CN1257004C - A flue gas denitrification (nitrogen) desulfurization agent - Google Patents
A flue gas denitrification (nitrogen) desulfurization agent Download PDFInfo
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Abstract
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技术领域technical field
本发明涉及一种脱硝(氮)脱硫剂，特别涉及一种烟气脱硝(氮)脱硫剂。The invention relates to a denitrification (nitrogen) desulfurizer, in particular to a flue gas denitrification (nitrogen) desulfurizer.
背景技术Background technique
燃煤电厂等传统上使用的烟气脱硫剂主要是以石灰石、氢氧化钙等为主。芬兰LIFAC法烟气脱硫是向锅炉炉膛内喷射石灰石粉，并在锅炉尾部烟道上增设了一个独立的活化反应器，将炉内未反应的CaO通过雾化水进行活化后，再次脱除烟气中的SO2。美国ABB公司的湿法烟气脱硫是采用石灰石作为吸收剂，与烟气中的SO2反应，生成副产品石膏；而ABB公司的NID系统(新型一体化脱硫系统)是一种半干法烟气脱硫系统，其基本原理是SO2和Ca(OH)2在湿润条件下进行反应，脱硫后的废渣以干态灰渣形式排出。日本研究的电子束烟气脱硫(EBA)是通过电子束照射烟气，使烟气中SO2与照射前加入的脱硫剂NH3进行中和反应，生成(NH4)2SO4，达到固硫、脱硫作用。这些方法所用的脱硫剂虽然易得且价格便宜，然而无论是芬兰LTFAC脱硫或美国ABB公司湿法、半干法脱硫，或是脱硫效率可达到75％以上日本电子束烟气脱硫(EBA)，脱硫系统装置均非常庞大，石灰石制粉制浆装置、氧化吸收装置、物料输送装置、电子束发生装置等设备操作复杂，且占地面积大、加药量大，因而一次性投资大(约占机组投资的15-20％)，运行成本高(约为0.045元RMB/KW.h)，所以在实际应用中受到很大的限制。The flue gas desulfurizers traditionally used in coal-fired power plants are mainly limestone and calcium hydroxide. Finnish LIFAC method flue gas desulfurization is to inject limestone powder into the boiler furnace, and add an independent activation reactor on the tail flue of the boiler, activate the unreacted CaO in the furnace through atomized water, and then remove the flue gas again SO 2 in . The wet flue gas desulfurization of ABB company in the United States uses limestone as an absorbent to react with SO2 in the flue gas to generate gypsum as a by-product; and the NID system (new integrated desulfurization system) of ABB company is a semi-dry flue gas desulfurization system. The basic principle of the desulfurization system is that SO 2 and Ca(OH) 2 react under wet conditions, and the waste residue after desulfurization is discharged in the form of dry ash. Electron beam flue gas desulfurization (EBA) studied in Japan uses electron beams to irradiate flue gas, so that SO 2 in the flue gas neutralizes the desulfurizing agent NH 3 added before irradiation to generate (NH 4 ) 2 SO 4 , achieving solidification. Sulfur, desulfurization. Although the desulfurizers used in these methods are easy to get and cheap, no matter it is Finnish LTFAC desulfurization or U.S. ABB company wet method, semi-dry desulfurization, or desulfurization efficiency can reach more than 75% Japanese electron beam flue gas desulfurization (EBA), The devices of the desulfurization system are very large, and the equipment such as the limestone pulverizing and pulping device, the oxidation absorption device, the material conveying device, and the electron beam generating device are complex to operate, occupy a large area, and have a large amount of dosing, so the one-time investment is large (about 15-20% of unit investment), high operating cost (about 0.045 yuan RMB/KW.h), so it is greatly restricted in practical application.
烟气中NO、NO2的脱除主要有两种方式，一种是将NO、NO2还原，如利用氨(NH3)作为还原剂，将其还原为氮气(N2)，例如采用电子束法、低压脉冲放电电晕等离子体法或使用催化剂进行还原；另一种是将其氧化，转化为硝酸盐，从而达到脱除NO和NO2的目的。There are two main ways to remove NO and NO 2 in flue gas. One is to reduce NO and NO 2 , such as using ammonia (NH 3 ) as a reducing agent to reduce it to nitrogen (N 2 ), for example, using electron Beam method, low-voltage pulse discharge corona plasma method or use catalyst for reduction; the other is to oxidize it and convert it into nitrate, so as to achieve the purpose of removing NO and NO 2 .
