CN101665844B - A method for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials - Google Patents
A method for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 57
- 239000006227 byproduct Substances 0.000 title claims abstract description 52
- 239000002893 slag Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000005245 sintering Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 20
- 230000023556 desulfurization Effects 0.000 title description 49
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000292 calcium oxide Substances 0.000 claims abstract description 13
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 claims abstract description 7
- 235000010261 calcium sulphite Nutrition 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims 4
- 239000003818 cinder Substances 0.000 claims 2
- 230000033228 biological regulation Effects 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000003795 desorption Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- 239000004568 cement Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002956 ash Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 239000003546 flue gas Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000011404 masonry cement Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
Description
技术领域technical field
本发明属于资源综合利用领域，特别是涉及一种以烧结脱硫副产物为辅料制备高炉矿渣微粉的方法，利用现有钢铁生产工序，在对干法半干法脱硫副产物预处理基础上，用于矿渣微粉生产制备。The invention belongs to the field of comprehensive utilization of resources, and in particular relates to a method for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials. The existing iron and steel production process is used on the basis of dry semi-dry desulfurization by-product pretreatment. It is prepared in the production of slag powder.
背景技术Background technique
钢铁企业是SO2排放大户，而烧结过程排放的SO2约占整个钢铁企业SO2排放总量的90％。随着我国经济发展和环保要求的不断提高，钢铁企业烧结烟气脱硫已迫在眉睫，开展烧结烟气脱硫治理对于钢铁企业SO2减排、改善大气质量和区域性酸雨控制具有积极意义。Iron and steel enterprises are major emitters of SO 2 , and the SO 2 emitted by the sintering process accounts for about 90% of the total SO 2 emissions of the entire iron and steel enterprise. With the continuous improvement of China's economic development and environmental protection requirements, sintering flue gas desulfurization in iron and steel enterprises is imminent. Carrying out sintering flue gas desulfurization treatment is of positive significance for iron and steel enterprises to reduce SO 2 emissions, improve air quality and control regional acid rain.
“十一五”规划纲要明确提出，到2010年全国SO2排放总量比“十五”期末削减10％。国家环保局出台的《国家酸雨和二氧化硫污染防治“十一五”规划》中指出，要落实14个烧结机烟气脱硫工程，制订钢铁行业二氧化硫减排规划，重点推进钢铁行业烧结机烟气脱硫工程，“十一五”期间，钢铁等非电行业形成40万吨的脱硫能力，同时调整了烧结烟气二氧化硫的排放标准，全面实施排污许可证制度，严格法律责任，依法防治污染等等，这都将促进提高钢铁行业污染物的排放标准，烧结脱硫治理已势在必行。The Outline of the "Eleventh Five-Year Plan" clearly states that by 2010, the total national SO 2 emissions will be reduced by 10% compared with the end of the "Tenth Five-Year Plan". The "National Acid Rain and Sulfur Dioxide Pollution Prevention and Control "Eleventh Five-Year"Plan" issued by the National Environmental Protection Agency pointed out that 14 sintering machine flue gas desulfurization projects should be implemented, and a plan for reducing sulfur dioxide emissions in the iron and steel industry should be formulated, focusing on promoting sintering machine flue gas desulfurization in the steel industry During the "Eleventh Five-Year Plan" period, iron and steel and other non-electric industries formed a desulfurization capacity of 400,000 tons. At the same time, they adjusted the emission standards of sulfur dioxide in sintering flue gas, fully implemented the pollutant discharge permit system, strictly enforced legal responsibilities, and prevented pollution according to law. All these will promote the improvement of the emission standards of pollutants in the iron and steel industry, and the treatment of sintering desulfurization is imperative.
目前国内外较成熟的脱硫工艺有数十种，但由于干法烧结脱硫工艺投资低、占地小、耗水少、工艺简单，并很好地克服了湿法脱硫工艺存在的一些问题和不足，逐渐成为了钢铁企业烧结脱硫的主流工艺。但由于烧结干法半干法脱硫副产物中含有较高的氧化钙及亚硫酸钙，严重影响了脱硫副产物的综合利用。目前，国内外还没有较好的可有效处理和综合利用的技术和工艺，致使脱硫副产物大都堆存处置，这不但占用了大量土地，而且在其堆存中还对周边环境造成了系列问题。At present, there are dozens of mature desulfurization processes at home and abroad, but due to the low investment, small footprint, low water consumption and simple process of the dry sintering desulfurization process, it has overcome some problems and shortcomings of the wet desulfurization process. , has gradually become the mainstream process of sintering desulfurization in iron and steel enterprises. However, due to the high content of calcium oxide and calcium sulfite in the by-products of sintering dry semi-dry desulfurization, it seriously affects the comprehensive utilization of desulfurization by-products. At present, there is no good technology and process that can be effectively treated and comprehensively utilized at home and abroad, resulting in the storage and disposal of most of the desulfurization by-products, which not only takes up a lot of land, but also causes a series of problems to the surrounding environment during its storage. .
