WO2013082856A1 - 湿法石灰石烟气脱硫浆液稳定剂及其使用方法 - Google Patents

湿法石灰石烟气脱硫浆液稳定剂及其使用方法 Download PDF

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WO2013082856A1
WO2013082856A1 PCT/CN2012/000580 CN2012000580W WO2013082856A1 WO 2013082856 A1 WO2013082856 A1 WO 2013082856A1 CN 2012000580 W CN2012000580 W CN 2012000580W WO 2013082856 A1 WO2013082856 A1 WO 2013082856A1
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desulfurization
slurry
flue gas
stabilizer
desulfurization slurry
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PCT/CN2012/000580
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WO2013082856A8 (zh
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徐锐
梅重民
伍发元
邓永强
毛荣军
田旭
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江苏省电力科学研究院
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Priority to US14/363,295 priority Critical patent/US9399191B2/en
Publication of WO2013082856A1 publication Critical patent/WO2013082856A1/zh
Publication of WO2013082856A8 publication Critical patent/WO2013082856A8/zh
Priority to ZA2014/04580A priority patent/ZA201404580B/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/606—Carbonates

Definitions

  • the invention relates to a wet limestone flue gas desulfurization slurry stabilizer and a using method thereof, and belongs to the technical field of wet flue gas desulfurization.
  • So 2 emitted by coal-fired power plants is the main source of atmospheric pollutants and the main cause of acid rain.
  • the wet limestone-gypsum flue gas desulfurization technology has the advantages of mature technology, high desulfurization efficiency, reliable operation and comprehensive utilization of by-products. It is the most widely used flue gas desulfurization process in the world.
  • the common flue gas denitration process adopts a selective catalytic reduction (SCR) process.
  • SCR selective catalytic reduction
  • a large amount of metal oxide catalyst is needed in the process.
  • the catalyst can oxidize S0 2 in the flue gas to S0 3 , so 3 forms a very fine sulfuric acid mist at the tail of the flue, and the wet limestone-gypsum desulfurization process This sulfuric acid mist has almost no removal ability, which causes corrosion of downstream equipment and discharge of acid mist.
  • the object of the present invention is to provide a desulfurization slurry stabilizer used in a wet limestone flue gas desulfurization process, which is used for stabilizing the pH value of the desulfurization slurry, suppressing the generation of desulfurization slurry bubbling, reducing the discharge of sulfuric acid mist, and improving the desulfurization efficiency.
  • the invention also provides a method of using the desulphurization slurry stabilizer.
  • a wet limestone flue gas desulfurization slurry stabilizer is provided by the stone Composition of ash, sodium formate and defoamer, each component and its mass percentage are: lime 30% - 70%, sodium formate 15% ⁇ ⁇ 10%, defoamer 15% ⁇ 0%.
  • Lime is quicklime or hydrated lime.
  • the antifoaming agent is a silicone polyether solid composite composed of 30% polydimethyl silicone oil, 10 ° /. Polyether, 30% sodium carbonate, 30% sodium silicate are mixed, and the mixture is dried and pulverized.
  • the method for using the wet limestone flue gas desulfurization slurry stabilizer is as follows: the slurry stabilizer is prepared by using water or desulfurization slurry outside the desulfurization tower into a uniform liquid having a mass concentration of 10%-30%, and is pumped into the inlet of the slurry circulation pump. After the slurry circulation pump and the slurry atomization spray device, the absorption zone and the reaction zone sequentially enter into physical and chemical interaction with the flue gas and the desulfurization slurry, and the effective concentration of the desulfurization slurry stabilizer is 200-1000 mg/L.
  • the specific composition of the desulfurization slurry stabilizer is selected according to the state of the desulfurization unit, and the optimum use concentration is determined based on the test results.
  • the application of the wet limestone flue gas desulfurization slurry stabilizer can achieve the effect of stabilizing the pH value of the desulfurization slurry, suppressing the generation of the desulfurization slurry foam, reducing the sulfuric acid mist emission, and improving the desulfurization efficiency. Its mechanism of action is as follows:
  • the silicone polyether composite is composed of a hydrophilic, anti-foaming long-lasting polyether and a hydrophobic and fast-breaking silicone, which can effectively prevent the generation of desulfurization slurry foam.
