CN106731783B - Integrated flue gas desulfurization and denitrification agent and use method thereof - Google Patents

Integrated flue gas desulfurization and denitrification agent and use method thereof Download PDF

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CN106731783B
CN106731783B CN201510813399.XA CN201510813399A CN106731783B CN 106731783 B CN106731783 B CN 106731783B CN 201510813399 A CN201510813399 A CN 201510813399A CN 106731783 B CN106731783 B CN 106731783B
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agent
flue gas
desulfurization
denitration
denitrification
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CN106731783A (en
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刘万超
李学鹏
张朝普
闫琨
和新忠
杨晨星
刘中凯
杜艳
鲍春
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Aluminum Corp of China Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8637Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/60Simultaneously removing sulfur oxides and nitrogen oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/20Reductants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/50Inorganic acids
    • B01D2251/506Sulfuric acid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/602Oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/604Hydroxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/60Inorganic bases or salts
    • B01D2251/606Carbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/70Organic acids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10Inorganic absorbents
    • B01D2252/102Ammonia
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/60Additives
    • B01D2252/602Activators, promoting agents, catalytic agents or enzymes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2256/00Main component in the product gas stream after treatment
    • B01D2256/12Oxygen
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/30Sulfur compounds
    • B01D2257/302Sulfur oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/40Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to an integrated flue gas desulfurization and denitration agent and a using method thereof, and is characterized in that the flue gas desulfurization and denitration agent comprises the following components: desulfurizer, iron-based denitration catalyst, activator and suspending agent. The method takes alkaline substances as a desulfurizer, takes desulfurization product sulfite as a reducing agent, takes an iron-based denitration catalyst as an active reaction factor, and realizes the simultaneous removal of sulfur dioxide and nitrogen oxide in the flue gas under a gas-liquid-solid three-phase homogenization suspension state, wherein NOx is reduced into nitrogen; activating the reacted absorption liquid by acid liquor, supplementing the suspending agent, and sending the absorption liquid into the reaction tower again by a circulating pump for recycling. The method is simple to operate, the desulfurization efficiency is more than 99%, the denitration efficiency is more than 90%, and the desulfurization and denitration effects are good. The material is recycled, the operation cost of desulfurization and denitrification is greatly reduced, the economic advantage is obvious, and the method is applicable to the treatment of flue gas or tail gas of various industrial boilers and industrial kilns.

Description

Integrated flue gas desulfurization and denitrification agent and use method thereof
Technical Field
An integrated flue gas desulfurization and denitration agent and a using method thereof relate to a desulfurization and denitration agent for flue gas treatment and a wet desulfurization and denitration method of flue gas.
Background
In recent years, the problem of environmental pollution is becoming more serious, and especially, the smoke pollution is more and more paid more attention by the society. SO in flue gas2And NOxAcid rain and light caused byEnvironmental pollution problems such as smog, haze and the like have deeply influenced the environment on which human beings live. With the recent increase of environmental protection requirement of the national ministry of environmental protection and the simultaneous control of SO2、NOxThe requirements for emissions are more stringent. The traditional desulfurization and denitration technology has high economic cost, complex process, large occupied area and high maintenance and operation cost, so that the application of the traditional desulfurization and denitration technology is seriously influenced and is rarely applied to actual industry. The pollution of coal burning industry, petrochemical industry, glass industry and coking enterprises in China is becoming more and more serious, and the full development of low-cost and high-efficiency flue gas purification technology is the most important, so that the combined desulfurization and denitrification technology with the advantages of low cost, compact structure and the like is more and more emphasized.
At present, in the aspect of flue gas purification, most of processes such as desulfurization, denitrification, flue gas dust removal and the like are in an independent development state, and respective technical systems and process flows are formed. For example, conventionally used methods for flue gas desulfurization are limestone-gypsum method, ammonia method, magnesium method, double alkali method, etc., and each method has its limitations and disadvantages, and the limestone-gypsum method is often easily clogged, scaled; the ammonia method and the magnesium method have higher operation cost, and the ammonia method is easy to cause ammonia to escape to form aerosol; the double alkali method has extremely high cost for long-term operation and serious scaling. At present, the common domestic desulfurization method is to separately build a desulfurization tower and spray the tower with alkali liquor to desulfurize the flue gas. The conventional methods for flue gas denitration are Selective Catalytic Reduction (SCR) and non-selective catalytic reduction (SNCR), wherein the reducing agent in the two denitration methods is generally an ammonia-containing compound, and can be ammonia water, liquid ammonia or urea. The operation method is to spray the solution containing the ammonia compound in the furnace. But the SNCR removal rate is low, and the temperature requirement is higher; the SCR operation cost is too high, and independent SCR denitration technology is lacked in China. At present, the current situation of desulfurization and denitrification is that the flue gas desulfurization and denitrification are separately operated and are respectively treated by using separate process methods, so that a plurality of sets of devices need to be built, the process is complex, the occupied area is large, the investment is large, the cost is high, the purification effect is poor, and the resource waste is caused.
