-EDTA solution 2Method, make NO and SO 2Absorption carry out simultaneously, overcoming the above-mentioned defective that prior art exists, reduce the treatment cost of wet desulphurization denitration, improve the market competitiveness of wet desulphurization denitration technology.
Design of the present invention is such:
Utilization contains the absorption liquid while absorption of N O and the SO of Fe (II)-EDTA and desulfurizing agent composition 2, the Fe (III) that Fe (II)-EDTA oxidation generates-EDTA employing active carbon is made catalyst and is come catalytic reduction to be regenerated as Fe (II)-EDTA, and the basic principle of Fe (II)-EDTA catalytic regeneration is following:
Because of impelling Fe (III)-EDTA, acidic-groups such as the carbonyl on the activated carbon, carboxyl, phenolic group dissociate into Fe (III) and EDTA (reaction (2)):
Figure GSB00000780985300021
Fe (III) has stronger oxidability, and the pi-electron structure of activated carbon had both had the ability of transmitting electronics, can become the center of Fe (III) ion reduction, SO 2Be dissolved in the inferior sulfate radical that produces in the absorbent solution as reducing agent, Fe (III) reducing/regenerating is become Fe (II) (reaction (3)), inferior sulfate radical is oxidized to sulfate radical.
Figure GSB00000780985300031
Fe (II) combines to generate Fe (II)-EDTA (reaction (4)) again with EDTA in solution, make absorbent be able to regeneration, and the ability that absorption liquid removes NO can keep for a long time.
Fe(II)+EDTA→Fe(II)-EDTA (4)
Method of the present invention realizes through the while desulfurization and denitrification reaction: in the reactor of routine, ferrous salt, disodium ethylene diamine tetraacetate (EDTA) and desulfurizing agent be dissolved in be used as absorption liquid in the aqueous solution, will contain NO and SO 2Waste gas feed, realize NO and SO 2Carry out when absorbing.
Described desulfurizing agent is bivalent metal oxide, oxyhydroxide or carbonate etc., can be calcium oxide (lime), magnesia, Mg (OH) 2Or calcium carbonate (lime stone) etc.
The NO concentration range is in the described waste gas: 100～1000ppm; SO 2Concentration range be 500～3000ppm.
Usually can contain oxygen, O in the waste gas 2Concentration be 0～20%.
Operating pressure is a normal pressure, and temperature range is: 10～90 ℃, optimum value is: 30～60 ℃.
The pH scope of solution is generally: 1～9, and optimum value is: 4～7.
The concentration range of ferrous salt is: 0.005～0.1mol l -1, be preferably 0.02～0.06mol l -1
The concentration range of EDTA is: 0.01～0.2mol l -1, be preferably 0.04～0.15mol l -1
The concentration of desulfurizing agent is 0～0.3mol l -1Be preferably 0.005～0.3mol l -1For example the concentration range of calcium oxide is: 0.005～0.3mol l-1 is recommended as 0.01～0.1mol l-1; Magnesian concentration range is: 0.005～0.3mol l -1, be recommended as 0.01～0.1mol l -1The concentration range of calcium carbonate is: 0.005～0.3mol l -1, be recommended as 0.01～0.1mol l -1
Common gas liquid ratio (volume flow ratio, M 3) be 10～300: 1, recommending gas liquid ratio is 200: 1.
Ferrous salt can be chosen any one kind of them from ferrous sulfate commonly used, frerrous chloride, ferrous nitrate, and preferably sulfuric acid is ferrous.
The present invention is to NO XAnd SO 2The reactor that absorbs does not simultaneously have special demands, NO XAnd SO 2Remove and can in common gas-liquid reactor such as packed tower, plate column or bubble tower etc., carry out.
