WO2017166439A1 - 一种含氮氧化物工业废气的处理方法及处理装置 - Google Patents

一种含氮氧化物工业废气的处理方法及处理装置 Download PDF

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WO2017166439A1
WO2017166439A1 PCT/CN2016/086089 CN2016086089W WO2017166439A1 WO 2017166439 A1 WO2017166439 A1 WO 2017166439A1 CN 2016086089 W CN2016086089 W CN 2016086089W WO 2017166439 A1 WO2017166439 A1 WO 2017166439A1
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denitration
permanganate
column
waste gas
containing nitrogen
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PCT/CN2016/086089
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English (en)
French (fr)
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李明玉
李艺春
张鑫
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广州绿华环保科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/79—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • B01D53/965—Regeneration, reactivation or recycling of reactants including an electrochemical process step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants

Definitions

  • the invention relates to the field of exhaust gas denitration, in particular to a method and a device for using a permanganate denitration agent.
  • the denitration technology that is suitable for boilers, industrial furnaces, metal surface treatment, steel, coking and other industries with low nitrogen oxide waste gas and high efficiency is the research focus of many scholars.
  • the most studied wet denitration techniques are the oxidative absorption method and the complex absorption method.
  • the complex absorption method is easy to be oxidized due to the commonly used complexing agent Fe 2+ , and it is necessary to add an antioxidant.
  • the regeneration system is complicated, the energy consumption is high, the running cost is high, and it is difficult to promote the use; the oxidation absorption method often has high removal efficiency and fast absorption rate.
  • the combination of simple equipment and convenient operation can be combined with the mature wet denitration technology at the present stage.
  • the oxidative absorption method is a process in which NO is oxidized to NO 2 by an oxidizing agent, and then treated by absorption with water or alkali solution, or an oxidizing agent is added to an alkali solution, and is absorbed while oxidizing.
  • KMnO 4 has been proved to be an effective denitrifying oxidant, and the ideal denitration efficiency can be obtained in both acidic and alkaline environments.
  • KMnO 4 has become a major industrial application due to its own defects. technical challenge.
  • KMnO 4 is more expensive, and high-concentration manganese-containing wastewater will cause water and body metal pollution if not treated, so the wastewater treatment cost is high; in addition, it is also the most important, using KMnO 4 as denitration oxidant, KMnO 4 self-denitration top of the column is injected into the exhaust gas from off the bottom of the input denitrification column, KMnO.
  • the object of the present invention is to overcome the technical defects of high cost and easy fouling and clogging of the permanganate denitration agent in the prior art, and to provide a method and a device for treating industrial waste gas containing nitrogen oxides by using a permanganate denitration agent.
  • the present invention provides a method of treatment of industrial waste gas containing nitrogen oxides, comprising the steps of: (1) the delivery of NO x containing exhaust gas to the bottom of a column of denitration, the denitration permanganate transport agent to top of the stripper column denitration, the denitration permanganate agent to the NO x converted to nitrate, the rest of the liquid flow to the column bottom denitration; (2) the bottom of the stripper column the denitration raffinate delivery In an electrolytic cell, the electrolytic cell is energized to electrolyze manganate in the remaining liquid to permanganate to form the permanganate denitration agent; and (3) to be electrolyzed The permanganate denitration agent is delivered to the top of the denitration column.
  • the concentration of the nitrate reaches a preset value
  • the remaining liquid at the bottom of the denitration column is sent to a separation system, and the nitrate is recovered after evaporation and crystallization.
  • the method for treating the nitrogen-containing oxide industrial waste gas further comprises replenishing the alkali in the electrolytic tank.
  • the method for treating industrial waste gas containing nitrogen oxides further comprises replenishing the electrolytic cell Electrolyte.
  • the industrial waste gas containing nitrogen oxides is further comprising, prior to the NO x -containing exhaust gas is fed to the bottom of the column denitration of flue gas fed to a desulfurization apparatus for desulfurizing process.
