CN105536505A - Dry flue gas desulfurization method through industrial-ore-washing filter cake - Google Patents
Dry flue gas desulfurization method through industrial-ore-washing filter cake Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 29
- 230000023556 desulfurization Effects 0.000 title claims abstract description 29
- 238000005406 washing Methods 0.000 title claims abstract description 28
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003546 flue gas Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000012065 filter cake Substances 0.000 title 1
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 235000015895 biscuits Nutrition 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- KRCAYUPYTQNRQM-UHFFFAOYSA-I aluminum;iron(2+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Fe+2] KRCAYUPYTQNRQM-UHFFFAOYSA-I 0.000 claims description 2
- HHSPVTKDOHQBKF-UHFFFAOYSA-J calcium;magnesium;dicarbonate Chemical compound [Mg+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HHSPVTKDOHQBKF-UHFFFAOYSA-J 0.000 claims description 2
- LWNKHILEJJTLCI-UHFFFAOYSA-J calcium;magnesium;tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mg+2].[Ca+2] LWNKHILEJJTLCI-UHFFFAOYSA-J 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 229960005191 ferric oxide Drugs 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011268 retreatment Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
- B01D53/83—Solid phase processes with moving reactants
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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
- B01D53/508—Sulfur oxides by treating the gases with solids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/602—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/12—Methods and means for introducing reactants
- B01D2259/128—Solid reactants
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- Environmental & Geological Engineering (AREA)
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- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
本发明涉及一种资源化利用工业矿石水洗泥饼制备高效衍生脱硫剂，用于火力发电厂等工业烟气脱硫，属难处理固体废物资源化利用及污染气体控制的环境保护技术领域。本发明采用工业矿石水洗泥饼制得衍生脱硫剂。该脱硫剂主要由钙镁、铁铝组成，各百分比分别占总金属含量的80~90%及10%~20%。工业矿石水洗泥饼衍生材料高效脱硫的机理，在于水洗泥饼衍生脱硫剂具有高比表面积及孔隙率，其组分中的CaMgFeAl混合氧化物起到协同作用促进烟气中的二氧化硫脱除。该法得到的脱硫剂不仅对固体废物进行了资源化利用、降低了脱硫剂成本，并且具备高效的脱硫效果。The invention relates to a high-efficiency derivative desulfurizer prepared by resource utilization of industrial ore washing mud cake, which is used for desulfurization of industrial flue gas in thermal power plants and the like, and belongs to the technical field of environmental protection of refractory solid waste resource utilization and pollution gas control. The invention uses industrial ore to wash mud cake to prepare derivative desulfurizer. The desulfurizer is mainly composed of calcium magnesium, iron and aluminum, each percentage accounts for 80-90% and 10%-20% of the total metal content respectively. The mechanism of efficient desulfurization of industrial ore-washed mud cake-derived materials is that the water-washed mud cake-derived desulfurizer has high specific surface area and porosity, and the CaMgFeAl mixed oxides in its components play a synergistic role in promoting the removal of sulfur dioxide in flue gas. The desulfurizing agent obtained by the method not only utilizes the solid waste as a resource, reduces the cost of the desulfurizing agent, but also has a high-efficiency desulfurizing effect.
Description
技术领域technical field
本发明涉及一种工业矿石水洗泥饼干法高效处理二氧化硫污染气体方法，具体地说，是以钢铁厂固体废物矿石水洗泥饼为脱硫剂原料，对火电厂等工业排放的污染气体进行脱硫的处理方法，属于污染气体防治技术领域。The invention relates to a method for efficiently treating sulfur dioxide polluted gas by industrial ore washing mud biscuit method. Specifically, it uses the solid waste ore washing mud cake of iron and steel plants as a desulfurizer raw material to desulfurize the polluted gas discharged from thermal power plants and other industries. The method belongs to the technical field of pollution gas prevention and control.
