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CN103203166A - Technology for efficiently removing NOx pollutants in smoke - Google Patents

Technology for efficiently removing NOx pollutants in smoke Download PDF

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Publication number
CN103203166A
CN103203166A CN2012100082464A CN201210008246A CN103203166A CN 103203166 A CN103203166 A CN 103203166A CN 2012100082464 A CN2012100082464 A CN 2012100082464A CN 201210008246 A CN201210008246 A CN 201210008246A CN 103203166 A CN103203166 A CN 103203166A
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solution
flue gas
absorbent
nox
absorption
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童华
刘兆斌
吴丽莎
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

本发明提供一种高效率去除烟气中NOx的脱硝工艺，即首先采用亚氯酸钠溶液等作为氧化剂，对烟气中的NOx进行氧化，然后用亚硫酸钠溶液作为吸收剂，对烟气中的NOx进行处理，可获得大于75％的去除率。吸收剂由烟气中的二氧化硫与氢氧化钠反应制备，完成吸收后溶液与氢氧化钙反应，再生出氢氧化钠溶液重新用于吸收剂制备。本工艺较好地降低了NOx吸收成本，是一种高效、低成本的烟气脱硝工艺。The invention provides a high-efficiency denitrification process for removing NOx in flue gas, that is, firstly, sodium chlorite solution is used as an oxidant to oxidize NOx in flue gas, and then sodium sulfite solution is used as an absorbent to remove NOx in flue gas. NOx can be treated with a removal rate greater than 75%. The absorbent is prepared by reacting sulfur dioxide in the flue gas with sodium hydroxide. After the absorption is completed, the solution reacts with calcium hydroxide to regenerate the sodium hydroxide solution and reuse it for the preparation of the absorbent. The process reduces the NOx absorption cost well, and is a highly efficient and low-cost flue gas denitrification process.