  • the present invention further provides an apparatus for treatment of industrial waste gas containing nitrogen oxides, comprising a denitrification column, a cell, and a waste gas delivery device, the delivery device containing the NO x fed to the bottom of the de-NOx column, and permanganate denitration agent is delivered to the top of the stripper column denitration, the denitration permanganate agent to the NO x converted to nitrate, the remainder of the stream to the bottom of the de-NOx column, and then by the delivery device
  • the residual liquid at the bottom of the denitration column is sent to the electrolytic tank, and the electrolytic tank can electrolyze the manganese salt in the remaining liquid into permanganate to form the permanganate denitration agent.
  • the conveying device delivers the permanganate denitration agent after electrolysis to the top of the denitration column.
  • the treatment device for industrial waste gas containing nitrogen oxides further comprises a monitoring device connected to the conveying device, the monitoring device monitoring the concentration of the nitrate when the concentration of the nitrate reaches a preset In the value, the conveying device transports the remaining liquid at the bottom of the denitration column to a separation system, and the separation system recovers the nitrate after evaporating and crystallizing.
  • the processing device for industrial waste gas containing nitrogen oxides further comprises a chemical dosing device connected to the electrolytic cell for replenishing the alkali in the electrolytic cell.
  • the processing device for industrial waste gas containing nitrogen oxides further comprises a chemical dosing device connected to the electrolytic cell for replenishing the electrolyte into the electrolytic cell.
  • said nitrogen oxide industrial gas desulfurization apparatus further comprises a column connected to the denitration of the exhaust gas in the conveying means containing the NO x to the bottom of the column denitration before delivery
  • the exhaust gas is sent to the desulfurization device for desulfurization treatment.
  • the method and a processing device for treating industrial waste gas containing nitrogen oxides of the present invention have the following advantages: (1)
  • the permanganate denitration agent has strong oxidizing property and can efficiently remove NO in the exhaust gas. x , high decontamination rate; (2) using electrolysis technology to promote permanganate recycling, permanganate denitration agent in the denitrification tower oxidizes and absorbs nitrogen oxides to form by-product manganate, which is then transported to the electrolyzer Within the anode of the electrolysis cell: MnO 4 2- -e - ⁇ MnO 4 - , by-product +6-valent manganese can be converted into the desired +7-valent manganese by electrolysis, which not only recycles permanganate also achieve the purpose of reducing byproducts permanganate, both to meet the denitration requirements, reducing costs, low operating costs; (3) according to the present invention, the equipment used is simple, less investment, for all purification NO x -containing exhaust gases, such as
  • Figure 1 is a schematic illustration of a treatment apparatus for industrial waste gas containing nitrogen oxides of the present invention.
  • the invention provides a method and a processing device for treating industrial waste gas containing nitrogen oxides, which can recycle the oxidizing denitration agent permanganate, thereby reducing operating costs.
  • the exhaust gas passes through the dedusting device and is subjected to desulfurization treatment, and the desulfurized exhaust gas is input from the bottom of the denitration tower 3 via a conveying device.
  • the conveying device comprises a fan 5, the fan 5 is connected to the denitration tower 3 and the desulfurization device 7, and the output end of the fan 5 is provided with an aeration head 4, and the fan 5 can transport the desulfurized exhaust gas through the aeration head 4 to The bottom of the denitration tower 3.
  • the denitration column can be any device for denitration in the prior art, such as a spray tower or a pneumatic emulsion tower, which is not limited herein.
  • Permanganate denitration agent is an oxidizing agent for removing the exhaust gas NO x, in the present embodiment includes a base and a permanganate, permanganate denitration agent from the top of the de-NOx column 3 via a pump delivery device 2 is pumped down the exhaust gas-liquid contact permanganate denitrating agent to the NO x containing up and absorbing NO x in the exhaust gas oxidation, permanganate oxidation resistance is strong, the denitration rate of the exhaust gas , and can be adjusted according to the emission requirements, up to 99% or more, the exhaust gas denitration removal from the top of column 3 of the standard NOx discharged oxygen absorption NO x in the raffinate stream to the bottom of the de-NOx tower 3.