背景技术Background technique
目前，我国发电厂等工业主要仍以煤作为主要燃料进行发电，燃煤所产生的污染物是造成我国生态环境破坏的最大污染源，其中我国二氧化硫排放87%来自燃煤，排放总量连续多年在1400万吨以上，造成的酸雨污染面积约占国土面积1/3。加大火电厂等二氧化硫的控制力度尤为紧迫。目前烟气脱硫是最为有效控制二氧化硫排放的方法之一。At present, my country's power plants and other industries mainly use coal as the main fuel for power generation. The pollutants produced by coal combustion are the largest pollution source causing damage to my country's ecological environment. Among them, 87% of my country's sulfur dioxide emissions come from coal combustion, and the total emissions have been in China for many years. More than 14 million tons, the area of acid rain pollution caused accounts for about 1/3 of the country's land area. It is particularly urgent to increase the control of sulfur dioxide in thermal power plants. At present, flue gas desulfurization is one of the most effective methods to control sulfur dioxide emissions.
据统计，目前国外对二氧化硫的控制主要采用湿式石灰石-石膏脱硫法，因为其主要优点是脱硫效率高、运行可靠性好，但存在投资运行成本高、耗水量大以及后续需对水进行再处理等一系列问题。综合我国目前的二氧化硫污染现状和经济实力，全部采用这种具有很高脱硫效率但投资运行成本高的湿法烟气脱硫是难以接受的，作为火电厂企业，在确定环保指标达标的情况下，他们肯定是选择费用更低的脱硫剂，以及降低脱硫工艺的运行成本。According to statistics, at present, the wet limestone-gypsum desulfurization method is mainly used in foreign countries for the control of sulfur dioxide, because its main advantages are high desulfurization efficiency and good operation reliability, but there are high investment and operation costs, large water consumption and subsequent water retreatment. And so on a series of questions. Considering the current situation of sulfur dioxide pollution and economic strength in our country, it is unacceptable to adopt this kind of wet flue gas desulfurization with high desulfurization efficiency but high investment and operation costs. As a thermal power plant enterprise, when the environmental protection indicators are determined to be up to standard, They must choose a desulfurizer with lower cost and reduce the operating cost of the desulfurization process.
工业矿石水洗泥饼是一种难处理固体废物。我国每年会产生300万吨左右的工业矿石水洗泥饼。对于工业矿石水洗泥饼的处理，国内外的一些知名钢铁厂对工业矿石泥饼选择回炉再煅烧，然后压缩成球作为炼钢转炉护炉料。而一般的小型钢铁厂由于种种设备成本原因，或是对这种工业矿石水洗泥饼认识的不足，一般选择拉去填埋铺路，或者直接排入江河，既造成了环境污染，同时还得支付巨额的排污费。近几年随着环境问题的重视，这种工业矿石水洗泥饼也成为钢铁产业急需解决的一大难题。Industrial ore washing mud cake is a kind of solid waste that is difficult to treat. my country will produce about 3 million tons of industrial ore washing mud cake every year. For the treatment of industrial ore washed mud cake, some well-known steel mills at home and abroad choose to return the industrial ore mud cake to the furnace for calcination, and then compress it into balls as the steelmaking converter protection material. However, due to various equipment cost reasons or lack of understanding of this kind of industrial ore washing mud cake, ordinary small iron and steel plants generally choose to pull it to landfill for paving, or directly discharge it into rivers, which not only causes environmental pollution, but also has to pay for it. Huge sewage charges. In recent years, with the emphasis on environmental issues, this kind of industrial ore washing mud cake has also become a major problem that the steel industry needs to solve urgently.
据分析检测，这种工业矿石水洗泥饼中主要成分为CaCO3、MgCO3,含量在80~90%左右，脱硫性能较好。且其中还含有一些促进脱硫成分铁的氧化物和氧化铝，铁的氧化物为氧化铁、三氧化二铁、四氧化三铁中的一种或几种。同时其在处理后粒径在50um以下占80%，综合可见其能够有效的在干法烟气脱硫工艺中作为脱硫剂使用。According to the analysis and detection, the main components of this industrial ore washing mud cake are CaCO 3 and MgCO 3 , the content is about 80~90%, and the desulfurization performance is good. And it also contains some iron oxides and aluminum oxides that promote desulfurization, and the iron oxides are one or more of iron oxide, ferric oxide, and ferric oxide. At the same time, 80% of its particle size is below 50um after treatment. It can be seen that it can be effectively used as a desulfurizer in the dry flue gas desulfurization process.