申请号为200410015724.X的专利《以脱硫灰渣为缓凝剂的水泥的制造方法》描述了一种水泥制造方法，将脱硫灰渣用作缓凝剂，按水泥熟料、脱硫灰渣、粉煤灰和高炉矿渣以80～98∶2～6∶0～15∶0～15的重量比制备水泥。Application No. 200410015724.X patent "Manufacturing method of cement using desulfurized ash as retarder" describes a cement manufacturing method, using desulfurized ash as a retarder, according to cement clinker, desulfurized ash, Fly ash and blast furnace slag are used in the weight ratio of 80-98:2-6:0-15:0-15 to prepare cement.
申请号为200610085414.4的专利《砌筑水泥》描述了一种利用循环流化床锅炉排放的脱硫灰为主要原料制备低等级砌筑水泥的方法，水泥配方为：脱硫灰50％～70％、石膏2％～6％、水泥熟料24％～48％。The patent "Masonry Cement" with application number 200610085414.4 describes a method for preparing low-grade masonry cement using desulfurized ash discharged from circulating fluidized bed boilers as the main raw material. The cement formula is: 50% to 70% desulfurized ash, gypsum 2% to 6%, cement clinker 24% to 48%.
申请号为200610068783.2的专利《利用脱硫灰烧成硫铝酸盐水泥的工艺技术》描述了一种利用脱硫灰通过高温煅烧制备硫铝酸盐水泥的工艺技术，该技术无需矾土，无需或只需少量石膏，就能实现硫铝酸盐水泥的生产。Patent Application No. 200610068783.2 "Technology for Burning Sulphoaluminate Cement Using Desulfurized Ash" describes a technology for preparing sulphoaluminate cement by using desulfurized ash through high-temperature calcination. This technology does not require alumina, or only A small amount of gypsum is needed to produce sulphoaluminate cement.
申请号为200710003052.4的专利《以脱硫灰钙为原料制造纤维的方法》和申请号为200710003054.3的专利《一种脱硫灰钙纤维纸浆及其为原料的造纸方法》描述了利用脱硫灰制备纤维纸浆及其为原料的造纸方法。Patent Application No. 200710003052.4 "Method for Manufacturing Fiber Using Desulfurized Ash Calcium as Raw Material" and Patent Application No. 200710003054.3 "A Desulfurized Ash Calcium Fiber Pulp and Its Papermaking Method as Raw Material" describe the use of desulfurized ash to prepare fiber pulp and It is the paper making method of the raw material.
经检索，现有专利主要集中在利用电厂脱硫灰制备水泥缓凝剂、砌筑水泥以及烧制水泥等领域，没有检索到利用电厂脱硫灰制备矿渣微粉的相关专利；未发现有关烧结烟气干法半干法脱硫副产物综合利用的发明专利。After searching, the existing patents mainly focus on the fields of preparing cement retarder, masonry cement, and firing cement by using desulfurized ash from power plants. Invention patent for the comprehensive utilization of by-products of semi-dry desulfurization.
发明内容Contents of the invention
本发明的目的在于提供一种以烧结脱硫副产物为辅料制备高炉矿渣微粉的方法，，利用现有钢铁生产工序，将烧结干法脱硫副产物作为辅料，用于矿渣微粉生产，使用烧结干法脱硫副产物作为辅料生产矿渣微粉，在生产过程中实现了氧化钙的稳定化和亚硫酸钙的氧化处理，改善了矿渣粉的反应性能，解决了干法脱硫副产物的综合利用难题，可以实现钢铁企业烧结干法脱硫副产物的大规模利用。The purpose of the present invention is to provide a method for preparing blast furnace slag powder by using sintering desulfurization by-products as auxiliary materials, using the existing iron and steel production process, using sintering dry desulfurization by-products as auxiliary materials for the production of slag fine powder, using sintering dry method The desulfurization by-products are used as auxiliary materials to produce slag micropowder. In the production process, the stabilization of calcium oxide and the oxidation treatment of calcium sulfite are realized, the reaction performance of slag powder is improved, and the problem of comprehensive utilization of dry desulfurization by-products is solved. It can realize Large-scale utilization of sintering dry desulfurization by-products in iron and steel enterprises.
