微波强化焦化废盐中有机物脱除性能研究

doi:10.11949/0438-1157.20251195

摘要/Abstract

摘要：

焦化废盐成分复杂、有机污染物含量高，其无害化与资源化处理是行业面临的重大挑战。本文系统分析了焦化废盐的理化性质，并通过热重分析对比了其在无氧与有氧条件下的热解/燃烧特性。进一步通过常规热解与微波热解系统对比研究，探究了加热方式、温度对有机物去除效率的影响及微波的选择性活化机制。结果表明，微波热解在550℃下即可实现93%的有机物去除率，效果显著优于常规热解。此外，微波热解技术还展现出降低反应温度、抑制CO₂及有毒芳烃生成、并富集高纯度合成气的综合优势。本研究为焦化废盐的可控热解与资源化利用提供了一条高效、低污染的技术路径，具有重要的科学价值与应用前景。

关键词: 微波热解, 焦化废盐, 有机物脱除

Abstract:

The composition of coking waste salt is complex and the content of organic pollutants is high. The harmless and resource treatment of coking waste salt is a major challenge for the industry. In this paper, the physicochemical properties of coking waste salt were systematically analyzed, and the pyrolysis / combustion characteristics of coking waste salt under anaerobic and aerobic conditions were compared by thermogravimetric analysis. The effects of heating method and temperature on the removal efficiency of organic matter and the selective activation mechanism of microwave were further investigated by comparing the conventional pyrolysis and microwave pyrolysis systems. The results show that microwave pyrolysis can achieve 93% organic matter removal rate at 550 °C, which is significantly better than conventional pyrolysis. In addition, microwave pyrolysis technology also shows the comprehensive advantages of reducing reaction temperature, inhibiting the formation of CO₂ and toxic aromatic hydrocarbons, and enriching high-purity syngas. This study provides an efficient and low-pollution technical path for the controllable pyrolysis and resource utilization of coking waste salt, which has important scientific value and application prospect.

Key words: microwave pyrolysis, coking waste salt, organic matter removal

中图分类号:

X 705

王飞, 赵世雄, 卫亮哲, 鲁香港, 吕宏洲, 李彩慧. 微波强化焦化废盐中有机物脱除性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251195.

Fei WANG, Shixiong ZHAO, Liangzhe WEI, Xianggang LU, Hongzhou LÜ, Caihui LI. Study on microwave enhanced removal performance of organic matter in coking waste salt[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251195.

图/表 19

表1 废盐样品的工业分析和元素分析结果汇总表

Table 1 Summary of industrial analysis and elemental analysis results of waste salt samples

样品	工业分析(%)				元素分析(%)
样品	M	A	V	FC*	S	Na	O	CI	C *	Si	Ca
废盐	0.7	91.86	4.11	3.33	25.94	25.87	20.88	15.60	7.43	2.29	1.97

图1 焦化废盐XRD图

Fig. 1 XRD pattern of coking waste salt

表2 焦化废盐各组分的占比

Table 2 The proportion of each component of coking waste salt

废盐组分类别	可溶解盐(NaCl+ Na₂SO₄)	不溶物	有机物	水分
百分比	78%	13.86%	7.44%	0.7%

图2 焦化废盐无机、有机组分分析

Fig. 2 Analysis of inorganic and organic components of coking waste salt

表3 焦化废盐有机物测定

Table 3 Determination of organic matter in coking waste salt

保留时间	名称	分子式	占比(%)
9.421	苯乙烯	C₈H₈	3.79
13.925	1-十二烯	C₁₂H₂₄	10.23
25.251	2,4-二叔丁基苯酚	C₁₄H₂₂O	14.57
28.285	菲	C₁₄H₁₀	4.84
30.153	含氮/硫杂环化合物	C₈H₁₅NOS	7.18
31.212	氯化苄	C₇H₇CI	22.76
36.173	邻苯二甲酸二丁酯	C₁₆H₂₂O₄	15.80
47.253	苯并蒽	C₁₈H₁₂	6.62

图3 焦化废盐燃烧、热解TG/DTG曲线

Fig.3 TG / DTG curves of coking waste salt combustion and pyrolysis

图4 焦化废盐燃烧/热解动力学拟合

Fig. 4 Kinetic fitting of combustion / pyrolysis of coking waste salt

表4 焦化废盐热分解反应动力学参数

Table 4 Kinetic parameters of thermal decomposition reaction of coking waste salt

气氛	温度区间	E (kJ/mol)	ln(A) (min^-1)	R²
氮气	53~118℃	445.67	1.75	0.96505
	214~219℃	8.11	-7.17	0.96950
	558~570℃	321.15	-4.33	0.95986
	736~774℃	9503.09	11.40	0.98114
空气	53-118℃	218.26	-1.93	0.98053
	177-192℃	28.72	-6.19	0.99070
	412-418℃	14.37	-7.99	0.97024
	712-768℃	4516.97	3.80	0.96136

图5 焦化废盐燃烧、热解气体分布

Fig.5 Coking waste salt combustion, pyrolysis gas distribution

图6 焦化废盐有氧燃烧色谱图

Fig.6 Aerobic combustion chromatogram of coking waste salt

表5 焦化废盐燃烧新产生有毒有机物测定

Table 5 Determination of new toxic organic compounds produced by coking waste salt combustion

保留时间	名称	分子式
7.728	氯苯	C₆H₅Cl
9.567	吡啶-N-氧化物	C₅H₅NO
13.605	对二氯苯	C₆H₄Cl₂
14.705	苯甲醇	C₇H₈O
25.696	十二醛	C₁₂H₂₄O

表6 焦化废盐燃烧/热解有机残留对比

Table 6 Comparison of organic residues in combustion / pyrolysis of coking waste salt

高毒物质	有氧燃烧峰面积	无氧热解峰面积	倍数	危害
氯化苄	219166	99552	2.20	皮肤/黏膜强刺激
甲苯	400801	191862	2.09	损害肝肾功能
壬醛	240263	118989	2.02	挥发性刺激物
苯酚	859609	794672	1.08	难降解易累积
2,4-二叔丁基苯酚	1172126	512422	2.29	干扰代谢
邻苯二甲酸酐	1669609	673437	2.48	挥发性刺激物

表7 微波热解与常规热解动力学参数对比

Table 7 Comparison of kinetic parameters between microwave pyrolysis and conventional pyrolysis

加热方式	E (kJ/mol)	ln(A) (min^-1)	R²
常规热解	4.21	-3.64	0.9832
微波热解	3.55	-2.56	0.9655

图7 微波与常规热解下不同温度下的有机物去除率及动力学拟合曲线对比

Fig.7 Comparison of organic matter removal rate and kinetic fitting curve at different temperatures under microwave and conventional pyrolysis

图8 微波与常规热解随温度变化具体有机物峰面积对比

Fig. 8 Comparison of specific organic peak area of microwave and conventional pyrolysis with temperature change

图9 微波与常规加热下特征峰对比

Fig.9 Comparison of characteristic peaks under microwave and conventional heating

图10 微波与常规加热烟气百分比对比

Fig.10 Comparison of the percentage of microwave and conventional heating flue gas

表8 微波热解与常规热解的参数及能耗对比

Table 8 Comparison of parameters and energy consumption between microwave pyrolysis and conventional pyrolysis

加热方式	加热功率	加热时间	能耗
常规加热	1000 W	35min	0.58 kWh
微波加热	1000 W	20min	0.33 kWh

图11 焦化废盐有机物微波热解影响特性

Fig.11 Effect characteristics of microwave pyrolysis of coking waste salt organic matter

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