Aiming at the situation, a tool for integrated desulfurization and denitrification is developedThe technological method has the advantages of bringing deep influence on popularization and application of flue gas purification and saving a large amount of financial resources, material resources and space. At present, an integrated desulfurization and denitrification process method is reported. Patents CN101053747A, CN101773778A and CN103357260A disclose integrated desulfurization and denitrification processes with different processes respectively. Patent CN101053747A proposes a process for performing desulfurization and denitrification by first oxidizing NO in flue gas and then using ammonia as an absorbent, which consumes a large amount of oxidants such as hydrogen peroxide and ozone, but the oxidants are generally expensive, and the above process and apparatus both consume ammonia during denitrification, which results in high cost. Patent CN101773778A proposes a method for oxidizing NO in flue gas into NO in advance2Then absorbed by alkali liquor, and the NO which is not oxidized is removed by sulfite (NH)4)2SO3、NH4HSO3Reduction to N2Therefore, the desulfurization and denitrification integrated process is realized, but the denitrification rate of the process can only reach about 60 percent, which is caused by incomplete front oxidation and insufficient rear reduction. In patent CN103357260A, an integrated process for flue gas desulfurization and denitration by using a ferrous complexing agent to enhance urea is proposed, wherein the integrated process is in full contact with a mixed absorption liquid containing urea and a ferrous complexing agent fe (ii) EDTA in an absorption tower reaction zone to absorb SO in flue gas2And NOx. Complexing agent EDTA is expensive, is not easy to recycle, has high consumption in the denitration process, and ferrous iron is easy to be oxidized into ferric iron to lose the denitration capability. The prior art has high investment and operation cost and unsatisfactory flue gas purification treatment effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the integrated flue gas desulfurization and denitrification agent and the use method thereof, wherein the integrated flue gas desulfurization and denitrification agent has the advantages of good desulfurization and denitrification effect, simple operation, material recycling, capability of greatly reducing the desulfurization and denitrification operation cost and wide applicability.
The purpose of the invention is realized by the following technical scheme.
The integrated flue gas desulfurization and denitration agent is characterized by comprising the following components: desulfurizer, iron-based denitration catalyst, activator and suspending agent.
The integrated flue gas desulfurization and denitrification agent is characterized in that in the flue gas desulfurization and denitrification agent, the dosage of an iron-based denitration catalyst is 3-8% of the total weight of a desulfurizing agent, the dosage of an activating agent is 2-3 times of the mole number of the iron-based denitration catalyst, and the dosage of a suspending agent is 0.5-10% of the weight of the iron-based denitration catalyst.
The integrated flue gas desulfurization and denitrification agent is characterized in that the desulfurization agent is one or a mixture of limestone, lime, magnesium oxide, sodium hydroxide, sodium carbonate, ammonia and ammonium sulfite.
The invention discloses an integrated flue gas desulfurization and denitration agent, which is characterized in that the iron-based denitration catalyst comprises the following components in percentage by weight: 85% -90% of Fe2O30.4 to 10 percent of SiO20.5% -5% of V2O50.5 to 5 percent of TiO2
The integrated flue gas desulfurization and denitrification agent is characterized in that the activating agent is one or a mixture of acetic acid, sulfuric acid, hydrochloric acid and adipic acid.
The integrated flue gas desulfurization and denitrification agent is characterized in that the suspending agent is one or a mixture of more of polyaluminium chloride, polyferric chloride, polyacrylamide, polyferric sulfate and polyaluminium sulfate.
Experiments prove that the integrated flue gas desulfurization and denitrification agent has high denitration efficiency which can reach more than 90 percent when the dosage of the iron-based denitration catalyst is 3 to 8 percent of the total weight of the desulfurizer and the dosage of the activating agent is 2 to 3 times of the mole number of the iron-based denitration catalyst; when the using amount of the suspending agent is 0.5-10% of the weight of the iron-based denitration catalyst, uniform suspension of the flue gas desulfurization and denitration agent can be formed, the contact probability of the flue gas desulfurization and denitration agent and the flue gas is increased, the reaction is sufficient, and NO in the flue gas is fully reactedxIs efficiently reduced into nitrogen, and the desulfurization and denitrification effects are obviously improved.
The flue gas desulfurization and denitration agent of the invention uses sulfite produced by desulfurization of desulfurizer therein asUse of reducing agents for denitration reactions, e.g. CaSO produced by desulfurization3、MgSO3、Na2SO3、(NH4)2SO3And the like. In the practical industrial application process, if SO is contained in the flue gas2The content of the sodium sulfite is not high, and the generated sulfite is less, so that the reducing agent in the denitration step is insufficient, and the denitration is not thorough, therefore, the reducing agent sulfite can be directly added into the flue gas desulfurization and denitration agent.