  • the wet limestone-gypsum desulfurization process has little ability to remove fine sulfuric acid mist, which will cause corrosion of downstream equipment and discharge of acid mist.
  • the desulfurization slurry stabilizer passes through the slurry circulation pump and the slurry atomization spray device, and the Ca(OH) 2 in the desulfurization slurry stabilizer can be generated with the sulfuric acid mist in the absorption zone of the solid, liquid and gas three-phase reaction of the absorption tower. The reaction reduces the emission of sulfuric acid mist.
  • the main control step affecting the desulfurization reaction rate is the mass transfer process at the gas-liquid two-phase interface.
  • the sodium formate in the desulfurization slurry stabilizer can improve the mass transfer process of the desulfurization chemical reaction and improve the reaction. Activity, reduce the amount of limestone, and improve the efficiency of desulfurization.
  • the invention is suitable for flue gas desulfurization of coal-fired power plants.
  • the desulfurization slurry stabilizer of the present embodiment is composed of slaked lime, sodium formate and antifoaming agent, and each component and its mass percentage are: slaked lime 55%, sodium formate 23%, and defoamer 22%.
  • a 660 MW coal-fired power plant equipped with SCR wet limestone desulfurization unit adding the above-mentioned composition of desulfurization slurry stabilizer, the stabilizer added 700 mg / L, the desulfurization efficiency before desulfurization stabilizer is 91.5 - 92.3%, the desulfurization system discharges flue gas
  • the content of S0 3 in the medium is 49.4 mg/m 3 .
  • the desulfurization efficiency is 94.2-95.7% after adding the slurry stabilizer, and the S0 3 content in the flue gas is 11.2 mg/m 3 , and the slurry has no foaming phenomenon.
  • the desulfurization slurry stabilizer of the present embodiment is composed of slaked lime, sodium formate and antifoaming agent, and the composition and the mass percentage thereof are: slaked lime 52%, sodium formate 30%, and defoaming agent 17%.
  • the wet limestone desulfurization unit of a coal-fired power plant has a high sulfur content in the coal-burning content, and the volume design of the desulfurization absorption tower is limited.
  • the dicarboxylic acid desulfurization synergist with adipic acid as the main component is often used to improve the desulfurization efficiency, but organic
  • the acid-based desulfurization synergist will reduce the pH of the desulfurization slurry from 5.4 to 5.1. When the S0 2 content in the flue gas fluctuates, the pH is often difficult to stabilize and the desulfurization system cannot operate normally.
  • the stabilizer addition amount is 900 mg/L
  • the desulfurization efficiency before desulfurization stabilizer is 88.1-91.5%
  • the desulfurization slurry pH value is 5.0-5.2
  • the desulfurization efficiency after adding the slurry stabilizer is 90.3-93.5%.
  • the pH of the desulfurization slurry is 5.3-5.4, which is suitable for the fluctuation of S0 2 content in the flue gas. Significantly enhanced.
  • the desulfurization slurry stabilizer of the present embodiment is composed of slaked lime, sodium formate and antifoaming agent, and each component and its mass percentage are: slaked lime 50%, sodium formate 30%, and defoamer 20%.
  • a 350 MW coal-fired power plant is not equipped with a wet limestone desulfurization unit equipped with a denitration system.
  • the desulfurization slurry stabilizer of the above composition ratio is added.
  • the stabilizer is added in an amount of 700 mg/L, and the desulfurization efficiency before desulfurization stabilizer is 88.9-95%.
  • the desulfurization system is discharged.
  • the S0 3 content in the flue gas is 36.8 mg/m 3 .
  • the desulfurization efficiency is 93.9-95.1% after adding the slurry stabilizer, and the S0 3 content in the flue gas is 9.9 mg/m 3 .
  • the desulfurization slurry stabilizer of the present embodiment is composed of slaked lime, sodium formate and antifoaming agent, and each component and its mass percentage are: quicklime 40%, sodium formate 30%, and defoamer 30%.
  • a 300MW MW high-sulfur coal wet limestone desulfurization unit in a coal-fired power plant is added with a desulfurization slurry stabilizer of the above composition ratio.
  • the stabilizer is added in an amount of 1000 mg/L, and the desulfurization efficiency is 84-92% before the desulfurization stabilizer is added.
  • the desulfurization system The S0 3 content in the flue gas is 64.3 mg/m 3 . Under the same operating conditions, the desulfurization efficiency is 91.9-93.4% after adding the slurry stabilizer, and the S0 3 content in the flue gas is 22.1 mg/m 3 .

