CN102580485A - Flue gas desulfurization method for preparing desulfurizer by utilizing magnesite tailings obtained through flotation - Google Patents
Flue gas desulfurization method for preparing desulfurizer by utilizing magnesite tailings obtained through flotation Download PDFInfo
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- CN102580485A CN102580485A CN2012100449562A CN201210044956A CN102580485A CN 102580485 A CN102580485 A CN 102580485A CN 2012100449562 A CN2012100449562 A CN 2012100449562A CN 201210044956 A CN201210044956 A CN 201210044956A CN 102580485 A CN102580485 A CN 102580485A
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- desulfurization
- flue gas
- slurry
- flotation
- desulfurizer
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 58
- 230000023556 desulfurization Effects 0.000 title claims abstract description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000003546 flue gas Substances 0.000 title claims abstract description 27
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 title claims abstract description 23
- 239000001095 magnesium carbonate Substances 0.000 title claims abstract description 23
- 229910000021 magnesium carbonate Inorganic materials 0.000 title claims abstract description 23
- 235000014380 magnesium carbonate Nutrition 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000005188 flotation Methods 0.000 title claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 239000003517 fume Substances 0.000 claims 1
- 230000020477 pH reduction Effects 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012271 agricultural production Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
Description
技术领域 technical field
本发明涉及火力发电厂烟气脱硫领域，特别是一种利用浮选后菱镁矿尾矿制备脱硫剂的烟气脱硫方法。The invention relates to the field of flue gas desulfurization in thermal power plants, in particular to a flue gas desulfurization method for preparing a desulfurizing agent from magnesite tailings after flotation.
背景技术 Background technique
电力热力行业二氧化硫排放量占总二氧化硫排放量的88.5％，烟气中SO2的直接排放会对自然生态环境、工农业生产和人类的健康等方面造成危害。目前我国烟气脱硫主要是湿式钙基脱硫工艺，而钙基脱硫具有运行成本高，系统复杂且易结垢，脱硫后产物再利用效率低，副产品难以处理，造成二次污染的缺点。而镁基脱硫在美国和日本已运行20多年，具有脱硫效率高、脱硫系统运行稳定、投资少、运行维护费用低、可回收副产物等优点。但脱硫剂轻烧氧化镁制备过程中存在烟气污染、制造成本高等问题，使湿法镁基脱硫工艺的推广受到影响。中国专利公开(公告)号CN1320945C，名称为“利用菱镁矿石粉进行烟气脱硫的方法”，介绍了利用菱镁矿原矿石粉经球磨机研磨为250-300目的粉末，代替轻烧氧化镁用于湿法烟气脱硫工艺中，以降低湿法镁基烟气脱硫工艺的运行成本，利于湿法镁基烟气脱硫技术的推广应用。但菱镁矿原矿具有脱硫效率低，只有25％左右，且脱硫时效短的缺点，无法满足火力发电企业对烟气脱硫剂的使用要求。Sulfur dioxide emissions in the power and heat industry account for 88.5% of the total sulfur dioxide emissions. The direct emission of SO 2 in flue gas will cause harm to the natural ecological environment, industrial and agricultural production, and human health. At present, flue gas desulfurization in my country is mainly wet calcium-based desulfurization process, and calcium-based desulfurization has the disadvantages of high operating cost, complex system and easy scaling, low efficiency of product reuse after desulfurization, difficult disposal of by-products, and secondary pollution. Magnesium-based desulfurization has been in operation in the United States and Japan for more than 20 years, and has the advantages of high desulfurization efficiency, stable operation of the desulfurization system, low investment, low operation and maintenance costs, and recyclable by-products. However, there are problems such as flue gas pollution and high manufacturing cost in the preparation process of desulfurization agent light-burned magnesia, which affects the promotion of wet magnesium-based desulfurization process. Chinese Patent Publication (Announcement) No. CN1320945C, titled "Using Magnesite Ore Powder to Carry Out Flue Gas Desulfurization Method", introduces the use of magnesite raw ore powder to be ground into 250-300 mesh powder by ball mill to replace lightly burned magnesia In the wet flue gas desulfurization process, the operating cost of the wet magnesium-based flue gas desulfurization process is reduced, which is beneficial to the popularization and application of the wet magnesium-based flue gas desulfurization technology. However, raw magnesite ore has the disadvantages of low desulfurization efficiency, only about 25%, and short desulfurization time, which cannot meet the requirements of thermal power enterprises for the use of flue gas desulfurizers.