本发明的技术方案是将烧结干法脱硫副产物作为辅料，用于制备高炉矿渣微粉，脱硫副产物的掺入量不超过高炉矿渣(干态)、脱硫副产物总重量的10％，使矿渣微粉中的SO3含量满足国家标准相关规定要求。The technical solution of the present invention is to use sintering dry desulfurization by-products as auxiliary materials for the preparation of blast furnace slag micropowder. The SO3 content in the micropowder meets the requirements of the relevant national standards.
从炼铁厂水冲渣池中输出的高炉矿渣含水率为10％～40％，将炼铁厂水冲渣池中输出的高炉矿渣按比例与烧结脱硫副产物搅拌混匀，成为混合物料，搅拌的同时，矿渣中的游离水与脱硫副产物中的游离氧化钙发生反应，实现游离氧化钙的稳定化处理；随后混合物料进行烘干，在游离水脱除过程中，脱硫副产物中的亚硫酸钙发生氧化反应，生成硫酸钙；烘干后的物料进行粉磨，最终形成高炉矿渣微粉。The water content of the blast furnace slag exported from the water flushing slag pool of the ironworks is 10% to 40%. The blast furnace slag exported from the water flushing slag pool of the ironworks is mixed with the by-products of sintering desulfurization in proportion to form a mixed material. While stirring, the free water in the slag reacts with the free calcium oxide in the desulfurization by-products to achieve the stabilization of the free calcium oxide; then the mixed material is dried, and the desulfurization by-products in the desulfurization by-product Calcium sulfite undergoes an oxidation reaction to generate calcium sulfate; the dried material is ground to form blast furnace slag powder.
所生产的矿渣微粉，其化学成分和反应性能满足国家标准相关规定要求。The chemical composition and reaction performance of the produced slag powder meet the requirements of the relevant national standards.
本发明的优点在于：The advantages of the present invention are:
(1)利用现有钢铁生产工序，在矿渣微粉生产的特定工序中添加烧结干法脱硫副产物，由于干法半干法脱硫副产物的掺入降低了水冲矿渣烘干前的含水率，降低了矿渣微粉的生产能耗，促进了循环经济的发展。(1) Utilize the existing iron and steel production process, add sintering dry desulfurization by-products in the specific process of slag fine powder production, because the incorporation of dry semi-dry desulfurization by-products reduces the water content of the slag before drying, The production energy consumption of slag micropowder is reduced, and the development of circular economy is promoted.
(2)利用原有矿渣微粉生产工序，在将脱硫副产物与含水矿渣混合并经烘干后，实现了干法脱硫副产物中氧化钙的稳定化和亚硫酸钙的氧化处理，为脱硫副产物的大宗利用奠定了基础。(2) Utilizing the original slag micropowder production process, after the desulfurization by-products are mixed with water-containing slag and dried, the stabilization of calcium oxide and the oxidation treatment of calcium sulfite in the dry desulfurization by-products are realized, which is a desulfurization by-product The mass application of products has laid the foundation.
(3)在矿渣中掺入脱硫副产物后，由于脱硫副产物中氧化钙、硫酸钙的引入，改善了矿渣微粉的反应性能，能保证矿渣微粉性能达到国家标准相应规定。(3) After adding desulfurization by-products into the slag, due to the introduction of calcium oxide and calcium sulfate in the desulfurization by-products, the reaction performance of the slag micro-powder is improved, and the performance of the slag micro-powder can be guaranteed to meet the corresponding requirements of the national standard.
附图说明Description of drawings
如图1所示为本发明所涉及的一种以烧结脱硫副产物为辅料制备高炉矿渣微粉的工艺流程图。As shown in Fig. 1, it is a process flow chart for preparing blast furnace slag micropowder by using sintering desulfurization by-products as auxiliary materials involved in the present invention.