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  • Health & Medical Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

一种湿法石灰石烟气脱硫浆液稳定剂及其使用方法，该稳定剂由石灰、甲酸钠、消泡剂组成，各组成成分及其质量百分比为：石灰30-70%、甲酸钠15-40%、消泡剂15-40%；该脱硫浆液稳定剂的使用方法包括在脱硫塔外部将浆液稳定剂用水或脱硫浆液配制成质量浓度为10-30%的均匀液体，用泵和浆液雾化喷淋装置将脱硫浆液喷入脱硫塔的吸收区和反应区。

Description

湿法石灰石烟气脱硫浆液稳定剂及其使用方法 技术领域
本发明涉及一种湿法石灰石烟气脱硫浆液稳定剂及其使用方法， 属湿法烟 气脱硫技术领域。
背景技术
燃煤电厂排放的 so2是大气污染物主要来源和导致酸雨的主要因素。 湿法 石灰石一石膏烟气脱硫技术具有工艺成熟、 脱硫效率高、 运行可靠、 副产品可 综合利用等优点， 是当前世界上应用最为广泛的烟气脱硫工艺。
由于煤炭市场的变化， 火电厂实际燃烧煤种来源广、 变化多、 杂质多， 实 际燃煤含硫量与设计煤种含硫量差异很大， 烟气性质及烟气中 so2含量波动大， 会导致脱硫系统超负荷运行、浆液容易起泡、 浆液 pH值下降、脱硫效率下降等 问题， 严重影响烟气中 S02的达标排放。
为控制火电厂烟气中氮氧化物的排放， 部分火电厂加装了烟气脱硝系统， 常见的烟气脱硝工艺采取选择性催化还原（SCR)工艺。该工艺中需要用到大量 的金属氧化物催化剂， 催化剂能将烟气中的 S02氧化成 S03， so3在烟道尾部会 形成非常细小的硫酸酸雾， 湿法石灰石一石膏脱硫工艺对这种硫酸酸雾几乎没 有去除能力， 会造成下游设备腐蚀和酸雾的排放。
发明内容
本发明目的是提供一种湿法石灰石烟气脱硫工艺中使用的脱硫浆液稳定 剂，用于稳定脱硫浆液 pH值、抑制脱硫浆液泡沬的产生、降低硫酸酸雾的排放、 提高脱硫效率。 本发明还提供该脱硫浆液稳定剂的使用方法。
本发明的技术方案是， 本发明一种湿法石灰石烟气脱硫浆液稳定剂， 由石 灰、 甲酸钠、消泡剂组成， 各组成成分及其质量百分比为： 石灰 30%— 70%、 甲 酸钠 15%~^10%、 消泡剂 15%~ 0%。
石灰为生石灰或消石灰。
消泡剂为有机硅聚醚固体复合物， 该有机硅聚醚固体复合物由 30%聚二甲 基硅油、 10°/。聚醚、 30%碳酸钠、 30%硅酸钠混合， 再将混合物干燥粉碎而成。
湿法石灰石烟气脱硫浆液稳定剂的使用方法为： 在脱硫塔外部将浆液稳定 剂用水或脱硫浆液配制成质量浓度为 10%— 30%的均匀液体，用泵打入浆液循环 泵的入口， 经过浆液循环泵和浆液雾化喷淋装置， 依次进入吸收区和反应区与 烟气和脱硫浆液发生物理化学作用， 脱硫浆液稳定剂有效作用的浓度范围为 200— 1000mg/L。脱硫浆液稳定剂的具体组成根据脱硫机组的状态进行选择， 最 佳使用浓度根据试验结果确定。
湿法石灰石烟气脱硫浆液稳定剂应用能够达到稳定脱硫浆液 pH值、 抑制 脱硫浆液泡沫的产生、 降低硫酸酸雾的排放、 提高脱硫效率的效果。 其作用机 理如下：
( 1 )烟气中 S02异常增大和添加有机酸类脱硫增效剂是石灰石脱硫浆液 pH值降低的常见原因， 本发明所涉及脱硫浆液稳定剂含有 Ca(OH)2， 其能够中 和过量的 离子， 稳定脱硫浆液 pH值。
(2)有机硅聚醚复合物由亲水性强、抑泡持久的聚醚和疏水性强、破泡迅 速的有机硅复合而成， 能有效防止脱硫浆液泡沫的产生。
(3 )湿法石灰石一石膏脱硫工艺对细小的硫酸酸雾几乎没有去除能力，会 造成下游设备腐蚀和酸雾的排放。 脱硫浆液稳定剂经过浆液循环泵和浆液雾化 喷淋装置， 在吸收塔的固、 液、 气三相反应的吸收区， 脱硫浆液稳定剂中的 Ca(OH)2, 能够与硫酸酸雾发生反应， 降低硫酸酸雾的排放。 (4)湿法石灰石一石膏脱硫工艺中，影响脱硫反应速率的主要控制步骤是 气液两相界面处的传质过程， 脱硫浆液稳定剂中的甲酸钠能够改善脱硫化学反 应传质过程， 提高反应活性， 减少石灰石用量， 提高脱硫效率。
本发明适用于燃煤电厂的烟气脱硫。
具体实施方式
实施例 1
本实施例的脱硫浆液稳定剂由消石灰、 甲酸钠、 消泡剂组成， 各组成成分及 其质量百分比为： 消石灰 55%， 甲酸钠 23%， 消泡剂 22%。
某燃煤电厂 660MW配备 SCR的湿法石灰石脱硫机组， 添加上述组成比例 的脱硫浆液稳定剂， 稳定剂加入量 700 mg/L, 加入脱硫稳定剂前脱硫效率 91.5—92.3%, 脱硫系统排出烟气中 S03含量 49.4mg/m3， 同等运行工况下， 加 入浆液稳定剂后脱硫效率 94.2— 95.7%， 排出烟气中 S03含量 11.2 mg/m3， 浆液 无起泡现象。
实施例 2
本实施例的脱硫浆液稳定剂由消石灰、 甲酸钠、 消泡剂组成， 各组成成分及 其质量百分比为： 消石灰 52%， 甲酸钠 30%， 消泡剂 17%。
某燃煤电厂湿法石灰石脱硫机组由于燃煤含量硫分高，脱硫吸收塔容积设计 有限， 常采用以己二酸为主要成分的二元羧基酸脱硫增效剂以提高脱硫效率， 但以有机酸为主体的脱硫增效剂会使得脱硫浆液 pH值由 5.4下降至 5.1左右， 当烟气中 S02含量波动时， 常导致 pH值难以稳定， 脱硫系统不能正常运行。添 加上述组成比例的脱硫浆液稳定剂， 稳定剂加入量 900 mg/L, 加入脱硫稳定剂 前脱硫效率 88.1— 91.5%， 脱硫浆液 pH值 5.0— 5.2， 加入浆液稳定剂后脱硫效 率 90.3— 93.5%, 脱硫浆液 pH值 5.3— 5.4， 对烟气中 S02含量波动的适应性明 显增强。
实施例 3
本实施例的脱硫浆液稳定剂由消石灰、 甲酸钠、 消泡剂组成， 各组成成分及 其质量百分比为： 消石灰 50%， 甲酸钠 30%， 消泡剂 20%。
某燃煤电厂 350MW没有配备脱硝系统的湿法石灰石脱硫机组， 添加上述组 成比例的脱硫浆液稳定剂， 稳定剂加入量 700 mg/L, 加入脱硫稳定剂前脱硫效 率 88.9— 91%, 脱硫系统排出烟气中 S03含量 36.8 mg/m3, 同等运行工况下， 加 入浆液稳定剂后脱硫效率 93.9— 95.1%， 排出烟气中 S03含量 9.9 mg/m3。
实施例 4
本实施例的脱硫浆液稳定剂由消石灰、 甲酸钠、 消泡剂组成， 各组成成分及 其质量百分比为： 生石灰 40%, 甲酸钠 30%， 消泡剂 30%。
某燃煤电厂 300MW燃用高硫煤的湿法石灰石脱硫机组， 添加上述组成比例 的脱硫浆液稳定剂， 稳定剂加入量 1000 mg/L, 加入脱硫稳定剂前脱硫效率 84—92%, 脱硫系统排出烟气中 S03含量 64.3 mg/m3， 同等运行工况下， 加入浆 液稳定剂后脱硫效率 91.9一 93.4%， 排出烟气中 S03含量 22.1 mg/m3。