The integrated flue gas desulfurization and denitrification agent is characterized by further comprising a reducing agent, wherein the reducing agent is sulfite, and the amount of the reducing agent is 0-100% of the total weight of the desulfurizing agent. When the flue gas desulfurization and denitrification agent is prepared, a reducing agent can be added.
The integrated flue gas desulfurization and denitrification agent is characterized in that the activating agent is preferably acetic acid and/or sulfuric acid.
The application method of the integrated flue gas desulfurization and denitration agent is characterized in that the application process is that the leacheate prepared by the sulfur-containing and nitrate-containing flue gas and the integrated flue gas desulfurization and denitration agent is subjected to countercurrent leaching to remove SO2And NOxAbsorption reaction, removing SO from flue gas2And NOxAnd (4) removing.
The use method of the integrated flue gas desulfurization and denitration agent is characterized in that the prepared leacheate is aqueous solution containing 5-20% of the integrated flue gas desulfurization and denitration dosage.
The application method of the integrated flue gas desulfurization and denitration agent is characterized in that the desulfurization and denitration liquid after adsorption reaction is supplemented with a suspending agent and activated by adding acetic acid for recycling.
The application method of the integrated flue gas desulfurization and denitration agent is characterized in that when sulfuric acid is added for activation after adsorption reaction, the addition amount of the sulfuric acid is 2-3 times of the mole number of the iron-based denitration catalyst.
The application method of the integrated flue gas desulfurization and denitrification agent is characterized in that the temperature of the sulfur-containing and nitrate-containing flue gas is 50-200 ℃.
The integrated flue gas of the inventionThe using method of the desulfurization and denitrification agent is characterized in that the leaching solution prepared from the sulfur-containing nitrate-containing flue gas and the integrated flue gas desulfurization and denitrification agent is subjected to countercurrent leaching in a leaching tower, wherein the liquid-gas ratio in leaching is 5-9L/m3And the empty tower gas velocity of the flue gas is 4-5 m/s.
The application method of the integrated flue gas desulfurization and denitrification agent is characterized by comprising the following steps in the application process:
(1) firstly, desulfurizing agent in a desulfurization and denitrification agent is adopted to desulfurize the flue gas;
(2) adding an iron-based denitration catalyst, an activating agent and a suspending agent in a desulfurization and denitration agent into the desulfurized absorption liquid, mixing to prepare a denitration reaction liquid, carrying out countercurrent contact on the prepared denitration reaction liquid and the desulfurized flue gas to carry out denitration and purification on the flue gas, activating the denitration absorption liquid by acid liquor, supplementing the suspending agent, and then sending the denitration absorption liquid into the reaction tower again by a circulating pump for recycling.
The application method of the integrated flue gas desulfurization and denitrification agent is characterized in that a reducing agent is added when a denitrification reaction liquid is prepared, wherein the reducing agent is sulfite, and the using amount of the reducing agent is 0-100% of the total weight of the desulfurizing agent.
The integrated flue gas desulfurization and denitrification agent takes alkaline substances as a desulfurizing agent, takes desulfurization product sulfite as a reducing agent, takes an iron-based denitrification catalyst as an active reaction factor, and realizes the simultaneous removal of sulfur dioxide and nitrogen oxide in flue gas in a gas-liquid-solid three-phase homogenization suspension state, wherein NOx is reduced into nitrogen; activating the reacted absorption liquid by acid liquor, supplementing the suspending agent, and sending the absorption liquid into the reaction tower again by a circulating pump for recycling.
The integrated flue gas desulfurization and denitrification agent and the use method thereof have the advantages of simple operation, desulfurization efficiency of more than 99 percent, denitrification efficiency of more than 90 percent and good desulfurization and denitrification effects. The material is recycled, the operation cost of desulfurization and denitrification is greatly reduced, the economic advantage is obvious, and the method is applicable to the treatment of flue gas or tail gas of various industrial boilers and industrial kilns. The flue gas desulfurization and denitrification agent has the desulfurization efficiency of more than 99 percent, the denitrification efficiency of more than 90 percent and good desulfurization and denitrification effects.