  • the denitration reaction equations occurring in the denitration column 3 are:
  • the reaction produces a by-product manganate which is less oxidizing than permanganate and which may be reduced to MnO 2 during the recycling process, and MnO 2 is a water-insoluble solid precipitate. Therefore, the denitration equipment is fouled and blocked, and the material and equipment need to be replaced in a short period of time; in addition, since it contains manganese metal, it cannot be discharged at will, and needs to be properly disposed before being discharged, thereby increasing the sewage treatment cost.
  • the processing apparatus of the present invention provides an electrolytic cell 1 for transporting the remaining liquid at the bottom of the denitration column 3 to the electrolytic cell 1, and the electrolytic cell 1 is energized to electrolyze the manganeseate in the remaining liquid to permanganate.
  • the electrolytic cell 1 can adopt any form of electrolysis method, such as a diaphragm method, an ion exchange method, etc., in this embodiment, a diaphragmless, dynamic electrolysis method is adopted, and the electrolysis temperature is controlled between 20 and 95 ° C, and the The current density of the electrolytic cell 1 can be adjusted, and preferably, the current density ranges from 5 to 150 mA/cm 2 .
  • electrolytic reaction equations occurring in the electrolytic cell 1 are:
  • the manganate loses electrons and regenerates the permanganate having strong oxidizing property, can be regenerated, can be recycled, and the hydrogen produced by electrolysis can be recycled or directly discharged.
  • the processing apparatus of the present invention further includes a monitoring device (not shown) connected to the conveying device, the monitoring device monitoring the concentration of the nitrate, and when the concentration of the nitrate reaches a predetermined value, the conveying device will denitrate the tower 3
  • the remaining liquid at the bottom is sent to a separation system 6, and the separation system 6 evaporates and crystallizes to recover the nitrate.
  • the remaining liquid contains manganate and permanganate, and is sent to the electrolytic cell 1 for electrolysis.
  • the present invention generates no waste water, no secondary pollution problem, and the NO x in the exhaust gas can be converted into nitrate have economic value.
  • the processing apparatus of the present invention further comprises a drug dosing device 8 connected to the electrolytic cell for replenishing the alkali in the electrolytic cell 1, and the dosage thereof can be increased or decreased according to actual needs.
  • a drug dosing device 8 connected to the electrolytic cell for replenishing the alkali in the electrolytic cell 1, and the dosage thereof can be increased or decreased according to actual needs.
  • an appropriate amount of an electrolyte such as a sulfate, a nitrate or a phosphate is added to the electrolytic cell 1 by the chemical dosing device 8.
  • Group II The mass concentration of 0.4% potassium permanganate solution from the top of the de-NOx spray tower 3 downward to the NO x concentration of 812.74mg / m 3 of exhaust gas from the bottom of the input NOx removal column 3, the raffinate
  • the electrolytic cell 1 was introduced into the electrolytic cell 1 for recycling, and the electrolytic temperature was 60 ° C, and the current density was 80 mA/cm 2 .
  • the exhaust gas denitration removal from the top of column 3 of the NOx discharge standard, NO x concentration in the exhaust emission detected is 56.08mg / m 3, the denitration rate of 93.1%.
  • Group III The mass concentration of 0.5% potassium permanganate solution from the top of the de-NOx spray tower 3 downward to the NO x concentration of 799.70mg / m 3 of exhaust gas from the bottom of the input NOx removal column 3, the raffinate After entering the electrolytic cell 1 and performing electrolysis, it was recycled, and the electrolysis temperature was 80 ° C, and the current density was 100 mA/cm 2 .
  • the exhaust gas denitration removal from the top of column 3 of the NOx discharge standard, NO x concentration in the exhaust emission detected is 6.00mg / m 3, the denitration rate reached 99.25%.
  • Group IV The mass concentration of 0.1% potassium permanganate solution from the top of the de-NOx spray tower 3 downward to the NO x concentration of 796.80mg / m 3 of exhaust gas from the bottom of the input NOx removal column 3, the raffinate After entering the electrolytic cell 1, it was recycled after electrolysis, and the electrolysis temperature was 95 ° C, and the current density was 150 mA/cm 2 .