发明内容 Contents of the invention
本发明提供了一种利用浮选后菱镁矿尾矿制备脱硫剂的烟气脱硫方法，将浮选后菱镁矿尾矿经柠檬酸酸化处理，促进MgCO3在脱硫浆液中的溶解电离，可显著提高脱硫效率达到90％以上，降低脱硫工艺运行成本。The invention provides a flue gas desulfurization method using magnesite tailings after flotation to prepare a desulfurizer. The magnesite tailings after flotation are acidified with citric acid to promote the dissolution and ionization of MgCO in the desulfurization slurry. The desulfurization efficiency can be significantly increased to more than 90%, and the operation cost of the desulfurization process can be reduced.
本发明提供利用菱镁矿尾矿制备脱硫剂的烟气脱硫方法技术方案如下：The present invention provides the technical scheme of flue gas desulfurization method using magnesite tailings to prepare desulfurizer as follows:
浮选后菱镁矿尾矿主要矿物相为碳酸镁，取小于200目的浮选后菱镁矿尾矿粉与水按质量百分比10％～40％的比例配成脱硫浆液，在脱硫浆液中加入质量百分比0.2％～1％的柠檬酸，对浆液进行酸化处理，促进MgCO3的溶解电离，熟化15～30min，制成脱硫剂。The main mineral phase of the magnesite tailings after flotation is magnesium carbonate. Take the magnesite tailings powder and water after flotation of less than 200 meshes to make a desulfurization slurry in the proportion of 10% to 40% by mass, and add citric acid with a mass percentage of 0.2% to 1% is used to acidify the slurry to promote the dissolution and ionization of MgCO 3 , and it is matured for 15 to 30 minutes to make a desulfurizer.
将脱硫剂送入脱硫塔中与烟气中的SO2反应。控制脱硫塔中脱硫反应温度在50℃～60℃，循环浆液PH值控制在5～6.5之间，在脱硫塔中脱硫浆液中的MgCO3与烟气中的SO2发生化学反应生成MgSO3，实现烟气中SO2的去除。The desulfurizer is sent into the desulfurization tower to react with SO2 in the flue gas. Control the desulfurization reaction temperature in the desulfurization tower at 50°C to 60°C, and control the pH value of the circulating slurry between 5 and 6.5. In the desulfurization tower, the MgCO 3 in the desulfurization slurry reacts with the SO 2 in the flue gas to form MgSO 3 . Realize the removal of SO 2 in the flue gas.
本发明与现有技术相比，显著的有益效果体现在：Compared with the prior art, the present invention has remarkable beneficial effects embodied in:
将浮选后菱镁矿尾矿经酸化处理后用于湿法烟气脱硫工艺中，可以克服目前火力发电厂湿法钙基脱硫设备运行成本高，系统复杂易结垢，脱硫后产物再利用效率低，副产品难以处理等缺点。减少湿法镁基脱硫剂轻烧氧化镁制备过程中的能源消耗和烟气污染，降低脱硫剂的制造成本，完善湿法镁基脱硫工艺，利于湿法镁基脱硫工艺的推广应用；同时可提高浮选后菱镁矿尾矿的综合利用率，减少浮选后菱镁矿尾矿对矿区周围环境的破坏，使尾矿资源变废为宝，为浮选后菱镁矿尾矿资源的再利用开辟一条新途径。使用本发明制备的脱硫剂，脱硫时效长，脱硫效率达到90％以上；再者可减少火力发电企业二氧化硫的排放量，从而实现资源的可持续利用及环境保护的双赢。The magnesite tailings after flotation are acidified and used in the wet flue gas desulfurization process, which can overcome the high operating cost of the current wet calcium-based desulfurization equipment in thermal power plants, the system is complex and easy to scale, and the desulfurized products can be reused Low efficiency, difficult to deal with by-products and other disadvantages. Reduce energy consumption and flue gas pollution in the preparation process of wet-process magnesium-based desulfurization agent light-burned magnesia, reduce the manufacturing cost of desulfurizer, improve the wet-process magnesium-based desulfurization process, and facilitate the popularization and application of wet-process magnesium-based desulfurization process; Improve the comprehensive utilization rate of magnesite tailings after flotation, reduce the damage to the surrounding environment of the mining area by magnesite tailings after flotation, and turn waste into treasure, which is a great contribution to the development of magnesite tailings resources after flotation. Reuse opens up a new avenue. The desulfurization agent prepared by the invention has a long desulfurization time limit and a desulfurization efficiency of more than 90 percent; moreover, it can reduce the emission of sulfur dioxide in thermal power generation enterprises, thereby realizing the sustainable utilization of resources and the win-win situation of environmental protection.