Detailed Description
The integrated flue gas desulfurization and denitration agent is prepared by the following steps: the flue gas desulfurization and denitrification agent comprises the following components: the catalyst comprises a desulfurizing agent, an iron-based denitration catalyst, an activating agent and a suspending agent, wherein the using amount of the iron-based denitration catalyst is 3-8% of the total weight of the desulfurizing agent, the using amount of the activating agent is 2-3 times of the mole number of the iron-based denitration catalyst, and the using amount of the suspending agent is 0.5-10% of the weight of the iron-based denitration catalyst; the desulfurizer is one or a mixture of more of limestone, lime, magnesium oxide, sodium hydroxide, sodium carbonate, ammonia and ammonium sulfite, and the iron-based denitration catalyst comprises the following components in percentage by weight: 85% -90% of Fe2O30.4 to 10 percent of SiO20.5% -5% of V2O50.5 to 5 percent of TiO2The activating agent is one or a mixture of more of acetic acid, sulfuric acid, hydrochloric acid and adipic acid, and the suspending agent is one or a mixture of more of polyaluminium chloride, polyferric chloride, polyacrylamide, polyferric sulfate and polyaluminium sulfate;
in a desulfurization and denitrification tower, the flue gas to be treated is in countercurrent contact with the prepared flue gas desulfurization and denitrification agent to realize desulfurization, denitrification and purification treatment of the flue gas to be treated, wherein the liquid-gas ratio of the flue gas desulfurization and denitrification agent is 5-9L/m3And the air velocity of the gas to be treated in the empty tower is 4-5 m/s.
The wet-process integrated desulfurization and denitrification method realizes the simultaneous removal of sulfur dioxide and nitrogen oxide in the flue gas under the wet-process condition, integrates the desulfurization and denitrification of the flue gas in one reaction tower, and has the advantages of small investment and convenient operation.
Optionally, the flue gas desulfurization and denitrification agent further comprises a reducing agent, wherein the reducing agent is sulfite, and the amount of the reducing agent is 0-100% of the total weight of the desulfurizing agent.
Preferably, the temperature of the flue gas to be treated is 50-200 ℃.
Preferably, the desulfurization and denitrification tower is a bubble tower, a turbulent tower or a spray tower, or the bubble tower and the turbulent towerAnd the spray tower is used in combination, the desulfurization and denitrification processes are carried out in a gas-liquid-solid three-phase homogenization suspension state, the reaction is sufficient, and NO in the flue gas is fully reactedxIs efficiently reduced into nitrogen, and has good desulfurization and denitrification effects.
Preferably, the flue gas after desulfurization, denitrification and purification treatment is demisted by a demister and then discharged, and the obtained absorption liquid at the bottom of the desulfurization and denitrification tower is activated by acid liquid, supplemented with the suspending agent and then sent into the desulfurization and denitrification tower again by a circulating pump for recycling. The tower bottom absorption liquid is activated by acid liquor, namely an activating agent is added into the tower bottom absorption liquid, the using amount of the activating agent is 2-3 times of the mole number of the iron-based denitration catalyst contained in the tower bottom absorption liquid, and the activating agent is one or a mixture of acetic acid, sulfuric acid, hydrochloric acid and adipic acid. The iron-based denitration catalyst in the tower bottom absorption liquid can be recycled after being activated.
The integrated desulfurization and denitrification method comprises the following operation steps:
(1) weighing reaction materials: taking a desulfurizing agent, an iron-based denitration catalyst, an activating agent and a suspending agent, wherein the using amount of the iron-based denitration catalyst is 3-8% of the total weight of the desulfurizing agent, the using amount of the activating agent is 2-3 times of the mole number of the iron-based denitration catalyst, and the using amount of the suspending agent is 0.5-10% of the weight of the iron-based denitration catalyst; the desulfurizer is one or a mixture of more of limestone, lime, magnesium oxide, sodium hydroxide, sodium carbonate, ammonia and ammonium sulfite, and the iron-based denitration catalyst comprises the following components in percentage by weight: 85% -90% of Fe2O30.4 to 10 percent of SiO20.5% -5% of V2O50.5 to 5 percent of TiO2The activating agent is one or a mixture of more of acetic acid, sulfuric acid, hydrochloric acid and adipic acid, and the suspending agent is one or a mixture of more of polyaluminium chloride, polyferric chloride, polyacrylamide, polyferric sulfate and polyaluminium sulfate;
(2) flue gas desulfurization treatment: using the desulfurizer in the step (1), and adopting a conventional desulfurization system to perform desulfurization treatment on the flue gas to be treated;
(3) flue gas denitration treatment: mixing the absorption liquid generated after desulfurization treatment in the step (2) with the iron-based denitration catalyst, an activating agent and a suspending agent to prepare a denitration reaction liquid, carrying out countercurrent contact on the flue gas treated in the step (2) and the prepared denitration reaction liquid in a reaction tower to realize denitration purification treatment on the flue gas, and feeding the denitration absorption liquid obtained after denitration purification treatment into the reaction tower again for recycling by a circulating pump after activating by acid liquor and supplementing the suspending agent.