发明创造内容Invention content
本发明的目的是提供一种可降低设备投资和运行成本，可分别或同时有效地脱除烟气中NO、NO2和SO2的烟气脱硝(氮)脱硫剂。The object of the present invention is to provide a flue gas denitrification (nitrogen) desulfurizer which can reduce equipment investment and operating cost, and can effectively remove NO, NO2 and SO2 in flue gas separately or simultaneously.
本发明所提供的烟气脱硝(氮)脱硫剂，由下述各重量份数比的组分组成：The flue gas denitrification (nitrogen) desulfurizer provided by the present invention is made up of the following components in various parts by weight ratios:
碳酸钙 40-100Calcium carbonate 40-100
氧化钙 5-20Calcium Oxide 5-20
碳酸镁 2.5-10Magnesium carbonate 2.5-10
二氧化钛 2.5-10Titanium dioxide 2.5-10
铁氧化物 2.5-10Iron oxide 2.5-10
稀土 2.5-4.5Rare earth 2.5-4.5
所述铁氧化物为三氧化二铁，氧化亚铁，四氧化三铁中的一种或几种。The iron oxide is one or more of ferric oxide, ferrous oxide and ferric oxide.
所述脱硝(氮)脱硫剂各组分的重量份数比最好为：The ratio of parts by weight of each component of the denitrification (nitrogen) desulfurizer is preferably:
碳酸钙 70Calcium carbonate 70
氧化钙 10Calcium Oxide 10
碳酸镁 7.5Magnesium Carbonate 7.5
二氧化钛 5Titanium dioxide 5
三氧化二铁 5Ferric oxide 5
稀土 2.5Rare earth 2.5
所述脱硝(氮)脱硫剂根据各组分含量的不同，可专门用于脱硝(氮)或脱硫。当专门用于脱硝(氮)时，所述脱硝(氮)脱硫剂包括下述各重量份数比的组分：The denitrification (nitrogen) desulfurizer can be specially used for denitrification (nitrogen) or desulfurization according to the content of each component. When being specially used for denitrification (nitrogen), the denitrification (nitrogen) desulfurizer includes the following components in parts by weight:
碳酸钙 40-60Calcium carbonate 40-60
氧化钙 10-20Calcium Oxide 10-20
碳酸镁 5-10Magnesium carbonate 5-10
二氧化钛 5-10Titanium dioxide 5-10
铁氧化物 5-10Iron oxide 5-10
稀土 2.5-4.5Rare earth 2.5-4.5
其中各组分优选的重量份数比如下：：Wherein the preferred parts by weight ratio of each component is as follows:
碳酸钙 60Calcium carbonate 60
氧化钙 15Calcium Oxide 15
碳酸镁 7.5Magnesium Carbonate 7.5
二氧化钛 7.5Titanium dioxide 7.5
三氧化二铁 7.5Ferric oxide 7.5
稀土 2.5Rare earth 2.5
当所述脱硝(氮)脱硫剂专门用于脱硫时，各组分的重量份数比如下：When described denitrification (nitrogen) desulfurizer is specially used in desulfurization, the parts by weight ratio of each component is as follows:
碳酸钙 50-70Calcium carbonate 50-70
氧化钙 10-20Calcium Oxide 10-20
碳酸镁 2-5.5Magnesium carbonate 2-5.5
二氧化钛 5-10Titanium dioxide 5-10
铁氧化物 5-10Iron oxide 5-10
稀土 2.5-4.5。Rare earth 2.5-4.5.
其中各组分优选的重量份数比如下：Wherein the preferred parts by weight ratio of each component is as follows:
碳酸钙 60Calcium carbonate 60
氧化钙 15Calcium Oxide 15
碳酸镁 5.5Magnesium Carbonate 5.5
二氧化钛 7.5Titanium dioxide 7.5
三氧化二铁 7.5Ferric oxide 7.5
稀土 4.5。Rare earth 4.5.
所述脱硝(氮)脱硫剂的粒度一般在140-280目之间。The particle size of the denitrification (nitrogen) desulfurization agent is generally between 140-280 mesh.
所述脱硝(氮)脱硫剂中的TiO2、La2O3和CeO2起到的是催化剂的作用。TiO 2 , La 2 O 3 and CeO 2 in the denitrification (nitrogen) desulfurization agent function as catalysts.
