钢铁联合企业典型废弃物的综合处理研究
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摘要
目前,钢铁产业发展的主要方向是环境友好、绿色生态化及资源的高效综合利用,其中烧结烟气、焦化废水和钢渣为钢铁联合企业的主要废弃物,对其进行有效处理是实现绿色生态化冶金奋斗目标的重点内容。然而,过去的研究工作基本上是孤立的,没有综合考虑三者间的内在联系,因而处理工艺没有取得重大突破。本论文以烧结过程脱硫、烧结烟气脱硫、钢渣综合利用于焦化废水的降解处理为核心,进行了实验研究和机理分析。
为了研究烧结过程中各种因素对S在烧结过程中分配规律的影响,研制开发了小型烧结实验设备。实验结果表明,该设备可以很好地模拟烧结生产过程,是进行烧结过程研究的一种新方法。由于用料量少,大幅度降低了劳动强度,因此可以一个人独立完成实验操作。
烧结生产过程产生的SO2约占钢铁工业排放总量的60%～90%,石灰既是烧结过程中不可缺少的原料,又是常用的脱硫剂。采用真空煅烧法可以获得高活性石灰。石灰的活性度与煅烧温度、恒温时间有关,最佳工艺条件是在950℃时恒温60min。石灰的活性度与其比表面积、比孔容积之间有很好的正线性关系。用温升速率法可以准确测定高活性石灰的活性度,且操作更简单、操作环境更友好,具有很好的再现性。石灰活性对烧结过程有重要影响。提高石灰活性度,有利于针状、细针状铁酸钙的形成,可以提高烧结矿品位、烧结矿强度及成品率,改善烧结矿冶金性能。石灰活性对烧结过程中硫的分配有较大影响。提高石灰活性度,烧结矿中硫含量提高,但仍满足优质烧结矿的要求,可以减少烧结烟气中SO2排放量。矿相显微镜分析和扫描电子显微镜(SEM)分析结果表明,烧结矿中硫以CaS形态存在,且主要分布在烧结矿的气孔部位。
烧结烟气中的SO2是酸性气体,而焦化废水中含有大量的氨等碱性物质,当他们接触时即发生中和反应。研究表明,利用焦化废水处理烧结烟气,可以有效脱除烧结烟气中的SO2,达到钢铁工业大气污染物排放标准。处理后焦化废水(即脱硫废水)的pH值降低,为后续铁炭内电解法处理废水工艺的进行提供了有利条件。
铁炭内电解法是近年发展起来的一种有效的废水处理方法。本论文利用钢渣和铁精粉、煤粉及少量黏结剂成功制备了高活性铁炭原电池,即高含碳金属化球团,该制备过程集成了海绵铁的制备和活性炭的制备过程,海绵铁与活性炭均匀分布其中,接触良好,组成了无数个铁炭原电池。研究结果表明,高含碳金属化球团对焦化废水中的酚类和氰化物有很好的降解效果,对COD有一定的降解效果,但对氨氮的去除效果较差。高含碳金属化球团对焦化废水的降解性能远高于45#钢屑、铸铁屑和海绵铁。气相色谱-质谱联用仪(GC-MS)和傅立叶红外光谱(FT-IR)研究结果表明,高含碳金属化球团对废水中有机污染物的去除不是简单的吸附,而是通过原电池加氢还原反应,使复杂的环打开变为单环、链状结构,最终实现彻底降解的。
通过对S在烧结过程中的分配规律和用钢渣制备高含碳金属化球团处理焦化废水的工艺及机理等方面的研究,探索出一条综合利用焦化废水脱除烧结烟气中的SO2、然后利用高含碳金属化球团处理焦化废水的新的处理途径,为钢铁联合企业提高铁素利用效率、水利用效率,发展循环经济和绿色制造技术提供新的思路。
At present China's iron & steel industry's development direction is to make the environment-friendly, green ecologicalization, high efficiency and comprehensive utilize the resources. Sintering flue gas, coking wastewater and steel slag are the main wastes of integrated steel companies. Effective handling these wastes is the main important task. However, the past researching work about handling wastes is essentially in isolation, without taking into account the inner link between the three parts, therefore there is no major breakthrough of the treatment process. In the paper the experiments were done, the mechanisms of desulfurization in sintering, flue gas and handling coking wastewater using steel slag were analyzed.
In order to study the distribution of Sulphur in sintering, the equipment which named as small-sintering test has been invented. The results have shown that it can simulate the sintering process very well. It is a new method for researching on the sintering production process. Because of less material and low labor intensity, the experiment can be operated independently by one man.