The wet integrated desulfurization and denitrification method is characterized in that the flue gas desulfurization treatment and the flue gas denitrification treatment are carried out separately. The flue gas desulfurization treatment can adopt a conventional desulfurization system, for example, the method commonly used in domestic desulfurization in the background art section, namely, a desulfurization tower is separately built, and alkali liquor is used for spraying to carry out desulfurization treatment on the flue gas. The absorption liquid produced after the desulfurization treatment contains sulfite as a main component and is used as a reducing agent for the following flue gas denitration treatment. The method has the advantages that the flue gas desulfurization treatment and the flue gas denitration treatment are independently carried out, so that the method can be simultaneously used with the conventional desulfurization system for direct matching, only one set of denitration equipment is needed, and the modification cost is low.
Preferably, in the step (3), a reducing agent is added when the denitration reaction liquid is prepared, wherein the reducing agent is sulfite, and the amount of the reducing agent is 0-100% of the total weight of the desulfurizing agent.
The invention has the following beneficial effects: the invention discloses a method for removing sulfur dioxide and nitrogen oxide in flue gas by wet method integration, which takes alkaline substance as desulfurizer, sulfite of desulfurization product as reducer, iron-based denitration catalyst as active reaction factor, realizes the simultaneous removal of sulfur dioxide and nitrogen oxide in flue gas under gas-liquid-solid three-phase homogenization suspension state, wherein NOx is reduced into nitrogen; activating the reacted absorption liquid by acid liquor, supplementing the suspending agent, and sending the absorption liquid into the reaction tower again by a circulating pump for recycling. The method is simple to operate, the desulfurization efficiency is more than 99%, the denitration efficiency is more than 90%, and the desulfurization and denitration effects are good. Because the materials can be recycled, the operation cost of desulfurization and denitrification is greatly reduced, the operation cost is lower than that of the existing desulfurization and denitrification method, the economic advantage is obvious, the problems of high infrastructure investment, high operation and maintenance cost, complex operation and the like of the existing desulfurization and denitrification technology are solved, and the method is applicable to the treatment of flue gas or tail gas of various industrial boilers and industrial kilns.
The wet integrated desulfurization and denitrification method provided by the invention also has the following advantages: no secondary pollution such as nitrate, nitrite and solid waste, low cost and easily available raw materials, large supply and low cost. And the applicability is strong, and the method can be widely applied to desulfurization, denitrification and purification of flue gas such as coal, gas, glass, ceramics and the like. Compared with the traditional desulfurization and denitration technology, the method has great advantages in the aspects of economy and resource utilization efficiency. The method of the invention is a wet reduction method for desulfurization and denitrification, does not need the oxidation process, and the reducing agent is not limited to (NH)4)2SO3The reducing agent is CaSO generated by desulfurization3、MgSO3、Na2SO3、(NH4)2SO3And one or more of the sulfites, and does not use expensive EDTA.
120-200 ℃ coal-fired flue gas from a dust remover, wherein the desulfurization and denitrification tower is a spray tower, and SO in the coal-fired flue gas2At a concentration of 2600mg/Nm3,NOxAt a concentration of 600mg/Nm3The amount of the treated flue gas is 10000m3The superficial gas velocity of the flue gas is 4m/s, the flue gas desulfurization and denitration agent provided by the embodiment is adopted, and the liquid-gas ratio is 5-8L/m3The mixed flue gas desulfurization and denitration agent is sprayed out through an atomizing nozzle of a spraying system and contacts with the flue gas in a countercurrent manner in a spraying tower to remove SO in the flue gas2And NOx(ii) a And activating the absorption liquid at the bottom of the spray tower by acetic acid, supplementing a suspending agent, and sending the absorption liquid into the spray layer of the desulfurization and denitrification tower again by the circulating pump for recycling. In the desulfurization and denitrification process, the desulfurization and denitrification system can discharge part of desulfurization and denitrification liquid at intervals through the slurry discharge pump in the spray tower. Meanwhile, at intervals, process water enters a demister cleaning demister of the desulfurization and denitrification spray tower through a process water pump. The temperature of the coal-fired flue gas in desulfurization and denitrification is reduced from 120-200 ℃ to 50-75 ℃, and the purified coal-fired flue gas is demisted by a demister and then discharged. Emitted smoke detectionThe result is SO2At a concentration of 25mg/Nm3,NOxAt a concentration of 40mg/Nm3The desulfurization rate of 99% and the denitration rate of 93% can be achieved.
In the desulfurization and denitrification process, the desulfurizer control measuring instrument is used for automatically monitoring and automatically supplementing a new desulfurizer or a regenerated desulfurizer, the reducer control measuring instrument is used for automatically monitoring and automatically supplementing a new reducer or a regenerated reducer, and an iron-based denitration catalyst is needed to be supplemented so as to ensure the composition of the used flue gas desulfurization and denitrification agent and realize the automatic and continuous desulfurization and denitrification purification.
The technical solution of the present invention will be described in detail by specific examples.