上述脱硝(氮)脱硫剂可以按照常规方法制备。The above-mentioned denitration (nitrogen) desulfurization agent can be prepared according to conventional methods.
本发明的脱硝(氮)脱硫剂在使用时，附加紫外线辐照会显著提高脱硝(氮)脱硫效果，可以对烟气分别或同时脱硝(氮)脱硫，在方法上属于干法脱硝(氮)脱硫，因而无需庞大的烟气活化反应装置及制粉制浆系统，加药装置相对简单。使用时，将脱硝(氮)脱硫剂直接喷入尾部烟道烟气中，使之与烟气充分混合，同时利用紫外线对混合烟气进行辐照，这一过程中会产生大量富有化学反应活性的氢氧(羟基)自由基(OH)、氧原子、过氧化羟基自由基(HO2)、O3等，不但能使NO、NO2和SO2在气相中被氧化，使之在颗粒状脱硝(氮)脱硫剂上转化为稳定的固态盐类物质，同时能够在颗粒状脱硝(氮)脱硫剂表面上发生光化学多相化学反应，可使烟气中NO、NO2和SO2在很短的时间内发生反应、转化，生成稳定的固态硝酸盐和硫酸盐物质，从而达到烟气同时脱硫脱硝(氮)的目的。研究表明，在适当的功率和脱硝(氮)脱硫剂添加量下，烟气中SO2脱除率可以达到95％以上，NO、NO2脱除率可以达到80％以上，脱硝(氮)脱硫的产物为硫酸钙和硝酸钙，可以做其它行业的原料。When the denitrification (nitrogen) desulfurizer of the present invention is used, additional ultraviolet radiation will significantly improve the denitrification (nitrogen) desulfurization effect, and the flue gas can be denitrified (nitrogen) and desulfurized separately or simultaneously, which belongs to dry denitrification (nitrogen) in terms of method. Desulfurization, so there is no need for a huge flue gas activation reaction device and a pulverizing and pulping system, and the dosing device is relatively simple. When in use, the denitrification (nitrogen) desulfurizer is directly sprayed into the tail flue gas to make it fully mixed with the flue gas, and at the same time, the mixed flue gas is irradiated with ultraviolet rays. In this process, a large amount of chemically reactive Hydroxyl (hydroxyl) radicals (OH), oxygen atoms, peroxide hydroxyl radicals (HO 2 ), O 3 , etc., can not only oxidize NO, NO 2 and SO 2 in the gas phase, but also make them in granular The denitrification (nitrogen) desulfurizer is converted into a stable solid-state salt substance, and at the same time, a photochemical multi-phase chemical reaction can occur on the surface of the granular denitrification (nitrogen) desulfurizer, which can make NO, NO 2 and SO 2 in the flue gas in a very Reaction and transformation occur in a short period of time to generate stable solid nitrate and sulfate substances, so as to achieve the purpose of simultaneous desulfurization and denitrification (nitrogen) of flue gas. Studies have shown that under the appropriate power and denitrification (nitrogen) desulfurization agent addition, the removal rate of SO2 in flue gas can reach more than 95%, the removal rate of NO and NO2 can reach more than 80%, and the denitrification (nitrogen) desulfurization The products are calcium sulfate and calcium nitrate, which can be used as raw materials for other industries.
本发明的脱硝(氮)脱硫剂的脱硝(氮)和脱硫效率高、化学反应活性强、药剂的利用率高、运行成本低廉，所需设备的总投资少、占地面积小、不产生二次污染、系统结构简单、运行操作简便，脱硝(氮)脱硫的产物可以再利用，脱硝(氮)脱硫剂既能加快反应，又能做反应产物的吸附剂，不但适用于发电厂、钢铁厂及其它工业厂矿新建大型锅炉烟气脱硝(氮)脱硫，还特别适合于已建燃烧设备的改造应用。The denitrification (nitrogen) desulfurization agent of the present invention has high denitrification (nitrogen) and desulfurization efficiency, strong chemical reactivity, high utilization rate of medicament, low operating cost, less total investment of required equipment, small floor area, and no secondary production. Secondary pollution, simple system structure, easy operation, denitrification (nitrogen) desulfurization products can be reused, denitrification (nitrogen) desulfurization agent can not only speed up the reaction, but also act as an adsorbent for the reaction product, not only suitable for power plants, steel plants And other industrial factories and mines newly built large-scale boiler flue gas denitrification (nitrogen) desulfurization, and is especially suitable for the transformation and application of existing combustion equipment.
