煤焦化残渣污染特性与环境风险研究

黄耿博; 杨延梅; 黄启飞; 李雪冰; 杨玉飞

doi:10.12153/j.issn.1674-991X.20210088

煤焦化残渣污染特性与环境风险研究

doi: 10.12153/j.issn.1674-991X.20210088

黄耿博^{1, 2,},
杨延梅¹,
黄启飞²,
李雪冰²,
杨玉飞^2, ,

1.
重庆交通大学河海学院
2.
中国环境科学研究院固体废物污染控制技术研究所

基金项目: 国家重点研发计划项目（2018YFC1900102）

详细信息

作者简介:
黄耿博（1995—），男，硕士研究生，主要研究方向为固体废物处理与处置，971979906@qq.com

通讯作者:
杨玉飞(1978—)，男，研究员，博士，主要研究方向为固体废物环境风险控制， cqyyf@163.com

中图分类号: X705
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出版历程
- 收稿日期: 2021-03-25

Study on pollution characteristics and environmental risk of coal coking residues

1.
School of River and Ocean Engineering, Chongqing Jiaotong University
2.
Research Institute of Solid Waste Management, Chinese Research Academy of Environmental Sciences

摘要

摘要: 以某煤焦化企业生产过程产生的焦油渣、煤焦油、硫铵酸焦油、焦粉、剩余污泥5种残渣为研究对象，采用气相色谱-质谱联用仪分析残渣中16种优先控制的多环芳烃（PAHs）浓度和环数分布，采用电感耦合等离子体质谱仪测定8种重金属浓度，通过计算残渣的苯并[a]芘（BaP）等效毒性和重金属潜在生态危害指数分析煤焦化残渣的环境风险。结果表明，5种残渣的PAHs总浓度为0.94~238 367 mg/kg，表现为煤焦油>焦油渣>硫铵酸焦油>焦粉>剩余污泥，焦油渣、煤焦油、硫铵酸焦油中高致突变性物质、致癌性物质浓度超过GB 5085.6—2007《危险废物鉴别标准毒性物质含量鉴别》标准限值；焦油渣、煤焦油、焦粉、剩余污泥中Zn浓度最高，硫铵酸焦油中As浓度最高；5种残渣的BaP等效毒性为0.31~9 586.96 mg/kg，煤焦油、焦油渣、硫铵酸焦油具有更高的致癌风险；Hg是5种残渣中潜在环境风险最大的重金属，5种残渣对土壤均具有很强的潜在生态风险。
- 煤焦化残渣 /
- 多环芳烃 /
- 重金属 /
- 环境风险
Abstract: The tar slag, coal tar, ammonium sulfate tar, coke powder and residual sludge were collected from a coal coking enterprise. The concentrations and different ring distribution of 16 priority controlled polycyclic aromatic hydrocarbons (PAHs) were analyzed by gas chromatography-mass spectrometry (GC-MS), and 8 heavy metals were analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Meanwhile, the environmental risks of coal coking residues were analyzed by calculating the BaP equivalent toxicity concentration and the potential ecological risk index of heavy metals. The results showed that the total PAHs concentrations of five residues ranged from 0.94 mg/kg to 238 367 mg/kg, with the order of coal tar > tar slag > ammonium sulfate tar > coke powder > residual sludge, and the concentrations of highly mutagenic and carcinogenic compounds in tar slag, coal tar and ammonium sulfate tar exceeded the limits of Identification Standards for Hazardous Wastes- Identification for Toxic Substance Content (GB 5085.6—2007). The concentration of Zn in tar slag, coal tar, coke powder and residual sludge was the highest, and ammonium sulfate tar had the highest concentration of As. The BaP equivalent toxic concentration of the five residues was 0.31-9 586.96 mg/kg, and coal tar, tar slag and ammonium sulfate tar had higher cancer risk. Hg had the highest potential environmental risk among the five residues, and all the five residues had a strong potential ecological risk to the soil.
- coal coking residue /
- PAHs /
- heavy metal /
- environmental risk