Example 1
A flue gas desulfurization and denitrification agent is prepared by mixing the following components: the catalyst comprises a desulfurizing agent, a reducing agent, an iron-based denitration catalyst, an activating agent and a suspending agent, wherein the desulfurizing agent is ammonia water, and the reducing agent is (NH)4)2SO3The dosage of the reducing agent is equal to the total weight of the desulfurizer, and the iron-based denitration catalyst comprises the following components in percentage by weight: 85% Fe2O35% of SiO25% of V2O55% of TiO2The dosage of the iron-based denitration catalyst is 3% of the total weight of the desulfurizer, the dosage of the activator is acetic acid, the dosage of the activator is 2 times of the mole number of the iron-based denitration catalyst, the suspending agent is a mixture of polyaluminium chloride and polyacrylamide, and the dosage of the suspending agent is 10% of the weight of the iron-based denitration catalyst. The desulfurization and denitrification agent is prepared into spray liquid with the concentration of 5 percent for use.
The wet integrated desulfurization and denitrification method by using the flue gas desulfurization and denitrification agent provided by the embodiment comprises the following steps:
the method comprises the following steps that coal-fired flue gas at 120-200 ℃ from a dust remover enters a desulfurization and denitrification tower through a variable-frequency draught fan, the desulfurization and denitrification tower is a spray tower, and SO in the coal-fired flue gas enters the desulfurization and denitrification tower2At a concentration of 2600mg/Nm3,NOxAt a concentration of 600mg/Nm3The amount of the treated flue gas is 10000m3The superficial gas velocity of the flue gas is 4m/s, and the flue gas desulfurization and denitrification agent and the liquid gas provided by the embodiment are adoptedThe ratio is 5 to 8L/m3The mixed flue gas desulfurization and denitration agent is sprayed out through an atomizing nozzle of a spraying system and contacts with the flue gas in a countercurrent manner in a spraying tower to remove SO in the flue gas2And NOx(ii) a And activating the absorption liquid at the bottom of the spray tower by acetic acid, supplementing a suspending agent, and sending the absorption liquid into the spray layer of the desulfurization and denitrification tower again by the circulating pump for recycling. In the desulfurization and denitrification process, the desulfurization and denitrification system can discharge part of desulfurization and denitrification liquid at intervals through the slurry discharge pump in the spray tower. Meanwhile, at intervals, process water enters a demister cleaning demister of the desulfurization and denitrification spray tower through a process water pump. The temperature of the coal-fired flue gas in desulfurization and denitrification is reduced from 120-200 ℃ to 50-75 ℃, and the purified coal-fired flue gas is demisted by a demister and then discharged. The detection result of the discharged flue gas is SO2At a concentration of 25mg/Nm3,NOxAt a concentration of 40mg/Nm3The desulfurization rate of 99% and the denitration rate of 93% can be achieved.
In the desulfurization and denitrification process, the desulfurizer control measuring instrument is used for automatically monitoring and automatically supplementing a new desulfurizer or a regenerated desulfurizer, the reducer control measuring instrument is used for automatically monitoring and automatically supplementing a new reducer or a regenerated reducer, and an iron-based denitration catalyst is needed to be supplemented so as to ensure the composition of the used flue gas desulfurization and denitrification agent and realize the automatic and continuous desulfurization and denitrification purification.
Example 2
A flue gas desulfurization and denitrification agent is prepared by mixing the following components: the desulfurizer is a mixture of magnesium oxide and sodium hydroxide, and the iron-based denitration catalyst comprises the following components in percentage by weight: 90% Fe2O39% of SiO20.5% of V2O50.5% of TiO2The dosage of the iron-based denitration catalyst is 8 percent of the total weight of the desulfurizer, the dosage of the activating agent is sulfuric acid, the dosage of the activating agent is 3 times of the mole number of the iron-based denitration catalyst, the suspending agent is a mixture of polyferric chloride and polyaluminium sulfate, and the dosage of the suspending agent is 0.5 percent of the weight of the iron-based denitration catalyst. The desulfurization and denitrification agent is used for preparing spray liquid with the concentration of 15 percent.
The wet integrated desulfurization and denitrification method by using the flue gas desulfurization and denitrification agent provided by the embodiment comprises the following steps:
180 deg.C flue gas from a dust collector of a petrochemical plant, SO in the flue gas2The concentration of (b) is 1800mg/Nm3,NOxHas a concentration of 2800mg/Nm3The amount of flue gas treated is 50000m3The superficial gas velocity of the flue gas is 4.5m/s, the flue gas desulfurization and denitration agent provided by the embodiment is adopted, and the liquid-gas ratio is 5-9L/m3The mixed flue gas desulfurization and denitration agent is sprayed out by the turbulator and contacts with the flue gas in a countercurrent manner to remove SO in the flue gas2And NOx(ii) a The absorption liquid at the bottom of the tower is activated by sulfuric acid and is fed into the turbulent tower again by the circulating pump for recycling after the suspending agent is supplemented. In the desulfurization and denitrification process, the desulfurization and denitrification system can intermittently discharge part of desulfurization and denitrification liquid through the slurry discharging pump in the turbulent flow tower. Meanwhile, at intervals, process water enters a demister cleaning demister of the desulfurization and denitrification turbulence tower through a process water pump. The temperature of the coal-fired flue gas is reduced from 180 ℃ to 75 ℃ in the desulfurization and denitrification processes, and the purified coal-fired flue gas is demisted by a demister and then discharged. The detection result of the discharged flue gas is SO2At a concentration of 15mg/Nm3,NOxAt a concentration of 150mg/Nm3The desulfurization rate of 99 percent and the denitration rate of 94 percent can be achieved.