Claims

权 利 要 求 书
1、 一种湿法石灰石烟气脱硫浆液稳定剂， 其特征在于， 脱硫浆液稳定剂由 石灰、 甲酸钠、 消泡剂组成， 各组成成分及其质量百分比为： 石灰 30%— 70%、 甲酸钠 15%— 40%、 消泡剂 15%~ 0%。
2、 根据权利要求 1所述的一种湿法石灰石烟气脱硫浆液稳定剂， 其特征在 于， 所述石灰为生石灰或消石灰。
3、 根据权利要求 1所述的一种湿法石灰石烟气脱硫浆液稳定剂， 其特征在 于， 所述消泡剂为有机硅聚醚固体复合物， 该有机硅聚醚固体复合物由 30%聚 二甲基硅油、 10%聚醚、 30%碳酸钠、 30%硅酸钠混合， 再将混合物干燥粉碎而 成。
4、 一种湿法石灰石烟气脱硫浆液稳定剂的使用方法， 其特征在于， 所述方 法在脱硫塔外部将浆液稳定剂用水或脱硫浆液配制成质量浓度为 10%— 30%的 均匀液体， 用泵打入浆液循环泵的入口， 经过浆液循环泵和浆液雾化喷淋装置， 依次进入吸收区和反应区与烟气和脱硫浆液发生物理化学作用， 脱硫浆液稳定 剂有效作用的浓度范围为 200— 1000mg/L。
PCT/CN2012/000580 2011-12-06 2012-05-02 湿法石灰石烟气脱硫浆液稳定剂及其使用方法 WO2013082856A1 (zh)

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