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Application of SDS dry desulfurization in coke oven flue gas treatment

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With the increasingly strict requirements of environmental protection emissions, the efforts of enterprises to control pollution are also increasing, and the treatment of coke oven flue gas is becoming more and more important. In the process of coke oven production, there will be waste gas containing dust, SO2, NOx and other harmful substances, which will cause pollution to the environment. In order to reduce the emission of harmful substances such as SO2 and NOx in the flue gas of coke oven, make it meet the requirements of environmental protection, and improve the quality of atmospheric environment, many advanced methods have been applied to practical projects. Lu Hao et al. [1] found that SCR denitrification technology has good sulfur resistance in low temperature environment, and the denitrification rate of flue gas reaches over 85%. Jinhui et al. [2] applied SCR technology to a project of Jiangsu Yizhou Coal Coking Co., Ltd., and solved the problem that coke oven flue gas could not be treated at low temperature. Wang Yan et al. [3] believed that the coke oven flue gas treatment should effectively integrate the three aspects of source control, low nitrogen combustion and end purification, and paid attention to them.

After purification by desulfurization, denitration and dust removal process, the flue gas emission concentration of coke oven reaches SO2 ≤ 30 mg / m3, NOx ≤ 150 mg / m3, and dust concentration ≤ 15 mg / m3, which meets the special emission limit requirements in emission standard for pollutants in Coking Chemical Industry (GB 16171-2012), and can meet the requirements of ultra-low emission standard.

With the increasingly strict requirements of environmental protection emissions, the efforts of enterprises to control pollution are also increasing, and the treatment of coke oven flue gas is becoming more and more important. In the process of coke oven production, there will be waste gas containing dust, SO2, NOx and other harmful substances, which will cause pollution to the environment. In order to reduce the emission of harmful substances such as SO2 and NOx in the flue gas of coke oven, make it meet the requirements of environmental protection, and improve the quality of atmospheric environment, many advanced methods have been applied to practical projects. Lu Hao et al. [1] found that SCR denitrification technology has good sulfur resistance in low temperature environment, and the denitrification rate of flue gas reaches over 85%. Jinhui et al. [2] applied SCR technology to a project of Jiangsu Yizhou Coal Coking Co., Ltd., and solved the problem that coke oven flue gas could not be treated at low temperature. Wang Yan et al. [3] believed that the coke oven flue gas treatment should effectively integrate the three aspects of source control, low nitrogen combustion and end purification, and paid attention to them.

After purification by desulfurization, denitration and dust removal process, the flue gas emission concentration of coke oven reaches SO2 ≤ 30 mg / m3, NOx ≤ 150 mg / m3, and dust concentration ≤ 15 mg / m3, which meets the special emission limit requirements in emission standard for pollutants in Coking Chemical Industry (GB 16171-2012), and can meet the requirements of ultra-low emission standard.

2. Process technology

The common desulfurization and denitrification methods of coke oven flue gas mainly include SDS dry desulfurization + medium and low temperature SCR denitrification, SDA (NA) semi dry desulfurization + medium and low temperature SCR denitrification, SDA (CA) semi dry desulfurization + GGH - medium and low temperature SCR denitrification and activated carbon dry desulfurization and denitrification.

2.1 SDS dry desulfurization process

The high-efficiency desulfurizer (particle size of 20-25 μ m) is injected into the flue by SDS dry deacidification jet and even distribution device and is heated and activated in the flue. Its specific surface area increases rapidly. The background is the HCl removal dry process system developed by the waste incineration industry. The main component of its by-product is NaCl, which can be recycled as raw material for soda production. After that, SDS dry deacidification technology has developed rapidly in Europe. After the supporting jet system fully contacts with the flue gas, physical and chemical reactions take place. SO2 and other acid substances in the flue gas are absorbed and purified. The open system and grinding system of this technology have been developed successively. At present, the process is mainly used for deacidification of waste incinerator tail gas in European market, but it has achieved good application results in other industries including coking, glass manufacturing, coal-fired power plant, hazardous waste incinerator, diesel power generation, biomass power generation, cement, etc.

The advantages of SDS dry desulfurization + medium and low temperature SCR denitrification process are high desulfurization and denitrification efficiency, no temperature drop, no water operation, low investment, small floor area, less by-products, low power consumption, no corrosion, simple equipment, easy operation and maintenance, small amount of desulfurization by-products, high content of sodium sulfate; the disadvantages are that a small amount of desulfurization by-products will be produced, which need to be comprehensively utilized.

2.2 SDA semi dry desulfurization process (including Na method and CA method)

The rotary spray drying (SDA) desulfurization technology was developed by Danish Niro in the early 1970s. In the desulfurization process, Cao or Na2CO3 water is added to form a Ca (OH) 2 slurry or Na2CO3 solution with a solid content of 20% ~ 25%. The solution is atomized into 30 ~ 80 μ m droplets by the high-speed rotation of the atomizer and then injected into the absorption tower. The Ca (oh) 2 slurry or Na2CO3 solution droplets (absorbers) in the tower absorb SO2 in the flue gas rapidly to remove SO2 and other acidic media. At the same time, the coke oven flue gas heat instantly dries the liquid drop sprayed into the tower, making it become a powder dry solid, which is collected by the bag filter.