In the desulfurization and denitrification process, the desulfurizer control measuring instrument is used for automatically monitoring and automatically supplementing a new desulfurizer or a regenerated desulfurizer, and an iron-based denitration catalyst is needed to be supplemented so as to ensure the composition of the used flue gas desulfurization and denitrification agent and realize the automatic and continuous desulfurization and denitrification purification.
Example 3
A flue gas desulfurization and denitrification agent is prepared by mixing the following components: the desulfurizer is sodium hydroxide, the reducing agent is sodium sulfite, the using amount of the reducing agent is 50% of the total weight of the desulfurizer, and the iron-based denitration catalyst comprises the following components in percentage by weight: 90% Fe2O30.4% SiO24.6% of V2O55% of TiO2The dosage of the iron-based denitration catalyst is the total weight of the desulfurizer5 percent of activating agent, the dosage of the activating agent is 2 times of the mole number of the iron-based denitration catalyst, the suspending agent is a mixture of polyaluminium sulfate and polyacrylamide, and the dosage of the suspending agent is 3 percent of the weight of the iron-based denitration catalyst. The desulfurization and denitrification agent is used for preparing 20 percent spray liquid.
The wet integrated desulfurization and denitrification method by using the flue gas desulfurization and denitrification agent provided by the embodiment comprises the following steps:
50 ℃ coal-fired flue gas from a dust remover enters a desulfurization and denitrification tower through a flue, and SO in the flue gas2At a concentration of 1300mg/Nm3,NOxAt a concentration of 300mg/Nm3The amount of flue gas treated is 80000m3The superficial gas velocity of the flue gas is 5m/s, and the liquid-gas ratio of the flue gas desulfurization and denitrification agent provided by the embodiment is 5-9L/m3The mixed flue gas desulfurization and denitration agent is blown out from the bubbling position of the bubbling tower system and contacts with the flue gas in a countercurrent manner to remove SO in the flue gas2And NOx(ii) a The absorption liquid at the bottom of the tower is activated by sulfuric acid and is fed into the bubble column again by a circulating pump for recycling after being supplemented with suspending agent. In the desulfurization and denitrification process, the desulfurization and denitrification system can discharge part of desulfurization and denitrification liquid at intervals through a slurry discharge pump in the bubble column. Meanwhile, at intervals, process water enters a demister cleaning demister of the desulfurization and denitrification bubbling tower through a process water pump. The temperature of the coal-fired flue gas is reduced from 50 ℃ to 35 ℃ in the desulfurization and denitrification processes, and the purified coal-fired flue gas is demisted by a demister and then discharged. The detection result of the discharged flue gas is SO2At a concentration of 15mg/Nm3,NOxAt a concentration of 30mg/Nm3And the desulfurization rate of 99 percent and the denitration rate of 90 percent can be achieved.
In the desulfurization and denitrification process, the desulfurizer control measuring instrument is used for automatically monitoring and automatically supplementing a new desulfurizer or a regenerated desulfurizer, the reducer control measuring instrument is used for automatically monitoring and automatically supplementing a new reducer or a regenerated reducer, and an iron-based denitration catalyst is needed to be supplemented so as to ensure the composition of the used flue gas desulfurization and denitrification agent and realize the automatic and continuous desulfurization and denitrification purification.