具体实施方式 Detailed ways
下面以实施例更详细描述本发明：Describe the present invention in more detail with embodiment below:
选择的浮选后菱镁矿尾矿，其主要矿物相为碳酸镁。将浮选后菱镁矿尾矿筛分后取小于200目的尾矿粉100kg加入到1000kg水中制成脱硫浆液，在浆液中加入2kg柠檬酸，对浆液进行酸化处理，以促进MgCO3的溶解电离，再熟化30min成为脱硫剂。The main mineral phase of the selected magnesite tailings after flotation is magnesium carbonate. Sieve the magnesite tailings after flotation and add 100kg of tailings powder less than 200 meshes into 1000kg of water to make a desulfurization slurry, add 2kg of citric acid to the slurry, and acidify the slurry to promote the dissolution and ionization of MgCO 3 , and then matured for 30 minutes to become a desulfurizer.
将脱硫剂送入脱硫塔中，控制脱硫塔中温度为55℃～60℃，循环浆液PH值为5.5，脱硫浆液中的MgCO3与烟气中的SO2反应生成MgSO3，从而实现烟气中SO2的去除，脱硫效率可达95％以上。Send the desulfurization agent into the desulfurization tower, control the temperature in the desulfurization tower to 55°C to 60°C, and the pH value of the circulating slurry to be 5.5. The MgCO 3 in the desulfurization slurry reacts with the SO 2 in the flue gas to form MgSO 3 , thereby realizing the flue gas In the removal of SO 2 , the desulfurization efficiency can reach more than 95%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528781A (en) * | 2014-11-26 | 2015-04-22 | 中化化肥有限公司成都研发中心 | Method for removing sulfur dioxide in flue gas and preparing magnesium sulfate by utilizing phosphorus floatation tailings |
| CN107398171A (en) * | 2017-06-14 | 2017-11-28 | 昆明理工大学 | A kind of method that acid gas in flue gas is removed using metal tailings |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3955966A (en) * | 1974-03-06 | 1976-05-11 | August Thyssen-Hutte Ag | Method for dispensing a fluidizable solid from a pressure vessel |
| CN1334324A (en) * | 2001-07-02 | 2002-02-06 | 广州市粤首实业有限公司 | Efficient sulfur-fixating agent for fuel coal and its preparing process and application |
| CN1727055A (en) * | 2005-07-26 | 2006-02-01 | 六合天融（北京）环保科技有限公司 | Method for carrying out flue gas desulfurization by using mineral powder of magnesite |
| WO2011031277A1 (en) * | 2009-09-14 | 2011-03-17 | Barry Hugghins | Method for wet flue gas desulfurization |
-
2012
- 2012-02-24 CN CN2012100449562A patent/CN102580485A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3955966A (en) * | 1974-03-06 | 1976-05-11 | August Thyssen-Hutte Ag | Method for dispensing a fluidizable solid from a pressure vessel |
| CN1334324A (en) * | 2001-07-02 | 2002-02-06 | 广州市粤首实业有限公司 | Efficient sulfur-fixating agent for fuel coal and its preparing process and application |
| CN1727055A (en) * | 2005-07-26 | 2006-02-01 | 六合天融（北京）环保科技有限公司 | Method for carrying out flue gas desulfurization by using mineral powder of magnesite |
| WO2011031277A1 (en) * | 2009-09-14 | 2011-03-17 | Barry Hugghins | Method for wet flue gas desulfurization |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528781A (en) * | 2014-11-26 | 2015-04-22 | 中化化肥有限公司成都研发中心 | Method for removing sulfur dioxide in flue gas and preparing magnesium sulfate by utilizing phosphorus floatation tailings |
| CN107398171A (en) * | 2017-06-14 | 2017-11-28 | 昆明理工大学 | A kind of method that acid gas in flue gas is removed using metal tailings |
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Application publication date: 20120718 |