CN113385013B - Method for flue gas denitration by using gaseous organic matter as SNCR additive - Google Patents

Method for flue gas denitration by using gaseous organic matter as SNCR additive Download PDF

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CN113385013B
CN113385013B CN202110718058.XA CN202110718058A CN113385013B CN 113385013 B CN113385013 B CN 113385013B CN 202110718058 A CN202110718058 A CN 202110718058A CN 113385013 B CN113385013 B CN 113385013B
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denitration
sncr
gaseous organic
organic matter
concentration
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CN113385013A (en
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王亚丽
宋易徽
崔素萍
韩晓宁
马晓宇
兰明章
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Beijing University of Technology
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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
    • B01D53/76—Gas phase processes, e.g. by using aerosols
    • 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
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    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Environmental & Geological Engineering (AREA)
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Abstract

Method for using gaseous organic matter as SNCA method for applying an R additive to an SNCR technology belongs to the technical field of smoke pollutant control. The invention uses the gas generating device to gasify the organic matters, and the gaseous organic matters are carried into the SNCR denitration system by the carrier gas to be subjected to denitration. At 750-950 ℃, the oxygen concentration is 1-3 vol%, the NO concentration is 1000ppm, and NH is generated 3 NO is carried out by using gaseous organic matter as SNCR additive under the condition that the molar ratio of the gaseous organic matter to NO is 1 x And (4) removing. Organic matters can generate dehydrogenation reaction in the anoxic combustion process, active groups H and OH are provided for SNCR denitration at low temperature, and NH is promoted 3 Reaction to generate key intermediate product NH 2 The SNCR denitration temperature window can be moved to a low temperature, and the optimal denitration temperature is reduced. The gaseous organic matter is used as the additive for SNCR denitration, so that the investment cost is low, the operation is simple, and the temperature window for SNCR denitration can be reduced.

Description

Method for flue gas denitration by using gaseous organic matter as SNCR additive
Technical Field
The invention belongs to the technical field of flue gas pollutant control, and particularly relates to a method for denitration by using a gaseous organic matter as an SNCR additive.
Background
With the advent of the haze era, the environmental pollution problem has received increasing attention, and Nitrogen Oxides (NO) have become more attractive x ) As one of the main pollution sources of the atmosphere, the method also attracts wide attention of all people. The nitrogen oxide can cause the formation of acid rain and photochemical smog, thereby causing great harm to the environment of China and having strong toxic action on human bodies. Selective non-catalytic reduction (SNCR) is an industrially common NOx emission reduction technology, and means that ammonia water or urea is used as a reducing agent to selectively reduce NO in flue gas into N within a temperature range of 900-1050 ℃ under the condition of NO catalyst 2 . SNCR as an economically efficient NO x The control technology is widely applied, but in practical application, due to the influence of factors such as temperature window, ammonia-nitrogen ratio, residence time and the like, the SNCR denitration efficiency can only reach 30-50% under the condition of using excessive reducing agent. The key to the SNCR reaction is the reactive groups OH and H, which are not sufficient at low temperaturesReactive group, resulting in NO reduction x And thus the use is greatly limited by the temperature window. In order to increase the application sites of the SNCR denitration technology and improve the denitration rate, more and more researches are focused on widening the temperature window of the SNCR.
Organic matters can be combusted at high temperature in an anoxic environment to generate dehydrogenation reaction, so that active groups H and OH are provided for SNCR (selective non-catalytic reduction) denitration, and NH is promoted 3 Formation of NH 2 And the SNCR denitration rate is improved. CH generated during combustion of organic matter i 、CO、H 2 Small molecule gases such as O can also react to generate active groups H and OH, and further promote the SNCR denitration. Therefore, by using an organic substance as an additive for SNCR denitration, the temperature window for SNCR denitration can be widened toward low temperatures, and the use places for SNCR denitration can be increased.
Disclosure of Invention
The invention aims to provide a method for applying gaseous organic matters as additives to SNCR technology, which can effectively remove NOx and reduce the temperature window of SNCR denitration.
The invention adopts the following specific technical scheme:
a method for denitration of flue gas by using gaseous organic matters as an SNCR additive is characterized by comprising the following steps: gasifying the liquid organic matter at 100 deg.c in a gas generator by means of water bath bubbling process, and maintaining the gasifying speed with N 2 And the carrier gas brings gaseous organic matters into a denitration system for flue gas denitration.
When the concentration of oxygen is 1-3 vol.%, the concentration of NO is 1000ppm, and NH 3 In a molar ratio of 1, N to NO 2 In the mixed gas as the balance gas, the total gas flow rate is 200mL/min, and SNCR denitration is carried out by using gaseous organic matters as additives under the conditions of 750-950 ℃, wherein the ratio of the concentration of the gaseous organic matters to the total gas flow rate is 1000 ppm: 200 mL/min.
The principle of promoting SNCR denitration by organic matters is as follows:
H+O 2 →O+OH (1)
NH 3 +OH→NH 2 +H 2 O (2)
NH 3 +O→NH 2 +OH (3)
NH 3 +H→NH 2 +H 2 (4)
NH 2 +NO→NNH+OH (5)
NNH→H+N 2 (6)
the invention has the following effects:
(1) organic matters can generate dehydrogenation reaction in the anoxic combustion process, active groups H and OH are provided for SNCR denitration at low temperature, and NH is promoted 3 Reaction to generate key intermediate product NH 2 And the denitration rate is improved. The addition of the organic matter can shift the SNCR denitration temperature window to a low temperature, the optimal denitration temperature is reduced, and the maximum denitration rate is almost unchanged.
(2) The gaseous organic matter is used as the SNCR additive, so that the investment cost is low and the operation is simple.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
First, organic matter was gasified by a gas generator, and denitration was performed by gaseous organic matter, and all the organic matter in the following examples was gaseous.
Example 1
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，2vol.％O 2 ，N 2 The total gas flow rate is 200mL/min as balance gas, 1000ppm gaseous ethanol is introduced into a tubular furnace with the diameter of 6mm under the temperature condition of 750 ℃, and the denitration rate reaches 90.4%.
Example 2
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，2vol.％O 2 ，N 2 The total gas flow rate is 200mL/min as balance gas, and when the temperature condition is 800 ℃, 1000ppm of gaseous benzene is introduced into a tubular furnace with the diameter of 6mm, and the denitration rate reaches 77.5%.
Example 3
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，2vol.％O 2 ，N 2 The total gas flow rate is 200mL/min as balance gas, 1000ppm of gaseous octane is introduced into a tubular furnace with the diameter of 6mm under the temperature condition of 750 ℃, and the denitration rate reaches 75.9%.
Example 4
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，2vol.％O 2 ，N 2 The total gas flow rate is 200mL/min as balance gas, when the temperature condition is 800 ℃, 1000ppm of gaseous octane is introduced into a tubular furnace with the diameter of 6mm, and the denitration rate reaches 73.0 percent.
Example 5
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，1vol.％O 2 ，N 2 The total gas flow rate is 200mL/min as balance gas, and when the temperature condition is 800 ℃, 1000ppm gaseous acetone is introduced into a tubular furnace with the diameter of 6mm, and the denitration rate reaches 75.0%.
Example 6
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，1vol.％O 2 ，N 2 The gas is balance gas, the total gas flow rate is 200mL/min, when the temperature condition is 800 ℃, 1000ppm gaseous ethanol is introduced into a tubular furnace with the diameter of 6mm, and the denitration rate reaches 90.4%.
Example 7
Under the smoke condition of 1000ppmNO and 1000ppmNH 3 ，3vol.％O 2 ，N 2 The gas is balance gas, the total gas flow rate is 200mL/min, when the temperature condition is 800 ℃, 1000ppm gaseous ethanol is introduced into a tubular furnace with the diameter of 6mm, and the denitration rate reaches 80.5 percent.
TABLE 1 denitration rate of each example
Figure BDA0003135766340000031