  • the exhaust gas denitration removal from the top of column 3 of the NOx discharge standard, NO x concentration in the exhaust emission detected is 78.56mg / m 3, the denitration rate reached 90.14%.
  • the permanganate denitration agent has strong oxidizing property and can efficiently remove NO in the exhaust gas. x , high denitration rate, can reach more than 90%; (2) using electrolysis technology to promote the regeneration of permanganate, permanganate denitration agent in the denitrification tower after oxidation and absorption of nitrogen oxides to produce by-product manganate, and then It is transported into the electrolytic cell and reacts at the anode of the electrolytic cell: MnO 4 2- e - ⁇ MnO 4 - , which can convert the by-product + 6-valent manganese into the desired +7-valent manganese by electrolysis, which not only makes high manganese acid recycling, while the purpose of reducing byproducts permanganate, both to meet the denitration requirements, reducing costs, low operating costs; (3) according to the present invention, the equipment used is simple, less investment, for all

Abstract

一种含氮氧化物工业废气的处理方法，包括步骤：(1)将含NO x的废气输送至一脱硝塔（3）的底部，将高锰酸盐脱硝剂输送至所述脱硝塔（3）的顶部，所述高锰酸盐脱硝剂将所述NO x转化为硝酸盐，其余液流至所述脱硝塔（3）底部；(2)将所述脱硝塔（3）底部的所述余液输送至一电解槽（1）中，所述电解槽（1）通电，以将所述余液中的锰酸盐电解为高锰酸盐，从而形成所述高锰酸盐脱硝剂；以及(3)将电解后的所述高锰酸盐脱硝剂输送至所述脱硝塔（3）的顶部。所述的处理方法可循环利用高锰酸盐进而降低运行费用，且不结垢堵塞脱硝塔（3），不污染环境。另外，还公开了一种含氮氧化物工业废气的处理装置。

Description

一种含氮氧化物工业废气的处理方法及处理装置 技术领域
本发明涉及废气脱硝领域，尤其涉及一种使用高锰酸盐脱硝剂的方法及装置。
背景技术