Description

The technology that NOx pollutes in a kind of efficient removal flue gas
Affiliated technical field
The present invention relates to a kind of technology of industrial smoke denitration, relate in particular to the oxidation absorption technique that a kind of cost is lower, denitration efficiency is higher.
Background technology
Along with the enhancing of the serious and human environmental consciousness of industrial pollution, NO in the industrial waste gas XRemoval more and more be subjected to the attention of various countries, China also in 2010 with NO XInclude regional overall control category in as restrictive index, and carry out overall control in China.Present gas denitrifying technology can be divided into dry method and wet method two classes.The technology that dry method is removed NOx comprises SCR, and technologies such as SNCR, wet method then are with absorbent solution flue gas to be washed to purify flue gas, remove NO to reach XPurpose.Wet method is that liquid absorption method is simple with its process equipment, characteristics such as operating temperature is low, less energy consumption.It is simple than dry method that wet method NOx removes technology, but exist the not high problem of absorption efficiency.NO in the industrial smoke XMain component is NO, be about about 95%, and NO is insoluble in water, and in the time of 50 ℃, the solubility of NO in water is 38mg/L, is SO 2And NO 2Below 1/1000.Therefore the conventional liq absorption process is invalid substantially to NO.And the oxidation absorption process becomes a kind of selection of necessity.The oxidation absorption process is exactly to utilize oxidant with the NO that is oxidized to of NO part 2, adopt the liquid absorbing and removing then.Oxidation absorption process oxidant commonly used has: nitric acid, potassium permanganate, chlorous acid, hypochlorous acid, hydrogen peroxide, ozone etc., absorbent commonly used has: NaOH, urea etc.Though the oxidation absorption process has improved the efficient of wet method denitration to a certain extent, compare with the dry method denitration efficiency, also differ greatly.Therefore, need to adopt suitable oxidant and absorption liquid by process means effectively, with denitration efficiency, the reduction operating cost of further raising oxidation absorption process, only in this way, the oxidation absorption process just can become a kind of efficiently, denitration technology cheaply.
Summary of the invention
The invention provides NO in a kind of processing industrial smoke XThe wet method denitrating technique.By this technology, can improve denitration efficiency effectively, and will finish the regeneration of absorption solution after the denitration, and be recycled, reduce the denitration cost as much as possible, to remedy the deficiency of existing oxidation absorption process.
This technology mainly comprises three steps: at first be oxidizing process, adopt oxidant that NO is oxidized into NO effectively 2, the oxidant of employing is NaClO 2Deng solution, oxidizing temperature is 5-50 ℃, its course of reaction is comparatively complicated, main reaction principle is: 2NO+ClO 2 -→ 2NO 2+ Cl -Second is NO 2Absorption process, the absorbent of employing is the Na of mass concentration 0.1%～30% 2SO 3Solution carries out absorption reaction at 5-50 ℃, and its reaction principle is: 5NO 2+ 4SO 3 2-→ 4SO 4 2-+ N 2↑+3NO 2 -The 3rd is acquisition and the regeneration of absorbent, utilizes the SO in the industrial smoke 2Generate Na with the sodium hydroxide solution reaction of mass concentration 0.1～30% 2SO 3, its reaction principle is: 2NaOH+SO 2→ Na 2SO 3+ H 2O; The regeneration of NaOH solution is to utilize the Na that reaction produces in the absorption tower 2SO 4With Ca (OH) 2Reaction, regeneration NaOH, its reaction principle is: Na 2SO 4+ Ca (OH) 2→ CaSO 4↓+2NaOH.
The present invention compares with other technologies, and following characteristics are arranged:
1. adopt NaClO 2Deng solution as oxidant, Na 2SO 3Solution has very high oxidation assimilation effect as absorbent;
2. absorbent can be by the SO in the flue gas 2Obtain with the NaOH reaction, the source easily;
3. the solution after finishing NOx and absorbing is with the calcium hydroxide NaOH that regenerates, and returns in denitration and absorb, and therefore the consumption of actual NOx absorption process is calcium hydroxide, and operating cost is lower;
