CN103263848A - Flue gas treatment method of catalysis and simultaneous desulfurization and denitrification - Google Patents

Flue gas treatment method of catalysis and simultaneous desulfurization and denitrification Download PDF

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CN103263848A
CN103263848A CN2013101849938A CN201310184993A CN103263848A CN 103263848 A CN103263848 A CN 103263848A CN 2013101849938 A CN2013101849938 A CN 2013101849938A CN 201310184993 A CN201310184993 A CN 201310184993A CN 103263848 A CN103263848 A CN 103263848A
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nitrogen
mass percent
flue gas
dioxide
nitric oxide
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CN103263848B (en
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何汉兵
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Central South University
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Central South University
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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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention provides a flue gas treatment method of catalysis and simultaneous desulfurization and denitrification. The method comprises the following steps of: enabling a mixed gas (sulfur dioxide, nitric oxide and nitrogen dioxide) to pass through an oxidation-reduction catalyst at high temperature so that an auto-oxidation-reduction reaction happens between the sulfur dioxide and the nitric oxide or nitrogen dioxide and the sulfur dioxide is converted into sulfur trioxide; recovering by use of waste iron and dilute acid to obtain a ferrous sulfate heptahydrate product; converting the nitric oxide or nitrogen dioxide into nitrogen; and performing follow-up cooling of the nitrogen and recovering, wherein the air speed is 3,000-30,000mL/(g.h), the reaction temperature is 100-800 DEG C, the desulfurization efficiency is over 95%, the denitrification efficiency is over 70%, the recovery rate of sulfur trioxide is over 90%, and the recovery rate of N2 is over 90%. The method provided by the invention can realize treatment of a waste by use of another waste and catalysis and simultaneous desulfurization and denitrification, and can recover a high added-value product; and the tail gas also can meet the existing emission standard.