About 60-90% SO2 emissions came from the sintering production process in metallurgical enterprises. Lime is not only an indispensable raw material for sintering production process, but also commonly used as desulfurization agent. The high active lime can be got by calcining limestone in vacuum condition. The activity of lime is related to the calcination's temperature and time. The best process condition for prepare high active lime is calcining limestone in vacuum at 950℃for 60 minutes. The activity of lime is corresponding related to special surface area and special porosity. The activity of lime can be accurately determined by temperature rising rate method. This method is not only with simple operation, benefit to environment, but also with well reproducibility. The sintering production process is significantly impacted by the activity of lime. The high activity of the lime is favorable for the formation of fine acicular and acicular structure calcium ferrite. The sinter's grade, intensity and the yield are increased with the rase of lime's activity. The sulfur assignment during sintering production process is greatly affected by the activity of lime. Sulphur content in sinter will increase with the increase of the activity of lime, but it is still satisfactory for technology standard of high quality sinters, the SO2 emissions from the flue gas can be reduced. The testing results of mineragraphic microscope and scanning electron microscopy (SEM) indicate that the Sulphur existences as CaS, and mainly distributes in the spiracle region of sinter.
The SO2 gas is a kind of acidic gas, while a large amounts of alkaline substances in coking wastewater, such as ammonia, the chemical reactions will take place when they meet together. The results show that the SO2 in sintering flue gas can be effectively removed by coking wastewater. The SO2 content in Sintering flue gas can meet the discharge standards. Sintering flue gas can decrease the pH value of coking wastewater, which provides favorable conditions for the following treatment of wastewater via iron-carbon internal electrolysis method.
Iron-carbon internal electrolysis method is an effective effluent disposal method which has been developing a few years. Metallization pellets with high carbon content (MPHC) has been success made from steel slag, iron powder, coal powder and a little of bonding agents. This preparation process integrates sponge iron preparation and the activated carbon preparation process. A number of sponge iron and activated carbon are uniform distribution in the MPHC. The results show that phenols and cyanide in coking wastewater can be effective removed by the MPHC, and the COD has certain degeneration, but the degradation of nitrogen is bad. The MPHC exhibited remarkable performance for the degradation of coking wastewater than steel 45#, cast iron and sponge iron. The results of GC-MS and FT-IR indicate that the degradation of organic pollutants in coking wastewater by the MPHC is not simply adsorption, but is removed complete by galvanic cell reaction.
The results of the distribution of Sulphur during sintering production process and the degradation mechanism of coking wastewater by the MPHC indicate that a new method was explored for removing the SO2 of sintering flue gas by comprehensive utilization of coking wastewater, then coking wastewater will be treated by the MPHC. Theoretical basis were provided for the integrated steelworks' to treat main wastes such as the sintering flue gas, coking wastewater and steel slag at highly effective and more economy.
为了研究烧结过程中各种因素对S在烧结过程中分配规律的影响,研制开发了小型烧结实验设备。实验结果表明,该设备可以很好地模拟烧结生产过程,是进行烧结过程研究的一种新方法。由于用料量少,大幅度降低了劳动强度,因此可以一个人独立完成实验操作。
烧结生产过程产生的SO2约占钢铁工业排放总量的60%～90%,石灰既是烧结过程中不可缺少的原料,又是常用的脱硫剂。采用真空煅烧法可以获得高活性石灰。石灰的活性度与煅烧温度、恒温时间有关,最佳工艺条件是在950℃时恒温60min。石灰的活性度与其比表面积、比孔容积之间有很好的正线性关系。用温升速率法可以准确测定高活性石灰的活性度,且操作更简单、操作环境更友好,具有很好的再现性。石灰活性对烧结过程有重要影响。提高石灰活性度,有利于针状、细针状铁酸钙的形成,可以提高烧结矿品位、烧结矿强度及成品率,改善烧结矿冶金性能。石灰活性对烧结过程中硫的分配有较大影响。提高石灰活性度,烧结矿中硫含量提高,但仍满足优质烧结矿的要求,可以减少烧结烟气中SO2排放量。矿相显微镜分析和扫描电子显微镜(SEM)分析结果表明,烧结矿中硫以CaS形态存在,且主要分布在烧结矿的气孔部位。
烧结烟气中的SO2是酸性气体,而焦化废水中含有大量的氨等碱性物质,当他们接触时即发生中和反应。研究表明,利用焦化废水处理烧结烟气,可以有效脱除烧结烟气中的SO2,达到钢铁工业大气污染物排放标准。处理后焦化废水(即脱硫废水)的pH值降低,为后续铁炭内电解法处理废水工艺的进行提供了有利条件。
铁炭内电解法是近年发展起来的一种有效的废水处理方法。本论文利用钢渣和铁精粉、煤粉及少量黏结剂成功制备了高活性铁炭原电池,即高含碳金属化球团,该制备过程集成了海绵铁的制备和活性炭的制备过程,海绵铁与活性炭均匀分布其中,接触良好,组成了无数个铁炭原电池。研究结果表明,高含碳金属化球团对焦化废水中的酚类和氰化物有很好的降解效果,对COD有一定的降解效果,但对氨氮的去除效果较差。高含碳金属化球团对焦化废水的降解性能远高于45#钢屑、铸铁屑和海绵铁。气相色谱-质谱联用仪(GC-MS)和傅立叶红外光谱(FT-IR)研究结果表明,高含碳金属化球团对废水中有机污染物的去除不是简单的吸附,而是通过原电池加氢还原反应,使复杂的环打开变为单环、链状结构,最终实现彻底降解的。
通过对S在烧结过程中的分配规律和用钢渣制备高含碳金属化球团处理焦化废水的工艺及机理等方面的研究,探索出一条综合利用焦化废水脱除烧结烟气中的SO2、然后利用高含碳金属化球团处理焦化废水的新的处理途径,为钢铁联合企业提高铁素利用效率、水利用效率,发展循环经济和绿色制造技术提供新的思路。
