CN103551022B - A kind of catalytic oxidation type flue gas circulating fluidized bed desulfurization synergisting method - Google Patents
A kind of catalytic oxidation type flue gas circulating fluidized bed desulfurization synergisting method Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 71
- 230000023556 desulfurization Effects 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 9
- 239000003546 flue gas Substances 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000007921 spray Substances 0.000 claims abstract description 10
- 239000006096 absorbing agent Substances 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 230000002195 synergetic effect Effects 0.000 claims abstract 3
- 230000003009 desulfurizing effect Effects 0.000 claims abstract 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid group Chemical group C(CCCC(=O)O)(=O)O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 10
- 239000003245 coal Substances 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明为一种催化氧化型烟气循环流化床脱硫增效方法，将吸水剂与喷淋水混合后一起喷入脱硫塔体内，将其与脱硫剂的质量百分含量为1.2％-1.23％的吸水剂与喷淋水混合后一起喷入脱硫塔体内；将与水的质量配比为0.03％-0.032％的表面活性剂、质量浓度为0.95g/L-1g/L的催化剂，在溶液总量不变的情况下至少分两次在不同位置喷入塔体；将氧化剂先溶于水单独从脱硫塔顶部喷入，其与水的质量配比为2.5％-2.8％，喷水量应为喷水总量的20％-30％。本发明的优点是材料易得、价格便宜、制备工艺简单，能有效提高脱硫效率，且对环境不会造成二次污染。The present invention is a catalytic oxidation flue gas circulating fluidized bed desulfurization synergistic method. The water absorbing agent is mixed with spray water and sprayed into the desulfurization tower body together, and the mass percentage of the desulfurizing agent and the desulfurization agent is 1.2%-1.23% % of the water-absorbing agent is mixed with the spray water and sprayed into the desulfurization tower body together; the surfactant with a mass ratio of 0.03%-0.032% and the catalyst with a mass concentration of 0.95g/L-1g/L are mixed in the desulfurization tower. When the total amount of the solution remains unchanged, spray it into the tower at least twice at different positions; dissolve the oxidant in water and spray it separately from the top of the desulfurization tower, and its mass ratio with water is 2.5%-2.8%. The amount should be 20%-30% of the total amount of water sprayed. The invention has the advantages of readily available materials, cheap price, simple preparation process, can effectively improve desulfurization efficiency, and will not cause secondary pollution to the environment.
Description
技术领域technical field
本发明涉及一种催化氧化型烟气循环流化床脱硫增效方法，该方法主要用于提高循环流化床脱硫塔的脱硫效率。The invention relates to a catalytic oxidation type flue gas circulating fluidized bed desulfurization efficiency enhancement method, which is mainly used for improving the desulfurization efficiency of a circulating fluidized bed desulfurization tower.
背景技术Background technique
我国是一个能源生产和消费的大国，其能源消耗量位居世界第二，而在能源消耗的结构中，煤炭资源占据了最大的比例。根据煤炭行业协会统计：2011年我国煤炭产量35.2亿吨，约占一次能源生产总量78.6％；煤炭消费总量35.7亿吨，约占一次能源消费总量72.8％。我国富煤、缺油、少气的资源状况决定了在今后较长的时期内，煤炭资源仍是我国的主要能源。我国的一次能源消耗行业，尤其是电力行业仍以燃煤机组为主。而由燃煤产生的大气污染问题，尤其是SO2的排放问题还将长期影响我国发展。my country is a big country in energy production and consumption, its energy consumption ranks second in the world, and in the structure of energy consumption, coal resources occupy the largest proportion. According to the statistics of the Coal Industry Association: in 2011, my country's coal output was 3.52 billion tons, accounting for 78.6% of the total primary energy production; the total coal consumption was 3.57 billion tons, accounting for 72.8% of the total primary energy consumption. my country's coal-rich, oil-deficient, and gas-poor resources determine that coal resources will remain my country's main energy source for a long time to come. my country's primary energy consumption industries, especially the power industry, are still dominated by coal-fired units. The air pollution caused by coal burning, especially the emission of SO 2 will affect the development of our country for a long time.
脱硫技术的研究已经有90多年，脱硫技术已有上百种，这些脱硫技术按工艺特点可分为三类，即：燃烧前脱硫、燃烧中脱硫、燃烧后脱硫。燃烧后脱硫即烟气脱硫是目前控制SO2排放的最有效、应用最广泛的脱硫技术。按吸收剂及脱硫产物在脱硫过程中的干湿状态可分为：湿法、干法和半干法。常见的湿法烟气脱硫技术有：石灰石/石灰-石膏法、亚硫酸钠循环吸收法、氧化镁及海水脱硫等等。湿法烟气脱硫技术比较成熟，在众多的脱硫技术中占据主导地位，但是湿法烟气脱硫存在初期投资大，系统复杂，占地面积大，能耗高，设备腐蚀严重，管道易堵塞，废水难以处理等问题。干法脱硫技术存在脱硫剂利用率低，脱硫效率低等缺点。The desulfurization technology has been researched for more than 90 years, and there are hundreds of desulfurization technologies. These desulfurization technologies can be divided into three categories according to the process characteristics, namely: desulfurization before combustion, desulfurization during combustion, and desulfurization after combustion. Post-combustion desulfurization, or flue gas desulfurization, is the most effective and widely used desulfurization technology to control SO 2 emissions. According to the dry and wet state of absorbent and desulfurization products in the desulfurization process, it can be divided into: wet method, dry method and semi-dry method. Common wet flue gas desulfurization technologies include: limestone/lime-gypsum method, sodium sulfite cycle absorption method, magnesium oxide and seawater desulfurization, etc. Wet flue gas desulfurization technology is relatively mature and occupies a dominant position among many desulfurization technologies. However, wet flue gas desulfurization has large initial investment, complex system, large floor area, high energy consumption, serious equipment corrosion, and easy blockage of pipelines. Difficult to deal with waste water and other issues. Dry desulfurization technology has the disadvantages of low utilization rate of desulfurization agent and low desulfurization efficiency.