4. easily be combined with existing flue gas desulfur device, if that the flue gas desulfurization course application is wet method Ca (OH) 2Absorption technique, then can be directly by the desulfurizer Ca (OH) that partly provides and delivers 2, and need not to build in addition Ca (OH) 2The pond of sizing mixing.
Description of drawings
Accompanying drawing is the schematic flow sheet of implementing this technology.
In the accompanying drawing: 1, oxidizing tower, 2, the absorption tower, 3, the oxidant preparing pool, 4, neutralization reaction pond, 5, the NaOH regenerated reactor, 6, reservoir, 7, delivery pump, 8, delivery pump, 9 delivery pumps, 10, delivery pump, 11, valve, 12, valve, 13, valve, 14, valve, 15, valve, 16, valve.17, valve, 18, valve, 19, filter.
The specific embodiment
Below in conjunction with embodiment this technology is described further.
Figure of description is to implement a kind of oxidation absorption process of this technology denitration schematic flow sheet.Describe a kind of oxidation absorption process denitrating system with reference to the accompanying drawings.This system comprises: oxidizing tower 1, absorption tower 2, oxidant preparing pool 3, neutralization reaction pond 4, NaOH regenerated reactor 5, filtering ponds 6, delivery pump 7, delivery pump 8, delivery pump 9, delivery pump 10, valve 11, valve 12, valve 13, valve 14, valve 15, valve 16, valve 17, valve 18, filter 19.
Flue gas after the desulfurization is sent into oxidizing tower 1 from the bottom, and discharge from the top after the oxidation of oxidizing agent solution counter current contacting, and the solution of finishing after the oxidation is back to oxidant preparing pool 3 or discharges from the valve 13 of bottom through valve 12.Flue gas after oxidizing tower 1 oxidation enters absorption tower 2 from the bottom, in absorption tower 2 with absorption liquid counter current contacting, NO XBe removed.Flue gas after the denitration is discharged at 2 tops from the absorption tower, and the solution of finishing after the absorption is drained into NaOH regenerated reactor 5 or is back to neutralization reaction pond 4 through valve 16 through valve 17.
Oxidant and fresh water (FW) are sent into oxidant preparing pool 3 in proportion, under stirring condition, are deployed into the solution of desired concn.This solution is delivered to oxidizing tower 1 top by delivery pump 7, and its flow is by valve 11 controls.
Contain SO 2Flue gas feeds neutralization reaction pond 4, and the filtrate that regeneration obtains or additional fresh hydrogen sodium hydroxide solution are also sent into this pond, and under stirring condition, reaction is made into absorbent solution.These slurries are delivered to 2 tops, absorption tower by delivery pump 8, and its flow is by valve 14 controls.Finishing reacted gas then sends in the flue gas after desulfurization.
The solution of finishing after NOx absorbs that discharge on absorption tower 2 is sent into NaOH regenerated reactor 5 through valve 17, and the calcium hydroxide slurry reaction with adding generates calcium sulfate and NaOH.These slurries are delivered to filter 19 by delivery pump 9 realize liquid-solid separation, filtrate is sent into reservoir 6, is back to neutralization reaction pond 4 through delivery pump 10 then, and its flow is by valve 18 controls.Slag effluxes.
Further specify the solution of the present invention and effect in conjunction with experiment.
Example 1: be about 90% at nitrogen, oxygen is about under 10% the inlet air conditions, service property (quality) concentration be 1% sodium chlorite as oxidant, mass concentration be 10% sodium sulfite as absorbent, record NO XConcentration is down to 12ppm by 57ppm, and denitration efficiency is 78.9%.
Example 2: utilizing mass concentration is that 3.35% calcium hydroxide and mass concentration are 6.5% sodium sulphate reaction, and regeneration sodium hydroxide is filtered.In filtrate, feed the SO that contains 4000ppm 2Gas, the mass concentration of sodium sulfite is about 3% among the regulator solution pH to 7-8, this moment solution.Get this solution as absorbent, mass concentration be 1% sodium chlorite as oxidant, be about 90% at nitrogen, oxygen is about and records two groups of data under 10% the inlet air conditions: import NO XBe down to the 11ppm of outlet by 55ppm, denitration efficiency is 80.0%.
Find out that by above-mentioned example this technology denitration efficiency is very high, the NaOH regeneration effect is better, and the absorbent absorption efficiency of utilizing the NaOH after regenerating to generate does not almost reduce.