因此为了解决燃煤造成的二氧化硫急需治理、工业矿石泥饼急需安全处理及利用的问题，本发明拟以工业矿石泥饼作为反应剂，来去除二氧化硫污染气体。Therefore, in order to solve the urgent need for treatment of sulfur dioxide caused by coal burning, and the urgent need for safe treatment and utilization of industrial ore mud cakes, the present invention intends to use industrial ore mud cakes as a reactant to remove sulfur dioxide polluted gases.
发明内容Contents of the invention
本发明旨在解决现有技术不足，提供一种工业矿石水洗泥饼干法脱硫工艺，是以钢铁厂固体废物工业矿石水洗泥饼为原料制备高效脱硫剂，对火电厂等工业排放的污染气体进行净化本发明解决上述技术问题的技术方案如下。The present invention aims to solve the deficiencies of the existing technology, and provides a desulfurization process of industrial ore washing mud biscuit method, which uses the solid waste industrial ore washing mud cake of the iron and steel plant as a raw material to prepare a high-efficiency desulfurizer, and desulfurizes the polluted gas discharged by thermal power plants and other industries. The technical solution for purifying the present invention to solve the above-mentioned technical problems is as follows.
一种工业矿石水洗泥饼干法烟气脱硫的方法，其特征在于具有如下过程和步骤：A method for flue gas desulfurization of industrial ore washing mud biscuit method, characterized in that it has the following processes and steps:
（1）工业矿石水洗泥饼通常含有Ca、Mg、Fe、Al等金属元素，对于任何工业矿石水洗泥饼，通过组分匹配原理制备得到衍生二氧化硫气体脱除剂；(1) Industrial ore washing mud cake usually contains metal elements such as Ca, Mg, Fe, Al, etc. For any industrial ore washing mud cake, a derivative sulfur dioxide gas remover is prepared through the principle of component matching;
首先对不同工业矿石水洗泥饼进行组分测定，并对不同工业矿石水洗泥饼按一定比例混合，使得泥饼中各组分的重量百分比为：钙镁碳酸盐和钙镁氢氧化物为80-90%；铁铝氢氧化物为10-20%；并混合搅拌8-12小时；然后将混合泥饼焙烧热处理，焙烧温度为800-1000℃；最终得到衍生脱硫剂First, different industrial ore washing mud cakes are subjected to component determination, and different industrial ore washing mud cakes are mixed in a certain proportion, so that the weight percentage of each component in the mud cake is: calcium magnesium carbonate and calcium magnesium hydroxide are 80-90%; 10-20% iron-aluminum hydroxide; mixed and stirred for 8-12 hours; then the mixed mud cake is roasted and heat-treated at a roasting temperature of 800-1000°C; finally, a derivative desulfurizer is obtained
（2）将上述步骤（1）所得工业矿石水洗泥饼衍生脱硫剂喷射到吸收塔内对待处理烟气进行干法脱硫；其中工业矿石水洗泥饼脱硫剂脱硫容量为150-200mg/g；颗粒的投加量与所处理烟气中二氧化硫浓度有关，对处理2000ppm二氧化硫的烟气，且固气比为1.5~2L/g；最终的烟气能够达到二氧化硫排放标准。(2) Spray the desulfurization agent derived from the industrial ore washing mud cake obtained in the above step (1) into the absorption tower for dry desulfurization of the flue gas to be treated; the desulfurization capacity of the industrial ore washing mud cake desulfurization agent is 150-200mg/g; The dosage is related to the concentration of sulfur dioxide in the treated flue gas. For flue gas with 2000ppm sulfur dioxide, the solid-gas ratio is 1.5~2L/g; the final flue gas can meet the sulfur dioxide emission standard.
本发明机理和效果的优点The advantage of mechanism and effect of the present invention
工业矿石水洗泥饼处理二氧化硫污染气体的机理，在于水洗泥饼脱硫剂具有高比表面积及孔隙率，并且其组分中的CaMgFeAl混合氧化物起到协同作用促进烟气中的二氧化硫脱除。The mechanism of industrial ore washing mud cake to treat sulfur dioxide polluted gas is that the washing mud cake desulfurizer has a high specific surface area and porosity, and the CaMgFeAl mixed oxide in its components plays a synergistic role in promoting the removal of sulfur dioxide in flue gas.