Description

A kind of catalysis is the flue gas processing method of desulphurization denitration simultaneously
Technical field
The invention belongs to the environmental protection science field, relate to a kind of catalysis flue gas processing method of desulphurization denitration simultaneously.
Background technology
Smoke gas treatment is one of environmental protection important contents at present, and the expection sulfur dioxide (SO2) emissions reduce 8% in country " the 12 " planning, and discharged nitrous oxides reduces 10%, so flue gas desulfurization and denitrification has become environmental protection field urgent problem.
The desulphurization denitration technology is divided into two classes simultaneously: (1) catalytic reduction method, utilize catalytic reducer with NO exactly XBe reduced into N 2, SO 2Be absorbed the back exhaust emissions, realize desulphurization denitration simultaneously; (2) oxidation absorption process is utilized various strong oxidizers such as NaClO 2, ClO 2, HClO 3, KMnO 4Deng, water-fast NO oxidation is generated NO 2Thereby, and SO 2Be absorbed simultaneously in the later stage.
Oxidizing process is the oxidant price comparison costliness that adopts usually of desulphurization denitration simultaneously, and the desulphurization denitration product is difficult to separate, and value is little; And reducing process while desulfurizing and denitrifying process temperature height, catalyst price comparison costliness, product is difficult to recycle.Therefore, need the consideration treatment of wastes with processes of wastes against one another to reduce cost and reach the purpose of desulphurization denitration simultaneously.
The present invention proposes a kind of catalysis method of desulphurization denitration simultaneously, especially at power plant and metallurgical works institute discharged flue gas, under hot conditions, allow mist (sulfur dioxide, nitric oxide and nitrogen dioxide gas) pass through oxidation reduction catalyst, make the automatic oxidation reduction reaction takes place between sulfur dioxide and nitric oxide or the nitrogen dioxide, gaseous sulfur dioxide is converted into sulfur trioxide, nitric oxide and nitrogen dioxide gas are converted into nitrogen, tail gas reclaims ferrous sulfate heptahydrate through scrap iron and dilute sulfuric acid, reclaim the follow-up cooling of nitrogen back, and desulfuration efficiency is more than 95%; Denitration efficiency is more than 70%, and the sulfur trioxide rate of recovery is more than 90%, N 2The rate of recovery is more than 90%.Can reach the treatment of wastes with processes of wastes against one another out of stock purpose and the recyclable high value added product of catalytic desulfurization simultaneously, tail gas also can reach existing discharge standard.
Summary of the invention
The purpose of this invention is to provide a kind of catalysis flue gas processing method of desulphurization denitration simultaneously.Utilize this method can reach the treatment of wastes with processes of wastes against one another out of stock purpose of catalytic desulfurization simultaneously, and recyclable high value added product, also can guarantee the rate of recovery of conversion ratio and product sulfur trioxide and the nitrogen of sulfur in smoke and nitrogen oxide, solve the not high and auxiliary product of existing denitrification efficiency and be difficult to the problem of separating and reclaiming.
A kind of catalysis is the flue gas processing method of desulphurization denitration simultaneously, under hot conditions, allow the flue gas that contains sulfur dioxide, nitric oxide and nitrogen dioxide gas pass through oxidation reduction catalyst, make sulfur dioxide respectively and the automatic oxidation reduction reaction takes place between the nitric oxide, nitrogen dioxide, Sulphur Dioxide is sulfur trioxide, nitric oxide and nitrogen dioxide gas are converted into nitrogen, absorb sulfur trioxide recovery ferrous sulfate heptahydrate through scrap iron and dilute sulfuric acid, recycle nitrogen cooling back.
Described flue gas comprises power plant and metallurgical works institute discharged flue gas.
Described oxidation reduction catalyst is following one or more: 1) ZrO 2Be 3% Pt with adding mass percent after H-ZSM-5 mixes according to mol ratio 1:3 again; 2) LaCoO 3With the mixture of Pd, Pd accounts for mass percent 0.5%; 3) TiO of mass percent 20% 2The Al of+mass percent 80% 2O 3In add mass percent again and account for 1% Pd and 5% V 2O 54) CeO of mass percent 10% 2Add mass percent among the MgO of+mass percent 90% again and account for 0.1% Pt.
The detailed process of described method is: oxidation reduction catalyst is inserted carry out high temperature in the tube furnace and be heated to 100-800 ℃, flue gas is regulated air speed 3000-30000mL/ (gh), by the pyro-oxidation-reduction catalyst.
Spray dilute sulfuric acid equipment is set behind tube furnace reclaims sulfur trioxide.
The present invention proposes a kind of catalysis flue gas processing method of desulphurization denitration simultaneously, especially at power plant and metallurgical works institute discharged flue gas, under hot conditions, allow mist (sulfur dioxide, nitric oxide and nitrogen dioxide gas) pass through oxidation reduction catalyst, make the automatic oxidation reduction reaction takes place between sulfur dioxide and nitric oxide or the nitrogen dioxide, Sulphur Dioxide is sulfur trioxide, nitric oxide and nitrogen dioxide gas are converted into nitrogen, tail gas reclaims the ferrous sulfate heptahydrate product through scrap iron and dilute sulfuric acid, reclaim the follow-up cooling of nitrogen back, heating-up temperature 100-800 ℃, flow air speed 3000-30000mL/ (gh), desulfuration efficiency are more than 95%; Denitration efficiency is more than 70%, and the sulfur trioxide rate of recovery is more than 90%, N 2The rate of recovery is more than 90%.Can reach treatment of wastes with processes of wastes against one another catalysis desulfurization simultaneously out of stock purpose and recyclable high value added product, tail gas also can reach existing discharge standard, carries out through engineering approaches flue gas Processing Test for next step and provides support.The present invention is significant to realizing the smoke catalytic heavy industrialization application of desulphurization denitration simultaneously.
The specific embodiment:
The invention will be further described below in conjunction with embodiment, rather than limitation of the present invention.
Embodiment 1: the oxidation reduction catalyst high-temperature catalytic is desulphurization denitration simultaneously
10g oxidation reduction catalyst (ZrO packs in the reactor of tube type resistance furnace 2With to add mass percent after H-ZSM-5 mixes according to mol ratio 1:3 again be 3% Pt), earlier logical nitrogen 5 minutes begins to heat up then, feeds nitrogen simultaneously, (the sulfur dioxide percent by volume is 60% to feed mist when being warmed up to 200 ℃, the nitric oxide percent by volume is 20%, and the nitrogen dioxide percent by volume is 10%, and all the other are nitrogen), its air speed is 6000mL/ (gh), duration of ventilation 30 minutes, tail gas detects through flue gas analyzer, and elemental sulfur and carbon calculate with gravimetric method.Desulfuration efficiency is 97.2%; Denitration efficiency 71.3%; The sulfur trioxide rate of recovery is more than 90.7%, N 2The rate of recovery 91.9% illustrates to have the effect of desulphurization denitration simultaneously of automatic oxidation reduction catalysis preferably.