因此，半干法脱硫技术作为兼有干法与湿法的一些特点，特别是在湿状态下脱硫在干状态下处理脱硫产物，以及兼有湿法脱硫反应速度快和干法无废水废酸排出、脱硫后产物易于处理的好处，而越来越受到人们的广泛关注。虽然，半干法脱硫有诸多优点，但是其脱硫效率比湿法的低，脱硫剂利用率也低于湿法脱硫影响了它的广泛应用。随着技术的改进循环流化床脱硫塔半干法脱硫可以循环利用脱硫剂，提高了脱硫剂的利用率，但距离人们理想中的效率仍有一段距离，所以人们仍需要一种材料易得、价格便宜、制备工艺简单，对环境不会造成二次污染的脱硫增效剂来提高脱硫效率。Therefore, the semi-dry desulfurization technology has some characteristics of both dry and wet methods, especially the desulfurization in wet state, the treatment of desulfurization products in dry state, and the fast reaction speed of wet desulfurization and the dry method without waste water and waste acid. The benefit of easy handling of the product after discharge and desulfurization has attracted more and more attention from people. Although semi-dry desulfurization has many advantages, its desulfurization efficiency is lower than that of wet desulfurization, and the utilization rate of desulfurizer is also lower than that of wet desulfurization, which affects its wide application. With the improvement of technology, the semi-dry desulfurization of the circulating fluidized bed desulfurization tower can recycle the desulfurizer, which improves the utilization rate of the desulfurizer, but there is still a distance from the ideal efficiency of people, so people still need a kind of material that is easy to get It is a desulfurization synergist with low price, simple preparation process, and no secondary pollution to the environment to improve desulfurization efficiency.
发明内容Contents of the invention
本发明是为了提供一种材料易得、价格便宜、制备工艺简单，对环境不会造成二次污染的脱硫增效方法。The purpose of the invention is to provide a desulfurization and efficiency-enhancing method with easy-to-obtain materials, low price, simple preparation process and no secondary pollution to the environment.
本发明的上述目的是通过以下技术方案实现的：Above-mentioned purpose of the present invention is achieved through the following technical solutions:
本发明的催化氧化型循环流化床半干法脱硫增效剂，其包括以下成分：质量百分含量为1.2％-1.23％吸水剂，质量百分含量为0.03％-0.032％表面活性剂，质量浓度约为0.95g/L-1g/L的催化剂，质量百分含量为2.5％-2.8％氧化剂。The catalytic oxidation type circulating fluidized bed semi-dry desulfurization synergist of the present invention comprises the following components: 1.2%-1.23% by mass of water-absorbing agent, 0.03%-0.032% by mass of surfactant, The mass concentration of the catalyst is about 0.95g/L-1g/L, and the mass percentage is 2.5%-2.8% of the oxidizing agent.
所述的吸水剂为氯化钙，表面活性剂为烷基苯磺酸钠，催化剂为戊二酸。The water absorbing agent is calcium chloride, the surfactant is sodium alkylbenzenesulfonate, and the catalyst is glutaric acid.
所述的氧化剂为双氧水。Described oxidizing agent is hydrogen peroxide.
所述的催化氧化型循环流化床脱硫塔脱硫增效剂的制备方法，制备步骤为：The preparation method of the catalytic oxidation type circulating fluidized bed desulfurization tower desulfurization synergist, the preparation steps are:
⑴在制备过程中用到的CaCl2，应与喷淋水混合后一起喷入脱硫塔体内，其与脱硫剂的质量配比为1.2％-1.23％。(1) The CaCl 2 used in the preparation process should be mixed with spray water and sprayed into the desulfurization tower body together, and the mass ratio of CaCl 2 and desulfurizer is 1.2%-1.23%.
⑵在制备过程中用到的表面活性剂和催化剂，应先溶于水中，其与水的质量配比表面活性剂为0.03％-0.032％，催化剂质量浓度约为0.95g/L-1g/L。⑵The surfactant and catalyst used in the preparation process should be dissolved in water first, the mass ratio of surfactant and water is 0.03%-0.032%, and the mass concentration of catalyst is about 0.95g/L-1g/L .