At present China's iron & steel industry's development direction is to make the environment-friendly, green ecologicalization, high efficiency and comprehensive utilize the resources. Sintering flue gas, coking wastewater and steel slag are the main wastes of integrated steel companies. Effective handling these wastes is the main important task. However, the past researching work about handling wastes is essentially in isolation, without taking into account the inner link between the three parts, therefore there is no major breakthrough of the treatment process. In the paper the experiments were done, the mechanisms of desulfurization in sintering, flue gas and handling coking wastewater using steel slag were analyzed.
In order to study the distribution of Sulphur in sintering, the equipment which named as small-sintering test has been invented. The results have shown that it can simulate the sintering process very well. It is a new method for researching on the sintering production process. Because of less material and low labor intensity, the experiment can be operated independently by one man.
About 60-90% SO2 emissions came from the sintering production process in metallurgical enterprises. Lime is not only an indispensable raw material for sintering production process, but also commonly used as desulfurization agent. The high active lime can be got by calcining limestone in vacuum condition. The activity of lime is related to the calcination's temperature and time. The best process condition for prepare high active lime is calcining limestone in vacuum at 950℃for 60 minutes. The activity of lime is corresponding related to special surface area and special porosity. The activity of lime can be accurately determined by temperature rising rate method. This method is not only with simple operation, benefit to environment, but also with well reproducibility. The sintering production process is significantly impacted by the activity of lime. The high activity of the lime is favorable for the formation of fine acicular and acicular structure calcium ferrite. The sinter's grade, intensity and the yield are increased with the rase of lime's activity. The sulfur assignment during sintering production process is greatly affected by the activity of lime. Sulphur content in sinter will increase with the increase of the activity of lime, but it is still satisfactory for technology standard of high quality sinters, the SO2 emissions from the flue gas can be reduced. The testing results of mineragraphic microscope and scanning electron microscopy (SEM) indicate that the Sulphur existences as CaS, and mainly distributes in the spiracle region of sinter.
The SO2 gas is a kind of acidic gas, while a large amounts of alkaline substances in coking wastewater, such as ammonia, the chemical reactions will take place when they meet together. The results show that the SO2 in sintering flue gas can be effectively removed by coking wastewater. The SO2 content in Sintering flue gas can meet the discharge standards. Sintering flue gas can decrease the pH value of coking wastewater, which provides favorable conditions for the following treatment of wastewater via iron-carbon internal electrolysis method.
Iron-carbon internal electrolysis method is an effective effluent disposal method which has been developing a few years. Metallization pellets with high carbon content (MPHC) has been success made from steel slag, iron powder, coal powder and a little of bonding agents. This preparation process integrates sponge iron preparation and the activated carbon preparation process. A number of sponge iron and activated carbon are uniform distribution in the MPHC. The results show that phenols and cyanide in coking wastewater can be effective removed by the MPHC, and the COD has certain degeneration, but the degradation of nitrogen is bad. The MPHC exhibited remarkable performance for the degradation of coking wastewater than steel 45#, cast iron and sponge iron. The results of GC-MS and FT-IR indicate that the degradation of organic pollutants in coking wastewater by the MPHC is not simply adsorption, but is removed complete by galvanic cell reaction.
The results of the distribution of Sulphur during sintering production process and the degradation mechanism of coking wastewater by the MPHC indicate that a new method was explored for removing the SO2 of sintering flue gas by comprehensive utilization of coking wastewater, then coking wastewater will be treated by the MPHC. Theoretical basis were provided for the integrated steelworks' to treat main wastes such as the sintering flue gas, coking wastewater and steel slag at highly effective and more economy.
引文
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