The desulfurization process is simple, and the absorption tower is an empty tower structure. The advantages of SDA (NA) semi dry desulfurization + medium and low temperature SCR denitrification are high desulfurization efficiency, no waste water generation, low water consumption, low power consumption, and no corrosion; the disadvantages are easy crystallization of desulfurizer, difficult maintenance, and difficult recycling of by-products. The advantages of SDA (CA) semi dry desulfurization + GGH - medium and low temperature SCR denitrification process are moderate desulfurization efficiency, no waste water generation, low water consumption, low power consumption and no corrosion; the disadvantages are large area, low flue gas temperature first and then rising, high energy consumption and difficult to use by-products.

2.3 activated carbon dry desulfurization and denitrification process

Based on the principle of physical-chemical adsorption, the activated carbon adsorbs SO2, H2O and O2 in the flue gas and catalyzes the reaction to generate sulfuric acid, which is then transferred to the micropore for storage. Under the catalysis of activated carbon, NOx in the flue gas reacts with ammonia water injected into the flue gas to generate N2 and H2O. The activated carbon releases the active adsorption site through the regeneration system to continue to absorb SO2. The flue gas containing SO2 discharged from the regeneration system enters the by-product recovery system. SO2 can be processed into a variety of sulfur chemical products.

Active carbon will produce wear and chemical consumption in the regeneration process, so it is necessary to supplement new active carbon regularly. The worn active carbon powder can be returned to the coal blending section for reuse.

The dry desulfurization and denitrification process of activated carbon uses the adsorption of activated carbon to absorb SO2, particulate matter and NOx in flue gas, so as to realize the purpose of simultaneous desulfurization, denitrification and dust removal. The disadvantage is that the flue gas temperature needs to be reduced to below 150 ℃; the desulfurization by-product contains sulfuric acid and produces polluted waste water at the same time, which has large one-time investment and high operation cost.

To sum up, no matter whether the advanced technology (desulfurization and denitrification efficiency), or the practicability of the technology, the area of investment has been invested.

本,废水,副产物利用等方面进行综合分析比较,SDS 干法脱硫及中低温SCR 脱硝工艺是最适合焦炉烟气净化的最佳工艺技术,其配置合理,控制水平达到国际先进水平,可确保脱硫脱硝系统长期、安全、稳定、连续地运行。

3. Process principle

3.1 SDS process principle

SDS dry deacidification spray technology is to spray high-efficiency desulfurizer (particle size is 20-25 μ m) uniformly in the pipeline, the desulfurizer is heated and activated in the pipeline, the specific surface area is rapidly increased, it is in full contact with the acid flue gas, physical and chemical reactions occur, SO2 and other acid substances in the flue gas are absorbed and purified.

The main chemical reactions are as follows:

2NaHCO3 +SO2+1/2O2 → Na2SO4 +2CO2+H2O

2NaHCO3 +SO3 → Na2SO4 +2CO2+H2O

The main reactions with other acidic substances (such as SO3, etc.) are as follows:

NaHCO3 +HCl → NaCl +CO2+H2O

NaHCO3 +HF → NaF +CO2+H2O

4. Process characteristics

4.1 technical characteristics of SDS desulfurization process

The operation and shutdown of the desulfurization unit will not affect the continuous operation of the coke oven. The load range of the desulfurization system is coordinated with the load range of the coke oven to ensure the reliable and stable continuous operation of the desulfurization system. The process features are as follows:

(1) The system is simple and easy to operate and maintain;

(2) Less investment at one time, small floor space;

(3) Low operation cost;

(4) Fully dry system, no water required;

(5) High desulfurization efficiency;

(6) Reasonable desulfurizer distribution device;

(7) It has high flexibility and can be adjusted at any time according to the emission index requirements;

(8) It has a good removal effect on acid substances;

(9) Strong adaptability to coke oven working condition;

(10) Less by-products, high purity of sodium sulfate, easy to recycle;

(11) The system is equipped with quick switch device of accident channel, which will not affect the normal production of coke oven in case of failure

。

5 composition of desulfurization and Denitration Process System

The flue gas desulfurization and denitration system of coke oven is composed of the following parts:

(1) SDS desulfurizer dosing and distribution device (key equipment is considered to be standby);

(2) Dust removal equipment and auxiliary equipment;

(3) Denitration reactor system and auxiliary equipment;

(4) Public and auxiliary equipment of desulfurization and denitrification system, including nitrogen supply system, circulating water supply, etc;

(5) Instrument, communication, power supply and distribution, online monitoring, fire control and control system, etc.

With the more and more strict requirements of environmental protection laws and regulations, parman developed the process of sodium bicarbonate dry deacidification based on the advanced process in Europe and America, which has been applied more and more. Sodium bicarbonate was used as adsorbent to remove various pollutants in flue gas. Its purification effect can be compared with other known ways, such as the spray adsorption method using lime milk as adsorbent. Dry flue gas purification can not only be used in coal power plants, hazardous waste treatment, municipal waste or alternative fuel incineration plants, but also widely used in industrial furnaces in glass, cement, metallurgy and other industries. Dry flue gas purification can economically remove the gas containing acid substances, such as SO2, HCI, etc., and reach the national standard flue gas emission standard. In recent years, the baking soda dry desulfuration and deacidification grinder produced and developed by our company has served many environmental protection companies in the country, successfully completed the flue gas desulfurization transformation project for many steel group owners in the country, so as to play the role of desulfuration and deacidification, flue gas purification. Today, our company cooperates

Hubei environmental protection technology Co., Ltd. is the grinding and pulverizing system of the hot blast furnace flue gas desulfurization transformation project of a united Special Steel Co., Ltd. in Tianjin. The equipment has been completed, contributing to the realization of a more beautiful blue sky and white clouds.

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