本发明的有益效果是：本发明通过利用废弃的工业矿石水洗泥饼进行组分匹配混合后制成脱硫剂，不仅充分的利用了废弃物、降低了脱硫成本，同时其具有良好的脱硫效果。The beneficial effects of the present invention are: the present invention uses the discarded industrial ore washed mud cake to carry out component matching and mixing to make a desulfurizer, which not only fully utilizes the waste, reduces the desulfurization cost, but also has a good desulfurization effect.
具体实施方式detailed description
本发明结合以下实施案例作进一步描述。The present invention is further described in conjunction with the following examples.
实施本例实施例的过程和步骤如下：The process and steps of implementing this embodiment are as follows:
（1）对工业矿石水洗泥饼预处理工序：取不同的工业矿石水洗泥饼按比例混合之后，其中主要成分为CaCO3、Ca(OH)2、MgCO3以及Mg(OH)2，质量含量为85%，铁及铝的氢氧化物含量约为15%。通过搅拌12h混合后的泥饼在900oC下焙烧，然后对其破碎，选取的脱硫剂粒径在80-100目。(1) Pretreatment process of industrial ore washing mud cake: After mixing different industrial ore washing mud cakes in proportion, the main components are CaCO 3 , Ca(OH) 2 , MgCO 3 and Mg(OH) 2 , the mass content The iron and aluminum hydroxide content is about 15%. After stirring for 12 hours, the mixed mud cake was roasted at 900 o C, and then crushed. The selected desulfurizer had a particle size of 80-100 mesh.
（2）烟气脱硫工序：将脱硫剂喷射到吸收塔内对待处理烟气进行干法脱硫，所述待处理的烟气中二氧化硫浓度在2000ppm，控制烟气流速在50ml/min，在处理15min后，所述处理后的烟气中二氧化硫浓度在74.6ppm，脱硫效率96.27%。(2) Flue gas desulfurization process: spray the desulfurizer into the absorption tower for dry desulfurization of the flue gas to be treated. The concentration of sulfur dioxide in the flue gas to be treated is 2000ppm, and the flue gas flow rate is controlled at 50ml/min. Finally, the concentration of sulfur dioxide in the treated flue gas was 74.6ppm, and the desulfurization efficiency was 96.27%.
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| CN106311739A (en) * | 2016-10-12 | 2017-01-11 | 上海大学 | Method for stabilizing heavy metal in soil through industrial ore washing mud cake stabilizer |
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| CN101791622A (en) * | 2010-03-17 | 2010-08-04 | 上海天顿环境工程有限公司 | Process method for converting metal magnesium slag into desulphurizer of boiler |
| CN102787210A (en) * | 2012-06-28 | 2012-11-21 | 辽宁中汇环保科技有限公司 | Calcareous premelted composite deoxidation and desulfurization agent for low-cost steel-making and method for preparing same |
| CN103537184A (en) * | 2013-10-30 | 2014-01-29 | 河北工业大学 | Method for preparing complex removal agent from steel and iron pickling waste residues to carry out desulfurization and denitrification |
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| CN101791622A (en) * | 2010-03-17 | 2010-08-04 | 上海天顿环境工程有限公司 | Process method for converting metal magnesium slag into desulphurizer of boiler |
| CN102787210A (en) * | 2012-06-28 | 2012-11-21 | 辽宁中汇环保科技有限公司 | Calcareous premelted composite deoxidation and desulfurization agent for low-cost steel-making and method for preparing same |
| CN103537184A (en) * | 2013-10-30 | 2014-01-29 | 河北工业大学 | Method for preparing complex removal agent from steel and iron pickling waste residues to carry out desulfurization and denitrification |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106311739A (en) * | 2016-10-12 | 2017-01-11 | 上海大学 | Method for stabilizing heavy metal in soil through industrial ore washing mud cake stabilizer |
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