CN107638785A - A kind of method of liquid phase oxidation denitration - Google Patents

A kind of method of liquid phase oxidation denitration Download PDF

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Publication number
CN107638785A
CN107638785A CN201710907887.6A CN201710907887A CN107638785A CN 107638785 A CN107638785 A CN 107638785A CN 201710907887 A CN201710907887 A CN 201710907887A CN 107638785 A CN107638785 A CN 107638785A
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solution
ferrous sulfate
oxidizing agent
sulfate heptahydrate
hydrogen peroxide
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CN107638785B (en
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王京刚
王佩
邵亚男
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The present invention relates to a kind of method of liquid phase oxidation denitration, and using hydrogen peroxide, ferrous sulfate heptahydrate and chelating agent, for wherein hydrogen peroxide as oxidant, ferrous sulfate heptahydrate is catalyst, is comprised the following steps that:(1) hydrogen peroxide that mass fraction is 30% is configured to the oxidizing agent solution of different quality containing;(2) pH to 2 ~ 6 of oxidizing agent solution is adjusted with acid solution;(3) ferrous sulfate heptahydrate and chelating agent are configured to the aqueous solution, and are added drop-wise in oxidizing agent solution.Benefit of the invention is that technological process is simple, reaction will not produce iron cement after terminating, and have ideal denitration efficiency.

