无机工业固体废弃物高温热化学转化的基础研究

doi:10.16085/j.issn.1000-6613.2024-0598

摘要/Abstract

摘要：

随着工业的持续发展，煤、油页岩、菱镁矿、铁矿等矿物资源的用量不断增加，产生大量无机工业固体废弃物，低效的固废处置方式造成了巨大的环境污染和资源浪费。基于常见典型工业固体废弃物的化学组成，结合热力学分析结果，提出一种工业固体废弃物高温热化学转化方法，直接将无机工业固体废弃物转化为高附加值材料。该高温热化学转化方法通过热力学分析确定理想的目标产物及反应温度，利用热质传递效率高和易于放大的流化床，使单一或多种固体废弃物混合物中的各化学成分间发生固-固高温热化学反应，制成所需的复相材料使用或经进一步加工制得具有更高附加值的终端产品。通过对菱镁矿浮选尾矿、硼泥、油页岩渣、铁尾矿、铝灰、煤矸石等多种固体废弃物实验，获得了相应的复相粉体材料，验证了该方法的可行性。同时，通过选择性混合多种固体废弃物，改变反应物组成，可以调控目标产物及其含量。实验结果表明，利用高温流态化热化学反应技术，无机工业固体废弃物可成功转化为高附加值产物。研究成果对实现无机工业固体废弃物的有效利用、减少资源浪费、保护生态环境、推动绿色、低碳和可持续发展提供了又一途径，也为相关固体废弃物的综合利用提供了具体数据支撑。

关键词: 无机工业固体废弃物, 高温热化学, 流态化, 颗粒技术, 复相粉体材料

Abstract:

With the continuous development of industry, the consumption of mineral resources such as coal, oil shale, magnesite and iron ore has been increasing, resulting in a large amount of inorganic industrial solid waste. Inefficient solid waste disposal methods to date have led to significant environmental pollution and resource waste. In this work, a high-temperature thermochemical conversion method for industrial solid waste was proposed, directly converting the solid waste into high-value-added materials. This conversion method determined the target products and reaction temperatures through thermodynamic analysis and utilizing fluidized beds to take their advantages, such as high heat and mass transfer efficiency, which were easy to scale up and to promote solid-solid high-temperature thermochemical reactions among various chemical components in solid wastes. This process produced composite powders for direct use or other higher-value end products through further processing. Experiments conducted with various solid waste materials, such as magnesite flotation tailings, boron mud, oil shale residue, iron tailings, alumina ash and coal gangue, had validated the feasibility of this method. Experimental results demonstrated that utilizing high-temperature fluidized bed thermochemical reaction technology can successfully convert inorganic industrial solid waste into high-value-added products. This research provided a new approach to effectively utilize inorganic industrial solid waste, reduce resource load, protect the ecological environment and promote green, low-carbon, and sustainable development.It also offered specific data support for the comprehensive utilization of related solid waste materials.

Key words: inorganic industrial solid waste, high-temperature thermochemistry, fluidization, particle technique, multiphase powder material

中图分类号:

X705

邹旭, 付亮亮, 胡枋伶, 宋佳, 高佳辉, 张庆瑾, 许光文, 白丁荣. 无机工业固体废弃物高温热化学转化的基础研究[J]. 化工进展, 2024, 43(7): 3756-3767.

ZOU Xu, FU Liangliang, HU Fangling, SONG Jia, GAO Jiahui, ZHANG Qingjin, XU Guangwen, BAI Dingrong. Basic research on high-temperature thermochemical reactions of industrial inorganic solid waste[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3756-3767.

图/表 15

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作者	主要原料	反应条件	样品形状	存在问题
丁达飞等^[32]	菱镁矿浮选尾矿	1500℃、5h	长方体	产品晶体发育较好，但传热效率慢，有1.7%~5.4%（质量分数）的MgO未转化
罗玉萍等^[22]	硼泥、镁砂	1500℃、8h	圆柱试样	制备时间较长，产品中有低熔点杂质，对产品性能有不利影响
李静等^[33]	高硅铁尾矿、高镁原料	1500~1600℃、4~6h	圆柱试样	反应温度较高、时间较长，耗能较高
李振等^[34]	菱镁矿浮选尾矿、硼泥、硅石	1550℃、3h	压块	硼泥中的Fe₂O₃等杂质降低镁橄榄石的纯度和共熔点，影响了材料的耐火性能
刘吉辉等^[35]	铁尾矿、轻烧镁粉	1527℃、2h	圆柱试样	随着温度的升高生成低熔点的铁橄榄石，降低了耐火材料性能
王素等^[36]	高镁型铁尾、矿轻烧镁砂、电熔镁砂	1500℃、6h	圆柱试样	需要对制得的产品进行二次磨细，造成人工损耗且反应时间较长能耗高
姚文贵等^[37]	铝土尾矿	1600℃、3h	圆柱试样	Fe₂O₃、TiO₂、K₂O、CaO等杂质降低了产品耐火性能
王新锋等^[38]	铝型材厂污泥、叶腊石	1600℃、3h	压块	试样强度较低、热稳定性较差
张倩^[39]	粉煤灰、煤矸石、铝灰	1200℃、10h	圆柱试样	传热效率较低，反应时间较长，耗能较高
周萍等^[40]	菱镁矿尾矿、二次铝灰	1400℃、3h	圆柱试样	制备的产品显气孔率较高，降低了复相材料的强度和硬度