具体实施方式Detailed ways
结合图1对本发明的具体实施方式描述如下：The specific embodiment of the present invention is described as follows in conjunction with Fig. 1:
在炼铁厂水冲渣池中输出的矿渣(含水10％～40％)中加入脱硫副产物，并搅拌均匀，在此过程中实现了脱硫副产物中氧化钙的稳定化处理；掺有脱硫副产物的湿态水渣进行烘干，在烘干过程中的高温、氧化气氛下，实现了脱硫副产物中亚硫酸钙的氧化处理，生成硫酸钙；烘干后的物料通过粉磨生成矿渣微粉。由于脱硫副产物中氧化钙、硫酸钙的引入，改善了矿渣微粉的反应性能，能保证矿渣微粉性能达到国家标准相应规定。Add desulfurization by-products to the slag (with a water content of 10% to 40%) exported from the water flushing slag pool of the ironworks, and stir evenly. In this process, the stabilization of calcium oxide in the desulfurization by-products is realized; mixed with desulfurization The wet slag of the by-product is dried, and the oxidation treatment of calcium sulfite in the desulfurization by-product is realized under the high temperature and oxidizing atmosphere during the drying process to generate calcium sulfate; the dried material is ground to generate slag Micronized. Due to the introduction of calcium oxide and calcium sulfate in the desulfurization by-products, the reaction performance of the slag powder is improved, and the performance of the slag powder can be guaranteed to meet the corresponding requirements of the national standard.
实施实例1Implementation example 1
通过实验模拟了上述工业应用过程：The above-mentioned industrial application process was simulated through experiments:
将脱硫副产物分别按0(A样)、3％(B样)、7％(C样)、10％(D样)、12％(E样)比例与含水率为20％的水冲矿渣混合，物料比例均以干基物料重量比计算，然后在105℃下恒温4小时，最后将烘干后的物料粉磨至比表面积为410m2/kg。The by-products of desulfurization were flushed with slag with water content of 20% in proportions of 0 (sample A), 3% (sample B), 7% (sample C), 10% (sample D), and 12% (sample E) Mixing, the ratio of the materials is calculated based on the weight ratio of the dry materials, and then the temperature is kept at 105°C for 4 hours, and finally the dried materials are ground to a specific surface area of 410m 2 /kg.
分析了纯矿渣粉样(A样)、3％脱硫副产物掺量(B样)、7％脱硫副产物掺量(C样)、10％脱硫副产物掺量(D样)、12％脱硫副产物掺量(E样)对矿渣微粉的化学成分、反应活性以及安定性的影响。Pure slag powder sample (sample A), 3% desulfurization by-product content (sample B), 7% desulfurization by-product content (sample C), 10% desulfurization by-product content (sample D), 12% desulfurization Effects of by-product content (E sample) on the chemical composition, reactivity and stability of slag powder.
采用《水泥标准稠度用水量、凝结时间、安定性检验方法》(GB/T 1346-2001)标准对安定性进行测定。The stability is measured by the standard of "Cement Standard Consistency Water Consumption, Setting Time, and Stability Test Method" (GB/T 1346-2001).
活性指数测定：采用《水泥胶砂强度检验方法(ISO法)》(GB/T 17671-1999)测定试样7d、28d的抗压强度，通过与基准样对比，计算活性指数。Determination of activity index: Measure the compressive strength of samples 7d and 28d using "Cement Mortar Strength Test Method (ISO Method)" (GB/T 17671-1999), and calculate the activity index by comparing with the reference sample.
试样测定结果见表1：The test results of the sample are shown in Table 1:
表1试样性能测定结果Table 1 Sample performance measurement results
如表1所示，在脱硫副产物掺量为3％、7％、10％时，7d、28d活性指数均优于基准样A样，而在脱硫副产物掺量为12％时，则活性指数较基准样较差。各试样SO3含量和安定性均符合国家相关标准要求。As shown in Table 1, when the content of desulfurization by-products is 3%, 7%, and 10%, the activity index of 7d and 28d is better than that of the reference sample A, while when the content of desulfurization by-products is 12%, the activity index The index is worse than the benchmark sample. The SO 3 content and stability of each sample are in line with the relevant national standards.
因此，本发明可在脱硫副产物掺量不大于10％时，所制备的复合粉性能满足国家相关标准要求。Therefore, the performance of the prepared composite powder can meet the requirements of relevant national standards when the content of desulfurization by-products is not more than 10%.
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