Description

A kind of method of liquid phase oxidation denitration
Technical field
The invention belongs to smoke catalytic technical field, and in particular to a kind of liquid phase oxidation denitration technology.
Background technology
One of the major pollutants of nitrogen oxides as air, a series of pernicious chemical reaction can be played in an atmosphere, Harm can also be produced to health simultaneously.In face of the resource constraint and emission reduction increasingly highlighted, in addition to technological progress, how Energy-consuming and discharged nitrous oxides are reduced while appropriate speed for economic growth is kept, this be realize sustainable development science and Realistic problem.
Due to the limitation of low-NO_x combustion technology in existing power plant's stove, NOx discharge can not reach gratifying journey Degree, in order to further reduce NOx discharge, it is necessary to which denitration process is carried out to the flue gas after burning.
In widely used Dry denitration method, using it is more be selective reduction denitration (SCR) and selective oxygen Change denitration (SCO) method.SCR method has its limitation.On the one hand, for present coal-fired plant flue gas denitration, in SCR In method of denitration, it is nitrogen by the nitric oxide reduction in flue gas, nitric oxide is not utilized effectively;On the other hand, For the consideration to catalyst activity, SCR catalytic device is typically located at high temperature section, i.e., catalyst is arranged on into boiler economizer Afterwards, before air preheater.Flue gas environmental condition on this position residing for catalyst is more severe, as dust concentration is higher, Heavy metal concentration is higher etc. so that catalyst is in easy to wear, easy and blocked, easily under conditions of poisoning so that catalyst needs frequency Numerous regular maintenance (such as soot blowing cleaning), shortens service life, increases operating cost.
Chinese patent literature CN1768902A discloses a kind of ozone oxidation and denitration method of boiler flue gas, and the gaseous oxidation takes off The advantages of nitre method, is denitration efficiency height, but the preparation price of ozone is higher, and gas is not easy to storage transport.
Chinese patent literature CN101352645A discloses a kind of flue gas catalytic oxidation denitration technique.Use with TiO2Or ZrO2-TiO2For carrier, Co is the catalyst of active component, using the oxygen contained in itself in flue gas, by oxidation of nitric oxide into After nitrogen dioxide soluble in water, using alkali liquor absorption, oxynitrides is removed.The invention is two in flue gas after control aoxidizes After the content of nitrogen oxide, nitrite that can be in the recovery denitration accessory substance of selectivity realizes the recycling of product.But denitration Required temperature is higher, and cost is higher.
The content of the invention
The problem of current denitrating flue gas is present for more than, the invention provides a kind of liquid phase oxidation method of denitration, reaction Green using medicine, technological process is simple, and reaction will not produce iron cement after terminating, and has ideal denitration effect Rate, cost is cheap, and effect is good.
The present invention adopts the following technical scheme that:A kind of method of liquid phase oxidation denitration, uses hydrogen peroxide, ferrous sulfate heptahydrate And chelating agent, for wherein hydrogen peroxide as oxidant, ferrous sulfate heptahydrate is catalyst, is comprised the following steps that:
(1) hydrogen peroxide that mass fraction is 30% is configured to the oxidizing agent solution of different quality containing;
(2) pH to 2 ~ 6 of oxidizing agent solution is adjusted with acid solution;
(3) ferrous sulfate heptahydrate and chelating agent are configured to the aqueous solution, and are added drop-wise in oxidizing agent solution.
In a preferred embodiment of the present invention, the mass fraction of the oxidizing agent solution described in step (1) be 1% ~ 7%。
In a preferred embodiment of the present invention, the chelating agent described in step (3) is oxalic acid, glycine, citric acid In one or more.
In a preferred embodiment of the present invention, the mol ratio of described ferrous sulfate heptahydrate and chelating agent is 1:(1~ 4), preferably 1:1.
In the preferred embodiment of the present invention, oxidizing agent solution is placed in 30-40 DEG C of water-bath, with pump to oxygen The mixed solution of ferrous sulfate heptahydrate and chelating agent is added dropwise in agent solution.
A kind of the problem of present invention produces a large amount of iron cements for Fenton process denitration technology, there is provided new solution.With showing There is technology to compare, the present invention has the following advantages that:
(1) drug price is cheap used in, can reduce cost;
(2) course of reaction and end will not produce the three wastes, environment friendly and pollution-free;
(3) NO clearance reaches the efficiency of presently relevant document report, up to 94%, and operating method is simple, and cost is low, and phase The removal efficiency answered does not reduce.
Embodiment
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, present invention specific examples below Illustrate, but the present invention is limited to absolutely not these examples.
Embodiment 1:
The hydrogen peroxide for taking 15mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 5%, with hydrochloric acid by solution PH is adjusted to 3, device is placed in 40 DEG C of water-bath, and mol ratio is added dropwise as 1 into reaction unit with pump:1 seven water sulfuric acid Ferrous and citric acid mixed solution, the clearance for measuring NO are 94.1%.
Embodiment 2:
The hydrogen peroxide for taking 5mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 1%, with hydrochloric acid by solution PH is adjusted to 2, device is placed in 30 DEG C of water-bath, and mol ratio is added dropwise as 1 into reaction unit with pump:1 seven water sulfuric acid Ferrous and glycine mixed solution, the clearance for measuring NO are 93.4%.
Embodiment 3:
The hydrogen peroxide for taking 35mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 7%, with hydrochloric acid by solution PH is adjusted to 6, device is placed in 30 DEG C of water-bath, and mol ratio is added dropwise as 1 into reaction unit with pump:1 seven water sulfuric acid Ferrous and oxalic acid mixed solution, the clearance for measuring NO is 91 .2%.
Embodiment 4:
The hydrogen peroxide for taking 50mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 10%, with hydrochloric acid by solution PH be adjusted to 3, device is placed in 40 DEG C of water-bath, mol ratio is added dropwise into reaction unit with pump as 1:1 seven water sulphur Sour ferrous with citric acid mixed solution, the clearance for measuring NO is 92.7%.
Embodiment 5:
The hydrogen peroxide for taking 15mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 5%, with hydrochloric acid by solution PH is adjusted to 3, device is placed in 40 DEG C of water-bath, and mol ratio is added dropwise as 1 into reaction unit with pump:5 seven water sulfuric acid Ferrous and glycine mixed solution, the clearance for measuring NO are 92.1%.
Embodiment 6:
The hydrogen peroxide for taking 15mL mass fractions to be 30% is configured to the aqueous solution that 250mL mass fractions are 5%, with hydrochloric acid by solution PH is adjusted to 3, device is placed in 40 DEG C of water-bath, and mol ratio is added dropwise as 1 into reaction unit with pump:7 seven water sulfuric acid Ferrous and glycine mixed solution, the clearance for measuring NO are 94.5%.
Although above-mentioned the embodiment of the present invention is described in conjunction with the embodiments, not the present invention is protected The limitation of scope, one of ordinary skill in the art should be understood that on the basis of technical scheme, those skilled in the art Various modifications or deformation that creative work can make need not be paid still within protection scope of the present invention.