作者	主要原料	反应条件	样品形状	存在问题
丁达飞等^[32]	菱镁矿浮选尾矿	1500℃、5h	长方体	产品晶体发育较好，但传热效率慢，有1.7%~5.4%（质量分数）的MgO未转化
罗玉萍等^[22]	硼泥、镁砂	1500℃、8h	圆柱试样	制备时间较长，产品中有低熔点杂质，对产品性能有不利影响
李静等^[33]	高硅铁尾矿、高镁原料	1500~1600℃、4~6h	圆柱试样	反应温度较高、时间较长，耗能较高
李振等^[34]	菱镁矿浮选尾矿、硼泥、硅石	1550℃、3h	压块	硼泥中的Fe₂O₃等杂质降低镁橄榄石的纯度和共熔点，影响了材料的耐火性能
刘吉辉等^[35]	铁尾矿、轻烧镁粉	1527℃、2h	圆柱试样	随着温度的升高生成低熔点的铁橄榄石，降低了耐火材料性能
王素等^[36]	高镁型铁尾、矿轻烧镁砂、电熔镁砂	1500℃、6h	圆柱试样	需要对制得的产品进行二次磨细，造成人工损耗且反应时间较长能耗高
姚文贵等^[37]	铝土尾矿	1600℃、3h	圆柱试样	Fe₂O₃、TiO₂、K₂O、CaO等杂质降低了产品耐火性能
王新锋等^[38]	铝型材厂污泥、叶腊石	1600℃、3h	压块	试样强度较低、热稳定性较差
张倩^[39]	粉煤灰、煤矸石、铝灰	1200℃、10h	圆柱试样	传热效率较低，反应时间较长，耗能较高
周萍等^[40]	菱镁矿尾矿、二次铝灰	1400℃、3h	圆柱试样	制备的产品显气孔率较高，降低了复相材料的强度和硬度

编号	原料名称	CaO	SiO₂	MgO	Fe₂O₃	Al₂O₃	K₂O	Cl	Na₂O	其他
M-1	菱镁矿浮选尾矿	1.35	29.97	64.96	0.86	2.86	—	—	—	—
M-2	硼泥	0.20	37.45	56.71	4.80	0.56	—	—	0.27	0.01
M-3	油页岩渣	1.58	58.78	0.93	11.20	20.88	1.49	—	0.70	4.44
M-4	铁尾矿	26.92	45.18	15.07	4.75	3.42	1.46	0.05	0.28	2.87
M-5	煤矸石	0.83	63.09	0.76	4.73	22.97	3.57	—	1.74	2.31
M-6	铝渣	1.58	3.05	9.17	0.35	60.96	0.73	12.64	8.82	2.70

编号	原料名称	CaO	SiO₂	MgO	Fe₂O₃	Al₂O₃	K₂O	Cl	Na₂O	其他
M-1	菱镁矿浮选尾矿	1.35	29.97	64.96	0.86	2.86	—	—	—	—
M-2	硼泥	0.20	37.45	56.71	4.80	0.56	—	—	0.27	0.01
M-3	油页岩渣	1.58	58.78	0.93	11.20	20.88	1.49	—	0.70	4.44
M-4	铁尾矿	26.92	45.18	15.07	4.75	3.42	1.46	0.05	0.28	2.87
M-5	煤矸石	0.83	63.09	0.76	4.73	22.97	3.57	—	1.74	2.31
M-6	铝渣	1.58	3.05	9.17	0.35	60.96	0.73	12.64	8.82	2.70

检测项目	细骨料指标要求（JG/T568—2019，细骨料）			检测结果
检测项目	Ⅰ	Ⅱ	Ⅲ	检测结果
含泥量/%	≤1.0	≤3.0	≤5.0	0.0
硫化物及硫酸盐含量/%	≤0.5	≤0.5	≤0.5	0.0
泥块含量/%	≤0.2	≤1.0	≤2.0	0.0
表观密度/kg·m^-3	≥2500	≥2500	≥2500	2790
坚固性	≤8.0	≤8.0	≤10.0	4.7
压碎指标/%	≤20	≤25	≤30	17
空隙率/%	≤43	≤45	≤47	21