具体实施方式Detailed ways
实施例1、静态NO、NO2和SO2脱除Embodiment 1, static NO, NO 2 and SO 2 removal
将本发明脱硝(氮)脱硫剂(由下述各重量份数比的组分组成：碳酸钙，70；氧化钙，10；碳酸镁，7.5；二氧化钛，5；三氧化二铁，5；稀土，2.5)200mg放入小型流动扩散反射反应装置的样品池内，利用傅立叶转换红外光谱监测颗粒状CTR脱硝(氮)脱硫剂表面组分的变化。用N2、O2、NO、NO2、SO2气体和H2O合成模拟烟气，NO、NO2、SO2浓度分别为20ppm，相对湿度40％，流动反应器出口连接NOx(NO+NO2)、SO2分析仪监测合成烟气中NO、NO2、SO2含量的变化。在紫外线辐照的条件下，颗粒状脱硝(氮)脱硫剂表面硝酸盐、硫酸盐生成的量显著增加。试验结果表明在紫外线辐照的条件下，合成烟气中NO、NO2、SO2在颗粒状脱硝(氮)脱硫剂表面能够生产稳定的硝酸盐、硫酸盐，可有效地脱除合成烟气中NO、NO2和SO2，脱除效率为98％。The denitrification (nitrogen) desulfurizer of the present invention (consists of the following components in parts by weight: calcium carbonate, 70; calcium oxide, 10; magnesium carbonate, 7.5; titanium dioxide, 5; ferric oxide, 5; rare earth , 2.5) 200mg was put into the sample cell of the small-scale flow diffusion reflection reaction device, and the change of the surface components of the granular CTR denitrification (nitrogen) desulfurization agent was monitored by Fourier transform infrared spectroscopy. Use N 2 , O 2 , NO, NO 2 , SO 2 gas and H 2 O to synthesize simulated flue gas, the concentrations of NO, NO 2 and SO 2 are respectively 20ppm, the relative humidity is 40%, and the outlet of the flow reactor is connected to NOx (NO+ NO 2 ), SO 2 analyzers monitor the changes of NO, NO 2 , SO 2 content in the synthetic flue gas. Under the condition of ultraviolet radiation, the amount of nitrate and sulfate on the surface of granular denitrification (nitrogen) desulfurization agent increased significantly. The test results show that under the condition of ultraviolet radiation, NO, NO 2 and SO 2 in the synthetic flue gas can produce stable nitrate and sulfate on the surface of the granular denitrification (nitrogen) desulfurizer, which can effectively remove the synthetic flue gas Among NO, NO 2 and SO 2 , the removal efficiency is 98%.
实施例2、动态NO、NO2和SO2脱除Embodiment 2, dynamic NO, NO 2 and SO 2 removal
用合成空气作为载气将本发明的脱硝(氮)脱硫剂(由下述各重量份数比的组分组成：碳酸钙，70；氧化钙，10；碳酸镁，7.5；二氧化钛，5；三氧化二铁，5；稀土，2.5)带入石英反应器内，与模拟烟气充分混合、接触。合成的模拟烟气中SO2含量为500ppm，NOx(NO+NO2)含量为500ppm。用NOx(NO+NO2)、SO2分析仪监测出口烟气中NO、NO2、SO2含量的变化。在紫外线辐照的条件下，SO2去除率达到95％，NOx(NO+NO2)去除率达到80％。利用等速采样器收集反应产物，测定其扩散反射傅立叶转换光谱，表明烟气中NO、NO2和SO2转化生成了硝酸盐和硫酸盐，达到烟气同时脱硝(氮)脱硫的目的。With synthetic air as carrier gas, the denitrification (nitrogen) desulfurizer of the present invention (made up of the following components in parts by weight: calcium carbonate, 70; Calcium oxide, 10; Magnesium carbonate, 7.5; Titanium dioxide, 5; three Ferric oxide, 5; rare earth, 2.5) is brought into the quartz reactor, fully mixed and contacted with the simulated flue gas. The content of SO 2 in the synthetic simulated flue gas is 500ppm, and the content of NOx (NO+NO 2 ) is 500ppm. Use NOx (NO+NO 2 ), SO 2 analyzer to monitor the changes of NO, NO 2 , SO 2 content in the outlet flue gas. Under the condition of ultraviolet irradiation, the removal rate of SO 2 reaches 95%, and the removal rate of NOx (NO+NO 2 ) reaches 80%. The reaction product was collected by an isokinetic sampler, and its diffuse reflectance Fourier transform spectrum was measured, indicating that NO, NO 2 and SO 2 in the flue gas were transformed into nitrate and sulfate, achieving the purpose of simultaneous denitrification (nitrogen) and desulfurization of the flue gas.