Example 4
The process flow of the embodiment is as follows: the 125 ℃ coal-fired flue gas from the dust remover enters the desulfurization and denitrification tower through the flue, and SO in the flue gas2At a concentration of 1300mg/Nm3,NOxAt a concentration of 300mg/Nm3The amount of flue gas treated is 80000m3The superficial gas velocity of the flue gas is 5m/s, and the adopted desulfurization and denitrification agent is desulfurization and denitrification liquid prepared by respectively regenerating and mixing liquid and solid filtered from the tower bottom liquid in the embodiment 3 of the invention. The regeneration step is as follows: adding a proper amount of lime solution into the liquid obtained by filtering, fully stirring for reaction, adjusting the alkalinity, and allowing the solution obtained by filter pressing through a filter press to enter a desulfurization and denitrification tower; activating the solid obtained by filtering through acetic acid and/or sulfuric acid treatment, supplementing a proper amount of suspending agent, and entering a desulfurization and denitrification tower to obtain a mixed desulfurization and denitrification liquid with a liquid-gas ratio of 5-9L/m3The mixed desulfurization and denitrification liquid is sprayed out by bubbling of a bubbling system and contacts with flue gas in a countercurrent manner to remove SO in the flue gas2And NOx(ii) a And the absorption liquid at the bottom of the tower is sent into the spraying layer again through the desulfurization and denitrification circulating pump for recycling. In the desulfurization and denitrification process, the desulfurization and denitrification system can discharge part of desulfurization and denitrification liquid at intervals through a slurry discharge pump in the bubble column. Meanwhile, at intervals, process water enters a demister cleaning demister of the desulfurization and denitrification bubbling tower through a process water pump. The temperature of the coal-fired flue gas is reduced from 125 ℃ to 50 ℃ in the desulfurization and denitrification processes, and the purified coal-fired flue gas is demisted by a demister and then discharged. The detection result of the discharged flue gas is SO2The concentration is 10mg/Nm3,NOxAt a concentration of 25mg/Nm3And the desulfurization rate of 99 percent and the denitration rate of 91 percent can be achieved.
In the desulfurization and denitrification process, the desulfurizer control measuring instrument is used for automatically monitoring and automatically supplementing a new desulfurizer or a regenerated desulfurizer, the reducer control measuring instrument is used for automatically monitoring and automatically supplementing a new reducer or a regenerated reducer, and an iron-based denitration catalyst is needed to be supplemented so as to ensure the composition of the used flue gas desulfurization and denitrification agent and realize the automatic and continuous desulfurization and denitrification purification.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (6)

1. The use method of the integrated flue gas desulfurization and denitration agent is characterized in that the flue gas desulfurization and denitration agent comprises the following components: a desulfurizing agent, an iron-based denitration catalyst, an activating agent and a suspending agent; wherein the dosage of the iron-based denitration catalyst is 3-8% of the total weight of the desulfurizer, the dosage of the activating agent is 2-3 times of the mole number of the iron-based denitration catalyst, and the dosage of the suspending agent is 0.5-10% of the weight of the iron-based denitration catalyst; the desulfurizer is one or a mixture of more of limestone, lime, magnesium oxide, sodium hydroxide, sodium carbonate, ammonia and ammonium sulfite; the iron-based denitration catalyst comprises the following components in percentage by weight: 85% -90% of Fe2O30.4 to 10 percent of SiO20.5% -5% of V2O50.5 to 5 percent of TiO2(ii) a The activating agent is one or a mixture of acetic acid, sulfuric acid, hydrochloric acid and adipic acid; the suspending agent is one or a mixture of more of polyaluminium chloride, polyferric chloride, polyacrylamide, polyferric sulfate and polyaluminium sulfate; the step of using the flue gas desulfurization and denitrification agent to carry out flue gas desulfurization and denitrification comprises the following steps:
(1) firstly, desulfurizing agent in a desulfurization and denitrification agent is adopted to desulfurize the flue gas;
(2) adding an iron-based denitration catalyst, an activating agent and a suspending agent in a desulfurization and denitration agent into the desulfurized absorption liquid, mixing to prepare a denitration reaction liquid, carrying out countercurrent contact on the prepared denitration reaction liquid and the desulfurized flue gas to carry out denitration and purification on the flue gas, activating the denitration absorption liquid by acid liquor, supplementing the suspending agent, and then sending the denitration absorption liquid into the reaction tower again by a circulating pump for recycling.
2. The use method of the integrated flue gas desulfurization and denitration agent according to claim 1, characterized in that the activating agent is acetic acid and/or sulfuric acid.
3. The use method of the integrated flue gas desulfurization and denitration agent according to claim 2, characterized in that when sulfuric acid is added for activation after adsorption reaction, the addition amount of sulfuric acid is 2-3 times of the mole number of the iron-based denitration catalyst.
4. The use method of the integrated flue gas desulfurization and denitrification agent according to claim 3, wherein the temperature of the sulfur-containing and nitrate-containing flue gas is 50-200 ℃.
5. The use method of the integrated flue gas desulfurization and denitration agent according to claim 4, characterized in that the leaching solution prepared from the sulfur-containing nitrate-containing flue gas and the integrated flue gas desulfurization and denitration agent is subjected to countercurrent leaching in a leaching tower, wherein the liquid-gas ratio during leaching is 5-9L/m3And the empty tower gas velocity of the flue gas is 4-5 m/s.
6. The use method of the integrated flue gas desulfurization and denitration agent according to claim 1, characterized in that a reducing agent is added during the preparation of the denitration reaction solution, wherein the reducing agent is sulfite, and the amount of the reducing agent is 0-100% of the total weight of the desulfurizing agent.
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