Claims (5)

  1. A kind of 1. method of liquid phase oxidation denitration, it is characterised in that using hydrogen peroxide, ferrous sulfate heptahydrate and chelating agent, wherein For hydrogen peroxide as oxidant, ferrous sulfate heptahydrate is catalyst, is comprised the following steps that:
    (1) hydrogen peroxide that mass fraction is 30% is configured to the oxidizing agent solution of different quality containing;
    (2) pH to 2 ~ 6 of oxidizing agent solution is adjusted with acid solution;
    (3) ferrous sulfate heptahydrate and chelating agent are configured to the aqueous solution, and are added drop-wise in oxidizing agent solution.
  2. 2. according to the method for claim 1, it is characterised in that the mass fraction of the oxidizing agent solution described in step (1) For 1% ~ 7%.
  3. 3. according to the method for claim 1, it is characterised in that chelating agent described in step (3) is oxalic acid, glycine, One or more in citric acid.
  4. 4. according to the method for claim 1, it is characterised in that described ferrous sulfate heptahydrate and the mol ratio of chelating agent are 1:(1 ~ 4), preferably 1:1.
  5. 5. according to the method for claim 1, it is characterised in that oxidizing agent solution is placed in 30-40 DEG C of water-bath, used The mixed solution of ferrous sulfate heptahydrate and chelating agent is added dropwise into oxidizing agent solution for pump.
CN201710907887.6A 2017-09-29 2017-09-29 Liquid-phase oxidation denitration method Active CN107638785B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102008882A (en) * 2010-11-22 2011-04-13 上海电力学院 Fenton reagent for denitration of power plant smoke and denitration method by using the same
CN103214079A (en) * 2013-04-27 2013-07-24 华南理工大学 Bidirectional flow internal circulation type PS advanced oxidation reactor and sewage treatment method
CN103435143A (en) * 2013-08-27 2013-12-11 华南理工大学 Method for advanced oxidation treatment of wastewater through complex ferrous activated persulfate or hydrogenperoxosulfate by multicomponent blending
CN103482751A (en) * 2013-10-14 2014-01-01 河海大学 Application of biodegradable chelating agent EDDS (Ethylenediaminedisuccinic Acid) to treatment on non-degradable organic wastewater
CN107082482A (en) * 2017-04-18 2017-08-22 东南大学 A kind of synergy of Fenton systems and discharge-reducing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102008882A (en) * 2010-11-22 2011-04-13 上海电力学院 Fenton reagent for denitration of power plant smoke and denitration method by using the same
CN103214079A (en) * 2013-04-27 2013-07-24 华南理工大学 Bidirectional flow internal circulation type PS advanced oxidation reactor and sewage treatment method
CN103435143A (en) * 2013-08-27 2013-12-11 华南理工大学 Method for advanced oxidation treatment of wastewater through complex ferrous activated persulfate or hydrogenperoxosulfate by multicomponent blending
CN103482751A (en) * 2013-10-14 2014-01-01 河海大学 Application of biodegradable chelating agent EDDS (Ethylenediaminedisuccinic Acid) to treatment on non-degradable organic wastewater
CN107082482A (en) * 2017-04-18 2017-08-22 东南大学 A kind of synergy of Fenton systems and discharge-reducing method

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