Reaction solution in the inventive method can be regenerated: above-mentioned reacted solution is fed to make in the reactor of catalyst of activated carbon regenerate; This reactor is liquid-solid reactor commonly used, and like fixed bed, slurry bed etc., activated carbon can be cocos active carbon commonly used, wood chip activated carbon, ature of coal activated carbon etc.; Regeneration temperature is 20～90 ℃; Optimum temperature is 50～80 ℃, and regeneration pH is 1～9, and best pH is 3～7.Reaction solution can continue to use after the regeneration.
In other words, method of the present invention can be carried out so continuously: above-mentioned absorption liquid imports from the top or the upper lateral part of reactor, and contains NO XAnd SO 2Waste gas from the bottom of reactor or the following side import and continue reaction; The gas that reacts later is said from the top or the upper lateral part of reactor continuously; And absorption liquid flows out from the bottom or the following side of reactor on the contrary; And importing contains in the liquid-solid reactor of activated carbon the use of process activating and regenerating continued.
The present invention makees absorbent through adopting Fe-EDTA solution, and activated carbon is done the method that catalyst, sulphite are reducing agent regeneration NO absorbing activity component Fe (II)-EDTA, realizes recycling of NO absorbent, realizes NO and SO 2Remove simultaneously and carry out, the cost that nitrogen oxide and sulfur dioxide are administered simultaneously descends greatly.
Description of drawings
Fig. 1 is a kind of flow chart of the present invention.
Symbol description.
In the accompanying drawing: the 1-reactor, the 2-liquid-solid reactor, the 3-absorption liquid, 4-contains NO XAnd SO 2Waste gas, 5-activated carbon, 6-circulating slot.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but can not limit of the present invention in.
Embodiment 1
Absorption experiment is carried out in the packed tower of diameter 2cm, high 100cm, the gas-liquid two-phase adverse current, and empty tower gas velocity is 0.1m/s, liquid spraying density is 5m 3/ m 2.hr, absorption liquid 500ml.
Wherein: ferrous sulfate concentration is 0.02mol l -1, EDTA concentration is 0.04mol l -1, the pH value is 6,
Gas flow is 200ml/minute, and temperature is 50 ℃;
Gas feed consists of NO:480ppm, SO 2: 1500ppm, O 2: 5.2%, all the other are nitrogen.
Absorption liquid gets into packed tower absorption of N O and SO by cat head 2In tower bottom flow is gone into circulating slot; Get into the fixed bed reactors that high 50cm, diameter 2cm be equipped with cocos active carbon from circulating slot again and carry out catalyst regeneration; Reaction temperature is that 80 ℃, the liquid speed with 25ml min-1 in regenerator flows from lower to upper, and the absorption liquid that leaves regenerator directly gets into absorption of N O and SO in the packed tower 2Gas vent concentration is carried out on-line analysis by infrared spectrometer, per two minutes automatically sampling once reach when stablizing in operation, gas vent concentration is NO:30ppm, SO 2: 150ppm.The flow chart of logistics is shown in accompanying drawing 1.
Embodiment 2
Reactor and operating condition be with embodiment 1, but also have 0.03mol l in the absorption liquid -1Calcium oxide, reach when stablizing in operation, gas vent concentration is NO:30ppm, SO 2: 40ppm.
Embodiment 3
Reactor and operating condition be with embodiment 1, but also have 0.03mol l in the absorption liquid -1Magnesia, reach when stablizing in operation, gas vent concentration is NO:30ppm, SO 2: 40ppm.
Embodiment 4
Reactor and operating condition be with embodiment 1, but also have 0.03mol l in the absorption liquid -1Lime stone, reach when stablizing in operation, gas vent concentration is NO:30ppm, SO 2: 40ppm.