实施例3、NO、NO2脱除Embodiment 3, NO, NO Remove
用合成空气作为载气将脱硝(氮)脱硫剂(由下述各重量份数比的组分组成：碳酸钙，60；氧化钙，15；碳酸镁，7.5；二氧化钛，7.5；三氧化二铁，7.5；稀土，2.5)带入石英反应器内，与模拟烟气充分混合、接触。合成的模拟烟气中NOx(NO+NO2)含量为500ppm。用NOx(NO+NO2)分析仪监测出口烟气中NO、NO2含量的变化。在紫外线辐照的条件下，NOx(NO+NO2)去除率达到80％。利用等速采样器收集反应产物，测定其扩散反射傅立叶转换光谱，表明烟气中NO、NO2转化生成了硝酸盐，达到烟气脱硝的目的。Use synthetic air as the carrier gas to denitrify (nitrogen) desulfurizer (consist of the following components in parts by weight: calcium carbonate, 60; calcium oxide, 15; magnesium carbonate, 7.5; titanium dioxide, 7.5; ferric oxide , 7.5; rare earth, 2.5) into the quartz reactor, fully mixed and contacted with simulated flue gas. The content of NOx (NO+NO 2 ) in the synthetic simulated flue gas is 500ppm. Use NOx (NO+NO 2 ) analyzer to monitor the change of NO and NO 2 content in the outlet flue gas. Under the condition of ultraviolet irradiation, the removal rate of NOx (NO+NO 2 ) reaches 80%. The reaction product was collected by an isokinetic sampler, and its diffuse reflectance Fourier transform spectrum was measured, indicating that NO and NO 2 in the flue gas were transformed into nitrate, which achieved the purpose of flue gas denitrification.
实施例4、SO2的脱除Embodiment 4, SO The removal of
用合成空气作为载气将脱硝(氮)脱硫剂(由下述各重量份数比的组分组成：碳酸钙，60；氧化钙，15；碳酸镁，5.5；二氧化钛，7.5；三氧化二铁，7.5；稀土，4.5；TiO2，1)带入石英反应器内，与模拟烟气充分混合、接触。合成的模拟烟气中SO2含量为500ppm。用SO2分析仪监测出口烟气中SO2含量的变化。在紫外线辐照的条件下，SO2去除率达到95％。利用等速采样器收集反应产物，测定其扩散反射傅立叶转换光谱，表明烟气中SO2转化生成了硫酸盐，达到烟气脱硫的目的。Use synthetic air as the carrier gas to denitrate (nitrogen) desulfurizer (consist of the following components in parts by weight: calcium carbonate, 60; calcium oxide, 15; magnesium carbonate, 5.5; titanium dioxide, 7.5; ferric oxide , 7.5; rare earth, 4.5; TiO 2 , 1) brought into the quartz reactor, fully mixed and contacted with simulated flue gas. The SO2 content in the synthesized simulated flue gas was 500ppm. Use a SO2 analyzer to monitor the change of SO2 content in the outlet flue gas. Under the condition of ultraviolet irradiation, the SO2 removal rate reaches 95%. The reaction product was collected by an isokinetic sampler, and its diffuse reflectance Fourier transform spectrum was measured, indicating that SO 2 in the flue gas was transformed into sulfate, which achieved the purpose of flue gas desulfurization.
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2003
- 2003-06-12 CN CN 03136387 patent/CN1257004C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301749A (en) * | 2013-06-21 | 2013-09-18 | 艾荻环境技术（上海）有限公司 | Method for simultaneously performing desulfurization and denitrification on smoke gas |
| CN103301749B (en) * | 2013-06-21 | 2015-12-02 | 艾荻环境技术（上海）有限公司 | The method of flue gas and desulfurizing and denitrifying |
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