随着我国经济的持续发展，能源消耗在逐年增加，NOx的排放量急速增加。氮氧化物对环境和人体、动植物的影响十分严重，NOx作为酸性气体，经氧化后溶于水生成HNO3、HNO2，并随雨水降到地面，形成酸雨。排入大气中的NOx与碳氢化合物等一次污染物在紫外线的作用下发生光化学反应产生二次污染物，这些一、二次污染物的混合物将形成光化学烟雾。NOx也是细颗粒物的前体物，细颗粒物对空气质量和能见度等有重要的影响，细颗粒物对人体呼吸系统、心血管系统、癌症、生殖与神经系统都有很严重的危害。基于氮氧化物危害的严重性，国家出台了一系列的法律法规控制氮氧化物的排放，例如“十二五”期间我国已把NOx作为约束性指标并纳入区域总量控制范围。
针对国内废气脱硝领域，适应于锅炉、工业窑炉、金属表面处理、钢铁、焦化等行业含氮氧化物废气的投资少、效率高的脱硝技术是不少学者的研究重点。湿法脱硝技术研究最多的是氧化吸收法和络合吸收法。络合吸收法因常用的络合剂Fe2+易被氧化，需要加入抗氧化剂，再生系统复杂，能耗高、运行成本高，难于推广使用；氧化吸收法往往具有去除效率高，吸收速率快、设备较为简单、运行方便等优点，能与现阶段成熟的湿法脱硝技术相结合，是相对有前途、有研究价值的一类技术。氧化吸收法是通过氧化剂将NO氧化成NO2，然后用水吸收或者碱溶液吸收进行处理，或者在碱溶液中添加氧化剂，边氧化边吸收。
其中，KMnO4已被证明是一种有效的脱硝氧化剂，无论在酸性或碱性环境 中，均能获得理想的脱硝效率，但KMnO4由于存在其自身缺陷使其在工业上的应用成为一大技术难题。首先，KMnO4价格较贵，而且高浓度的含锰废水如不处理会造成水体重金属污染，因此废水处理成本较高；另外，也是最主要的，使用KMnO4作为脱硝氧化剂，将KMnO4自脱硝塔的顶部喷入，废气自脱硝塔的底部输入，KMnO4将废气中的NOx转化为硝酸盐，少部分KMnO4在氧化脱硝的过程中首先被还原成K2MnO4，由于大部分KMnO4并未参与反应，为节约成本，会将脱硝塔底部的余液循环使用，将其再次喷入脱硝塔的顶部，在多次循环使用后部分K2MnO4被还原成MnO2，MnO2是不溶于水的固态沉淀物，从而造成脱硝设备结垢、堵塞，需要短周期更换材料与设备。由于存在上述缺陷，KMnO4氧化脱硝在工业上难以得到推广应用，是为本领域的一大技术难题。
发明内容
本发明的目的在于克服现有技术中高锰酸盐脱硝剂成本较高、易结垢堵塞的技术缺陷，提供一种使用高锰酸盐脱硝剂处理含氮氧化物工业废气的方法及装置。
为实现上述目的，本发明提供了一种含氮氧化物工业废气的处理方法，包括步骤：(1)将含NOx的废气输送至一脱硝塔的底部，将高锰酸盐脱硝剂输送至所述脱硝塔的顶部，所述高锰酸盐脱硝剂将所述NOx转化为硝酸盐，其余液流至所述脱硝塔底部；(2)将所述脱硝塔底部的所述余液输送至一电解槽中，所述电解槽通电，以将所述余液中的锰酸盐电解为高锰酸盐，从而形成所述高锰酸盐脱硝剂；以及(3)将电解后的所述高锰酸盐脱硝剂输送至所述脱硝塔的顶部。
较佳地，当所述硝酸盐的浓度达到预设值时，将所述脱硝塔底部的所述余液输送至一分离系统中，蒸发结晶后回收所述硝酸盐。
较佳地，所述含氮氧化物工业废气的处理方法还包括向所述电解槽内补充碱。
较佳地，所述含氮氧化物工业废气的处理方法还包括向所述电解槽内补充 电解质。
较佳地，所述含氮氧化物工业废气的处理方法还包括在将含NOx的所述废气输送至所述脱硝塔的底部之前将所述烟气输送至一脱硫装置进行脱硫处理。
本发明还提供一种含氮氧化物工业废气的处理装置，包括一脱硝塔、一电解槽及一输送装置，所述输送装置将含NOx的废气输送至所述脱硝塔的底部，并将高锰酸盐脱硝剂输送至所述脱硝塔的顶部，所述高锰酸盐脱硝剂将所述NOx转化为硝酸盐，其余液流至所述脱硝塔底部，所述输送装置再将所述脱硝塔底部的所述余液输送至所述电解槽内，所述电解槽可将所述余液中的锰酸盐电解为高锰酸盐，从而形成所述高锰酸盐脱硝剂，所述输送装置将电解后的所述高锰酸盐脱硝剂输送至所述脱硝塔的顶部。