Claims (8)

1. one kind removes SO in the waste gas simultaneously with Fe-EDTA solution 2With the method for NO, it is characterized in that in the absorption reactor thermally of routine operating pressure is normal pressure and temperature when being 10～90 ℃, feeds absorption liquid and contains SO 2React with the waste gas of NO, the gas-liquid volume flow ratio is 10～300: 1;
Described absorption liquid is that the pH that contains ferrous salt, disodium ethylene diamine tetraacetate and desulfurizing agent is 1～9 the aqueous solution; Wherein, the concentration range of ferrous salt is 0.005～0.1mol l -1The disodium ethylene diamine tetraacetate concentration range is 0.01～0.2mol l -1The concentration of desulfurizing agent is 0～0.3mol l -1
Described desulfurizing agent is bivalent metal oxide, oxyhydroxide or carbonate;
Reacted absorption liquid is to feed in the liquid-solid reactor of making catalyst of activated carbon in 1～9 o'clock to regenerate at 20～90 ℃ with pH.
2. the method for claim 1 is characterized in that temperature is 30～60 ℃ in the described absorption reactor thermally; Described gas-liquid volume flow is 200: 1.
3. the method for claim 1 is characterized in that the NO concentration range is 100～1000ppm in the described waste gas; SO 2Concentration range be 500～3000ppm; Containing concentration of oxygen in the waste gas is 0～20%.
4. the method for claim 1 is characterized in that the pH scope of described absorption liquid is: 4～7.
5. the method for claim 1, the concentration that it is characterized in that described molysite is 0.02～0.06mol l -1The concentration of described disodium ethylene diamine tetraacetate is 0.04～0.15mol l -1The concentration of described desulfurizing agent is 0.005～0.3mol l -1
6. the method for claim 1 is characterized in that described bivalent metal oxide is calcium oxide, magnesia or calcium carbonate; The concentration range of described calcium oxide is 0.005～0.3mol l -1Described magnesian concentration range is 0.005～0.3moll -1The concentration range of described calcium carbonate is 0.005～0.3mol l -1
7. the method for claim 1 is characterized in that described ferrous salt is ferrous sulfate, frerrous chloride or ferrous nitrate.
8. the method for claim 1 is characterized in that described activated carbon is cocos active carbon, wood chip activated carbon or ature of coal activated carbon, and regeneration temperature is 50～80 ℃; PH is 3～7.
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CN101785965B (en) * 2010-03-02 2013-06-12 浙江菲达环保科技股份有限公司 Complex absorption cycle semi-dry desulfurization and denitrification integral process and device
CN102824836A (en) * 2012-09-12 2012-12-19 河南绿典环保节能科技有限公司 Integrated wet-type oxidation, desulfurization, denitration and recycling method for smoke
CN103041688B (en) * 2012-12-31 2015-07-08 青岛大学 Method for desulfurization and denitrification of fume and coproduction of ammonium sulfate
CN104084025B (en) * 2014-07-17 2016-04-20 湖南平安环保股份有限公司 A kind of method of boiler smoke removal of nitrogen oxide
CN105536493B (en) * 2015-12-28 2018-04-06 昆明理工大学 One kind utilizes SO in phosphate ore pulp and mud phosphorus removing fire coal boiler fume2And NOXMethod
CN106621808A (en) * 2017-01-03 2017-05-10 北京清新环境技术股份有限公司 Wet type integrated purification system and method for recovery of residual heat in flue gas
CN107308783B (en) * 2017-08-31 2021-02-26 山东瑞嘉通风环保科技有限公司 Wet-process simultaneous desulfurization and denitrification process for flue gas
CN109825338A (en) * 2019-01-30 2019-05-31 维珂瑞（北京）环境科技有限公司 H in a kind of removal biogas2The LO-CAT system of S
CN110124451B (en) * 2019-05-13 2021-11-05 上海大学 Wet-type step-by-step SO removal in flue gas2And NO process
CN114432869B (en) * 2020-10-31 2023-05-30 中国石油化工股份有限公司 Method and device for treating coal-fired flue gas
CN115738599B (en) * 2022-11-23 2024-06-04 攀钢集团攀枝花钢铁研究院有限公司 At the same time absorb NOxPreparation method of complexing denitration liquid of CO

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