Claims (5)

1. the catalysis flue gas processing method of desulphurization denitration simultaneously, it is characterized in that, under hot conditions, allow the flue gas that contains sulfur dioxide, nitric oxide and nitrogen dioxide gas pass through oxidation reduction catalyst, make sulfur dioxide respectively and the automatic oxidation reduction reaction takes place between the nitric oxide, nitrogen dioxide, Sulphur Dioxide is sulfur trioxide, absorb sulfur trioxide recovery ferrous sulfate heptahydrate product through scrap iron and dilute sulfuric acid, nitric oxide and nitrogen dioxide gas are converted into nitrogen, and recycle nitrogen cooling back.
2. method according to claim 1 is characterized in that, described flue gas comprises power plant and metallurgical works institute discharged flue gas.
3. method according to claim 1 is characterized in that,
Described oxidation reduction catalyst is following one or more: 1) ZrO 2Be 3% Pt with adding mass percent after H-ZSM-5 mixes according to mol ratio 1:3 again; 2) LaCoO 3With the mixture of Pd, Pd accounts for mass percent 0.5%; 3) TiO of mass percent 20% 2The Al of+mass percent 80% 2O 3In add mass percent again and account for 1% Pd and 5% V 2O 54) CeO of mass percent 10% 2Add mass percent among the MgO of+mass percent 90% again and account for 0.1% Pt.
4. according to claim 1 or 2 or 3 described methods, it is characterized in that,
The detailed process of described method is: oxidation reduction catalyst is inserted carry out high temperature in the tube furnace and be heated to 100-800 ℃, flue gas is regulated air speed 3000-30000mL/ (gh), by the pyro-oxidation-reduction catalyst.
5. method according to claim 1 is characterized in that,
Spray dilute sulfuric acid equipment is set behind tube furnace reclaims sulfur trioxide.
CN201310184993.8A 2013-03-13 2013-05-17 Flue gas treatment method of catalysis and simultaneous desulfurization and denitrification Active CN103263848B (en)

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CN104707475B (en) * 2015-04-03 2016-08-24 中南大学 A kind of flue gas processing method of low temperature photocatalysis automatic oxidation reduction simultaneous SO_2 and NO removal
CN105126563B (en) * 2015-08-24 2017-11-28 秦皇岛玻璃工业研究设计院 The desulphurization denitration medium and desulphurization denitration apparatus and method of a kind of flue gas of glass melting furnace
CN105879668B (en) * 2016-06-08 2017-10-20 江阴东邦钢球机械有限公司 A kind of flue gas processing device
CN106513033A (en) * 2016-11-03 2017-03-22 新沂市中诺新材料科技有限公司 Method for preparing CeO2, NiO-ZSM-5/gamma-Al2O3 desulphurization denitration catalyst
CN107377002A (en) * 2017-06-29 2017-11-24 浙江农业商贸职业学院 A kind of high-performance nano catalyst of vehicle maintenance service
CN107694576A (en) * 2017-09-30 2018-02-16 中晶蓝实业有限公司 Dry desulfurization denitrfying agent and its production method and application
CN107876066A (en) * 2017-11-02 2018-04-06 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of palladium iridium bimetallic alloy perovskite auto-exhaust catalyst and products thereof and application

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CN102836717A (en) * 2012-09-10 2012-12-26 中南大学 Application of spinel-type oxide and method for catalytic desulfurization and denitrification

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CN101518718B (en) * 2008-02-28 2012-10-10 中国纺织科学研究院 Functional filter felt for eliminating harmful constituents of fume, preparation method and application method thereof
CN102527205B (en) * 2012-01-09 2013-12-11 广东电网公司电力科学研究院 Method and system for simultaneously removing sulfur, niter and mercury from smoke based on catalytic oxidation

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CN102489307A (en) * 2011-12-10 2012-06-13 山西潞安矿业(集团)有限责任公司 Catalyst for removing sulfur and saltpeter in smoke and preparing method thereof and application thereof
CN102836717A (en) * 2012-09-10 2012-12-26 中南大学 Application of spinel-type oxide and method for catalytic desulfurization and denitrification

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