较佳地，所述含氮氧化物工业废气的处理装置还包括与所述输送装置相连的一监控装置，所述监控装置监控所述硝酸盐的浓度，当所述硝酸盐的浓度达到预设值时，所述输送装置将所述脱硝塔底部的所述余液输送至一分离系统中，所述分离系统蒸发结晶后回收所述硝酸盐。
较佳地，所述含氮氧化物工业废气的处理装置还包括与所述电解槽相连的一药剂投加装置，用以向所述电解槽内补充碱。
较佳地，所述含氮氧化物工业废气的处理装置还包括与所述电解槽相连的一药剂投加装置，用以向所述电解槽内补充电解质。
较佳地，所述含氮氧化物工业废气的处理装置还包括与所述脱硝塔相连的一脱硫装置，所述输送装置在将含NOx的所述废气输送至所述脱硝塔的底部之前将所述废气输送至所述脱硫装置进行脱硫处理。
与现有技术相比，本发明的含氮氧化物工业废气的处理方法及处理装置具有以下几点优点：(1)高锰酸盐脱硝剂的氧化性强，能够高效脱除废气中的NOx，脱污率高；(2)利用电解技术促使高锰酸盐循环再生，高锰酸盐脱硝剂在脱硝塔内氧化吸收氮氧化物后生成副产物锰酸盐，然后被输送至电解槽内，在电解槽的阳极发生反应：MnO4 2--e-→MnO4 -，可以将副产物+6价锰通过电解转换为所需的+7价锰，不但使高锰酸盐循环利用，同时达到减少副产物锰酸盐的目的，既满足脱硝要求，又降低了成本，运行费用低；(3)本发明所用设备简单，投 资少，适用于所有含NOx废气的净化处理，如锅炉、工业窑炉、金属表面处理、钢铁、焦化等行业的废气，适用范围广，经济环境效益可观；(4)废气中的NOx可以转化为有高经济价值、用途广泛的硝酸盐，使得氮资源得到充分回收利用；(5)高锰酸盐在氧化脱硝的过程中首先被还原成锰酸盐，并在被循环利用之前使用电解槽将余液中的锰酸盐及时地转换成了高锰酸盐，防止了锰酸盐在进一步氧化脱硝的过程中被还原成二氧化锰，因此脱硝工艺能连续稳定运行，不存在现有的脱硝设备常存在的诸如结垢、堵塞和短周期更换材料与设备等问题。
附图说明
图1是本发明含氮氧化物工业废气的处理装置的示意图。
具体实施方式
现在参考附图描述本发明的实施例，附图中类似的元件标号代表类似的元件。
本发明提供了一种含氮氧化物工业废气的处理方法及处理装置，可循环利用氧化脱硝剂高锰酸盐，进而降低运行费用。
如图1所示，废气经过除尘后进入脱硫装置7进行脱硫处理，脱硫后的废气经输送装置自脱硝塔3的底部输入。具体地，输送装置包括一风机5，风机5与脱硝塔3及脱硫装置7相连，且风机5的输出端设有一曝气头4，风机5可将脱硫后的废气经曝气头4输送至脱硝塔3的底部。脱硝塔可为现有技术中所有用于脱硝的装置，例如喷淋塔或气动乳化塔，在此不做限制。高锰酸盐脱硝剂为氧化剂，用以脱除废气中的NOx，在本实施例中包括有高锰酸盐及碱，高锰酸盐脱硝剂自脱硝塔3的顶部经输送装置的泵2泵入，向下的高锰酸盐脱硝剂与向上的含NOx的废气气液接触，并将废气中的NOx氧化吸收，由于高锰酸盐的氧化性强，废气的脱硝率高，并可以根据排放要求进行调整，最高可达99％以上，脱硝后的废气自脱硝塔3的顶部达标排出，氧化吸收NOx后的余液流至脱硝塔3的底部。
具体地，在脱硝塔3内发生的脱硝反应方程式有：
3MnO4 -+NO+4OH-→3MnO4 2-+NO3 -+2H2O；
MnO4 -+NO2+2OH-→MnO4 2-+NO3 -+H2O；