Claims (1)

1. Flue gas by using gaseous organic matter as SNCR additiveThe denitration method is characterized by comprising the following steps: firstly, a water bath bubbling method is adopted, ethanol liquid is gasified at the heating temperature of 100 ℃, and N is used after the ethanol gasification speed is kept constant 2 Introducing 1000ppm ethanol into an SNCR (selective non-catalytic reduction) denitration system for carrier gas to perform flue gas denitration;
o of the environment of use 2 1% or 2% by volume, NO concentration 1000ppm, NH 3 In a molar ratio of 1, N to NO 2 In the mixed gas as the balance gas, the total gas flow rate is 200mL/min, gaseous organic matters are used as SNCR additives for denitration, and the ratio of the concentration of the gaseous organic matters to the total gas flow rate is 1000 ppm: 200 mL/min; when O is present 2 When the volume concentration is 1%, the reaction temperature is 800 ℃; when O is present 2 At a concentration of 2% by volume, the reaction temperature was 750 ℃.
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
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US5489419A (en) * 1992-10-13 1996-02-06 Nalco Fuel Tech Process for pollution control
JP2002530575A (en) * 1998-11-23 2002-09-17 モービル・オイル・コーポレイション Liquid urea additive for exhaust gas treatment
CN101721904A (en) * 2010-01-21 2010-06-09 山东大学 Composite denitration method by biomass direct reburning and selective non-catalytic reduction
US8535627B1 (en) * 2012-12-12 2013-09-17 Southwest Research Institute Ketone/water mixtures for NOx removal
CN106215652B (en) * 2016-08-31 2019-04-02 上海交通大学 A kind of the combination denitrating system and method for aluminium oxide calcining flue gas
CN209221862U (en) * 2017-12-15 2019-08-09 山西国峰煤电有限责任公司 A kind of circulating fluidized bed boiler SNCR denitration system
CN111715050B (en) * 2019-03-20 2021-10-15 中国科学院大连化学物理研究所 Method for improving urea denitration efficiency by adopting alkaline alcohol solution
CN212440697U (en) * 2020-03-05 2021-02-02 华电电力科学研究院有限公司 System for gaseous additive widens SNCR denitration technique reaction temperature window

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