Claims (8)

1.一种高效去除烟气中NOX污染的工艺，即首先采用液相氧化剂将烟气中NO氧化以提高NOx的氧化度，然后用亚硫酸钠溶液作为吸收剂对烟气中的NOx进行吸收。吸收剂由烟气中SO2与氢氧化钠溶液反应制备，完成脱硝后的溶液用氢氧化钙再生出氢氧化钠，再生浆液过滤后得到的滤液重新用于制备吸收剂。1. A process for efficiently removing NOx pollution in flue gas, that is, first using a liquid phase oxidant to oxidize NO in flue gas to increase the oxidation degree of NOx, and then using sodium sulfite solution as an absorbent to absorb NOx in flue gas. The absorbent is prepared by reacting SO2 in the flue gas with sodium hydroxide solution. The denitrated solution is regenerated with calcium hydroxide to produce sodium hydroxide, and the filtrate obtained after filtering the regenerated slurry is reused to prepare the absorbent. 2.根据权利要求1所述的处理方法，其特征在于，工艺基本构成要素包括：氧化、吸收，以及吸收液再生等步骤中的前两个或三个步骤。2. The treatment method according to claim 1, characterized in that the basic elements of the process include the first two or three steps of oxidation, absorption, and regeneration of the absorption liquid. 3.根据权利要求1所述的处理方法，其特征在于，所述的氧化剂可采用高锰酸钾、亚氯酸、次氯酸、双氧水等溶液。3. The treatment method according to claim 1, characterized in that, the oxidizing agent can use solutions such as potassium permanganate, chlorous acid, hypochlorous acid, hydrogen peroxide and the like. 4.根据权利要求1所述的处理方法，其特征在于，吸收剂为亚硫酸钠溶液，其浓度为0.1％～30％。4. The treatment method according to claim 1, characterized in that the absorbent is sodium sulfite solution with a concentration of 0.1% to 30%. 5.根据权利要求1所述的处理方法，其特征在于，吸收剂可由烟气中的二氧化硫与氢氧化钠溶液反应制取，氢氧化钠水溶液浓度为0.1～30％。5. The treatment method according to claim 1, characterized in that the absorbent can be prepared by reacting sulfur dioxide in the flue gas with sodium hydroxide solution, and the concentration of the sodium hydroxide aqueous solution is 0.1-30%. 6.根据权利要求1所述的处理方法，其特征在于，将完成NOx吸收后的溶液与氢氧化钙浆液反应，再生出氢氧化钠溶液，并重新用于吸收剂制备。6. The treatment method according to claim 1, characterized in that the solution after the NOx absorption is completed is reacted with the calcium hydroxide slurry to regenerate the sodium hydroxide solution, which is reused for the preparation of the absorbent. 7.根据权利要求1所述的处理方法，其特征在于，所述的氧化反应的温度范围为5～50℃。7. The treatment method according to claim 1, characterized in that, the temperature range of the oxidation reaction is 5-50°C. 8.根据权利要求1所述的处理方法，其特征在于，所述的吸收反应的温度范围为5～60℃。8. The treatment method according to claim 1, characterized in that, the temperature range of the absorption reaction is 5-60°C.
CN2012100082464A 2012-01-12 2012-01-12 Technology for efficiently removing NOx pollutants in smoke Pending CN103203166A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028096A (en) * 2014-06-20 2014-09-10 北京中冶隆生环保科技发展有限公司 Technology for pressurized turbulent wet-process flue gas denitration and denitration waste liquid reuse
CN105195000A (en) * 2015-10-09 2015-12-30 广州研华环境科技有限公司 Flue gas cleaning device and method
CN106512657A (en) * 2016-12-18 2017-03-22 上海镁锶钡实业有限公司 Inorganic waste gas absorbent and method for treating inorganic waste gas in air
WO2017096692A1 (en) * 2015-12-09 2017-06-15 深圳广昌达环境科学有限公司 Fuel gas denitration and desulfurization washing system and denitration and desulfurization method
CN108114596A (en) * 2017-12-18 2018-06-05 北京联飞翔科技股份有限公司 A kind of composition and its application method for purifying nitrogen oxides
CN108273825A (en) * 2017-12-29 2018-07-13 天津壹鸣环境科技股份有限公司 Recycling method of household garbage incineration fly ash
CN108744934A (en) * 2018-06-25 2018-11-06 山东首丰环保设备有限公司 A kind of method of redox denitration
CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid
CN109173637A (en) * 2018-10-30 2019-01-11 攀钢集团攀枝花钢铁研究院有限公司 The method of low-temperature flue gas liquid phase oxidation denitration
CN113117491A (en) * 2019-12-31 2021-07-16 中晶环境科技股份有限公司 Desulfurization and denitrification process based on calcium-based absorbent

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104028096A (en) * 2014-06-20 2014-09-10 北京中冶隆生环保科技发展有限公司 Technology for pressurized turbulent wet-process flue gas denitration and denitration waste liquid reuse
CN105195000A (en) * 2015-10-09 2015-12-30 广州研华环境科技有限公司 Flue gas cleaning device and method
WO2017096692A1 (en) * 2015-12-09 2017-06-15 深圳广昌达环境科学有限公司 Fuel gas denitration and desulfurization washing system and denitration and desulfurization method
CN106512657A (en) * 2016-12-18 2017-03-22 上海镁锶钡实业有限公司 Inorganic waste gas absorbent and method for treating inorganic waste gas in air
CN108114596A (en) * 2017-12-18 2018-06-05 北京联飞翔科技股份有限公司 A kind of composition and its application method for purifying nitrogen oxides
CN108273825A (en) * 2017-12-29 2018-07-13 天津壹鸣环境科技股份有限公司 Recycling method of household garbage incineration fly ash
CN108744934A (en) * 2018-06-25 2018-11-06 山东首丰环保设备有限公司 A kind of method of redox denitration
CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid
CN109173637A (en) * 2018-10-30 2019-01-11 攀钢集团攀枝花钢铁研究院有限公司 The method of low-temperature flue gas liquid phase oxidation denitration
CN113117491A (en) * 2019-12-31 2021-07-16 中晶环境科技股份有限公司 Desulfurization and denitrification process based on calcium-based absorbent

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Application publication date: 20130717