从上述脱硝反应方程式中可知，反应产生了副产物锰酸根，其氧化性低于高锰酸根，且其在重复利用的过程中可能被还原成MnO2，MnO2是不溶于水的固态沉淀物，从而造成脱硝设备结垢、堵塞，需要短周期更换材料与设备；另外，由于其含有金属元素锰，也不可随意排放，需要得到妥善处理后才可排放，这样增加了污水处理成本。为此，本发明的处理装置提供一电解槽1，将脱硝塔3底部的余液输送至该电解槽1中，电解槽1通电，以将余液中的锰酸盐电解为高锰酸盐。具体地，该电解槽1可采用任何形式的电解方法，例如隔膜法，离子交换法等，在本实施例中采用无隔膜、动态电解法，电解温度控制在20～95℃之间，且该电解槽1的电流密度可调节，较佳地，电流密度的范围为5～150mA/cm2。
具体地，电解槽1内发生的电解反应方程式有：
阳极，MnO4 2-e-→MnO4 -；以及
阴极：2H++2e-→H2↑。
从上述电解反应方程式可知，锰酸盐失电子重新生成具有强氧化性的高锰酸盐，得以再生，可循环利用，电解产生的氢气可回收利用或直接排放。
从上述脱硝反应方程式中亦可知，高锰酸盐脱硝剂将NOx转化为硝酸盐，其具有工业价值，可回收利用。具体地，本发明的处理装置还包括与输送装置相连的一监控装置(图未示)，监控装置监控硝酸盐的浓度，当硝酸盐的浓度达到一预设值时，输送装置将脱硝塔3底部的余液输送至一分离系统6中，分离系统6蒸发结晶后回收硝酸盐，余液含有锰酸盐及高锰酸盐，输送至电解槽1内进行电解。可见，本发明无废水产生，无二次污染问题，且可将废气中的NOx转化为有经济价值的硝酸盐。
较佳地，本发明的处理装置还包括与电解槽相连的一药剂投加装置8，用以向电解槽1内补充碱，其投加量可根据实际需要进行增减。另外，为了提高电解效率，会通过药剂投加装置8向电解槽1加入适量的电解质，如硫酸盐、硝酸盐或磷酸盐等。
依据以上含氮氧化物工业废气的处理方法及处理装置，同时进行以下几组数据测试。
第一组：将质量百分比浓度为0.5％的高锰酸钾溶液自脱硝塔3的顶部向下喷淋，将NOx浓度为1314.84mg/m3的废气自脱硝塔3的底部输入，余液进入电解槽1内进行电解后循环利用，电解温度为20℃，电流密度为5mA/cm2。脱硝后的废气自脱硝塔3的顶部达标排出，检测排放的废气的NOx浓度为65.74mg/m3，脱硝率达到了95％。
第二组：将质量百分比浓度为0.4％的高锰酸钾溶液自脱硝塔3的顶部向下喷淋，将NOx浓度为812.74mg/m3的废气自脱硝塔3的底部输入，余液进入电解槽1内进行电解后循环利用，电解温度为60℃，电流密度为80mA/cm2。脱硝后的废气自脱硝塔3的顶部达标排出，检测排放的废气的NOx浓度为56.08mg/m3，脱硝率达到了93.1％。
第三组：将质量百分比浓度为0.5％的高锰酸钾溶液自脱硝塔3的顶部向下喷淋，将NOx浓度为799.70mg/m3的废气自脱硝塔3的底部输入，余液进入电解槽1内进行电解后循环利用，电解温度为80℃，电流密度为100mA/cm2。脱硝后的废气自脱硝塔3的顶部达标排出，检测排放的废气的NOx浓度为6.00mg/m3，脱硝率达到了99.25％。
第四组：将质量百分比浓度为0.1％的高锰酸钾溶液自脱硝塔3的顶部向下喷淋，将NOx浓度为796.80mg/m3的废气自脱硝塔3的底部输入，余液进入电解槽1内进行电解后循环利用，电解温度为95℃，电流密度为150mA/cm2。脱硝后的废气自脱硝塔3的顶部达标排出，检测排放的废气的NOx浓度为78.56mg/m3，脱硝率达到了90.14％。
从以上四组数据可知，本发明的含氮氧化物工业废气的处理方法及处理装置具有高脱硝率，脱硝率均在90％以上。