⑶在制备过程中用到的氧化剂，应先溶于水单独从脱硫塔顶部喷入，其与水的质量配比为2.5％-2.8％。(3) The oxidizing agent used in the preparation process should be dissolved in water and sprayed separately from the top of the desulfurization tower, and its mass ratio with water is 2.5%-2.8%.
所述的催化氧化型循环流化床脱硫塔脱硫增效剂的使用方法：The method of using the catalytic oxidation type circulating fluidized bed desulfurization tower desulfurization synergist:
⑴在使用过程中用到的CaCl2是作为吸水剂与喷淋水按比例均匀混合后，一起喷入脱硫塔内。⑴The CaCl 2 used in the process of use is used as a water-absorbing agent and the spray water is evenly mixed in proportion, and then sprayed into the desulfurization tower together.
⑵在使用过程中用到的表面活性剂与催化剂溶于水后，在溶液总量不变的情况下至少分两次在不同位置喷入塔体。(2) After the surfactant and catalyst used in the use process are dissolved in water, they are sprayed into the tower at least twice at different positions under the condition that the total amount of the solution remains unchanged.
⑶在使用过程中用到的氧化剂，溶于水后在塔顶喷入，此处的喷水量应为喷水总量(包括塔顶喷水量)的20％-30％。(3) The oxidizing agent used in the process of use should be dissolved in water and sprayed into the top of the tower. The amount of water sprayed here should be 20%-30% of the total amount of water sprayed (including the amount of water sprayed on the top of the tower).
本发明中，氯化钙是作为吸水剂喷入脱硫塔中的，氯化钙具有较好的吸湿保水性，在脱硫塔内可以使脱硫剂较长时间的保持湿润，增加气液相反应时间。烷基苯磺酸钠可以减少水的表面张力，使二氧化硫更容易溶于水中与脱硫剂反应。戊二酸可以减少气-液界面的H+，增加液-固界面的H+，促进了SO2和Ca(OH)2的溶解。双氧水作为氧化剂可以将SO3-氧化成SO4-减少脱硫产物促进脱硫反应的正向进行。In the present invention, calcium chloride is sprayed into the desulfurization tower as a water-absorbing agent. Calcium chloride has good moisture absorption and water retention, and can keep the desulfurizer moist for a long time in the desulfurization tower, increasing the gas-liquid phase reaction time . Sodium alkylbenzene sulfonate can reduce the surface tension of water, so that sulfur dioxide can be more easily dissolved in water and react with desulfurizer. Glutaric acid can reduce H + at the gas-liquid interface, increase H + at the liquid-solid interface, and promote the dissolution of SO 2 and Ca(OH) 2 . As an oxidant, hydrogen peroxide can oxidize SO 3- to SO 4- to reduce desulfurization products and promote the positive progress of desulfurization reaction.
有益效果Beneficial effect
1、本发明催化氧化型脱硫增效剂材料易得、价格便宜、制备工艺简单，对环境不会造成二次污染，能较好的提高循环流化床脱硫塔脱硫效率。1. The catalytic oxidation type desulfurization synergist of the present invention is easy to obtain, cheap in price, simple in preparation process, does not cause secondary pollution to the environment, and can better improve the desulfurization efficiency of the circulating fluidized bed desulfurization tower.
2、将制备好的脱硫增效剂按使用方法加入到脱硫塔中，能够促进二氧化硫与消石灰溶解，及其反应的正向进行，从而提高脱硫效率。循环流化床脱硫塔在Ca/S为1.1-1.4时脱硫效率为90％左右，当加入该脱硫增效剂后脱硫效率可达到99％以上。2. Add the prepared desulfurization synergist into the desulfurization tower according to the usage method, which can promote the dissolution of sulfur dioxide and slaked lime, and the positive progress of the reaction, thereby improving the desulfurization efficiency. The desulfurization efficiency of the circulating fluidized bed desulfurization tower is about 90% when the Ca/S is 1.1-1.4, and the desulfurization efficiency can reach more than 99% after adding the desulfurization synergist.
3、制备的脱硫剂有较好的性能。所用的材料对设备不会造成腐蚀，除了发挥自己的功能外，不与其它物质发生反应，不会对脱硫塔造成不必要的损害。3. The prepared desulfurizer has better performance. The materials used will not cause corrosion to the equipment, and will not react with other substances except for their own functions, and will not cause unnecessary damage to the desulfurization tower.
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| CN1820822A (en) * | 2006-01-25 | 2006-08-23 | 北京朗新明环保科技有限公司 | Method for reinforcing lime stone slurry activity in smoke desulfurizing process and combined additive |
| CN101869824A (en) * | 2009-04-21 | 2010-10-27 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of flue gas desulfurization agent and flue gas desulfurization method |
| CN101721884A (en) * | 2009-12-10 | 2010-06-09 | 攀枝花新钢钒股份有限公司 | Smoke desulphurization agent and smoke desulphurization method |
| CN102847428A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Limestone-gypsum wet desulfurization additive |
| CN102580514A (en) * | 2012-02-29 | 2012-07-18 | 济宁新格瑞水处理有限公司 | Additive for strengthening wet flue gas desulfurization technology |
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