与现有技术相比，本发明的含氮氧化物工业废气的处理方法及处理装置具有以下几点优点：(1)高锰酸盐脱硝剂的氧化性强，能够高效脱除废气中的NOx，脱硝率高，可达到90％以上；(2)利用电解技术促使高锰酸盐循环再生，高锰酸盐脱硝剂在脱硝塔内氧化吸收氮氧化物后生成副产物锰酸盐，然后被输送至 电解槽内，在电解槽的阳极发生反应：MnO4 2-e-→MnO4 -，可以将副产物+6价锰通过电解转换为所需的+7价锰，不但使高锰酸盐循环利用，同时达到减少副产物锰酸盐的目的，既满足脱硝要求，又降低了成本，运行费用低；(3)本发明所用设备简单，投资少，适用于所有含NOx废气的净化处理，如锅炉、工业窑炉、金属表面处理、钢铁、焦化等行业的废气，适用范围广，经济效益可观；(4)废气中的NOx可以转化为有高经济价值、用途广泛的硝酸盐，使得氮资源得到充分回收利用；(5)高锰酸盐在氧化脱硝的过程中首先被还原成锰酸盐，并在被循环利用之前使用电解槽将余液中的锰酸盐及时地转换成了高锰酸盐，防止了锰酸盐在进一步氧化脱硝的过程中被还原成二氧化锰，因此脱硝工艺能连续稳定运行，不存在现有的脱硝设备常存在的诸如结垢、堵塞和短周期更换材料与设备等问题。
以上所揭露的仅为本发明的优选实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明申请专利范围所作的等同变化，仍属本发明所涵盖的范围。

Claims (10)

  1. 一种含氮氧化物工业废气的处理方法，其特征在于，包括步骤：
    (1)将含NOx的废气输送至一脱硝塔的底部，将高锰酸盐脱硝剂输送至所述脱硝塔的顶部，所述高锰酸盐脱硝剂将所述NOx转化为硝酸盐，其余液流至所述脱硝塔底部；
    (2)将所述脱硝塔底部的所述余液输送至一电解槽中，所述电解槽通电，以将所述余液中的锰酸盐电解为高锰酸盐，从而形成所述高锰酸盐脱硝剂；以及
    (3)将电解后的所述高锰酸盐脱硝剂输送至所述脱硝塔的顶部。
  2. 如权利要求1所述的含氮氧化物工业废气的处理方法，其特征在于：当所述硝酸盐的浓度达到预设值时，将所述脱硝塔底部的所述余液输送至一分离系统中，蒸发结晶后回收所述硝酸盐。
  3. 如权利要求1所述的含氮氧化物工业废气的处理方法，其特征在于：还包括向所述电解槽内补充碱。
  4. 如权利要求1所述的含氮氧化物工业废气的处理方法，其特征在于：还包括向所述电解槽内补充电解质。
  5. 如权利要求1所述的含氮氧化物工业废气的处理方法，其特征在于：还包括在将含NOx的所述废气输送至所述脱硝塔的底部之前将所述烟气输送至一脱硫装置进行脱硫处理。
  6. 一种含氮氧化物工业废气的处理装置，其特征在于，包括一脱硝塔、一电解槽及一输送装置，所述输送装置将含NOx的废气输送至所述脱硝塔的底部， 并将高锰酸盐脱硝剂输送至所述脱硝塔的顶部，所述高锰酸盐脱硝剂将所述NOx转化为硝酸盐，其余液流至所述脱硝塔底部，所述输送装置再将所述脱硝塔底部的所述余液输送至所述电解槽内，所述电解槽可将所述余液中的锰酸盐电解为高锰酸盐，从而形成所述高锰酸盐脱硝剂，所述输送装置将电解后的所述高锰酸盐脱硝剂输送至所述脱硝塔的顶部。
  7. 如权利要求6所述的含氮氧化物工业废气的处理装置，其特征在于：还包括与所述输送装置相连的一监控装置，所述监控装置监控所述硝酸盐的浓度，当所述硝酸盐的浓度达到预设值时，所述输送装置将所述脱硝塔底部的所述余液输送至一分离系统中，所述分离系统蒸发结晶后回收所述硝酸盐。
  8. 如权利要求6所述的含氮氧化物工业废气的处理装置，其特征在于：还包括与所述电解槽相连的一药剂投加装置，用以向所述电解槽内补充碱。
  9. 如权利要求6所述的含氮氧化物工业废气的处理装置，其特征在于：还包括与所述电解槽相连的一药剂投加装置，用以向所述电解槽内补充电解质。
  10. 如权利要求6所述的含氮氧化物工业废气的处理装置，其特征在于：还包括与所述脱硝塔相连的一脱硫装置，所述输送装置在将含NOx的所述废气输送至所述脱硝塔的底部之前将所述废气输送至所述脱硫装置进行脱硫处理。
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