HTML全文

图 1 某煤焦化企业炼焦工艺及产废节点

Figure 1. Coking process and pollutants producing nodes in a coal coking enterprise

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图 2 煤焦化残渣中16种PAHs组分浓度

Figure 2. Concetrations of sixteen PAHs in coal coking residues

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图 3 煤焦化残渣PAHs环数分布

Figure 3. Ring number distribution of PAHs in coal coking residues

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表 1 潜在生态风险评价等级划分标准

Table 1. Classification criteria for potential ecological risk assessment

${E}_{{\rm{j}}}^{i}$	单种重金属生态风险程度	$ \mathrm{R}\mathrm{I} $	重金属综合潜在生态风险程度
<40	轻微	<150	轻微
40~80	中等	150~300	中等
80~160	强	300~600	强
160~320	很强	≥600	很强
≥320	极强

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表 2 煤焦化残渣的PAHs等效致癌毒性

Table 2. PAHs equivalent carcinogenic toxicity of residues from coal coking process mg/kg

PAHs	TEF	煤焦油	焦油渣	硫铵酸焦油	焦粉	剩余污泥
Nap	0.001	102.96	39.43	19.12	—	—
Ace	0.001	17.41	8.44	5.44	—	—
Acy	0.001	1.29	0.52	0.20	—	—
Flu	0.001	16.71	6.38	2.29	—	—
Phe	0.001	0.46	0.19	2.77	0.01	—
Ant	0.01	118.39	51.52	7.68	0.02	—
Fla	0.001	27.39	12.64	1.54	0.01	—
Pyr	0.001	18.37	6.94	0.97	0.01	—
BaA	0.1	1 007.90	379.40	132.00	0.46	—
Chr	0.001	9.10	3.65	1.16	—	—
BbF	0.1	667.70	250.60	82.60	0.40	0.03
BkF	0.1	496.20	197.50	65.20	0.33	—
BaP	1	6 008.00	2 36.00	672.00	3.94	0.28
InP	0.1	236.90	102.80	30.70	0.18	—
DahA	1	839.00	290.00	98.00	1.11	—
BghiP	0.01	19.20	7.96	1.94	0.02	—
ΣBEQ	—	9 586.96	3 716.97	1 123.62	6.48	0.31
注：—表示未检出或浓度低于1.0×10⁻² mg/kg。

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表 3 煤焦化残渣中8种重金属浓度

Table 3. Concentrations of 8 heavy metals in coal coking residues mg/kg

项目	Cu	Pb	Zn	Ni	Hg	Cd	Cr	As	总量
焦油渣	9.40±2.37	137.00±12.50	420.00±68.55	4.30±0.50	0.60±0.10	3.50±0.75	8.20±0.85	0.68±0.12	583.68±85.71
煤焦油	0.60±0.10	42.50±4.18	46.60±6.01	—	0.43±0.05	0.90±0.25	0.80±0.19	0.44±0.05	92.27±10.80
硫铵酸焦油	8.30±1.31	—	4.30±0.81	21.80±2.41	1.75±0.36	0.10±0.06	14.30±1.36	39.60±6.56	90.15±12.82
焦粉	29.70±4.17	31.00±3.51	122.00±11.02	14.40±2.64	0.60±0.11	0.20±0.07	30.00±5.61	6.24±0.44	234.14±27.48
剩余污泥	26.80±4.04	4.90±0.75	90.20±7.61	8.00±1.17	1.27±0.16	—	23.50±3.31	3.24±0.78	157.91±17.75
济南市土壤背景值^[17]	25.10	24.10	68.40	30.10	0.04	0.15	68.50	10.40	226.79
注：—表示未检出。

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表 4 煤焦化残渣重金属潜在生态危害指数

Table 4. Potential ecological risk index of heavy metals in coal coking residues

项目	单因子潜在生态危害指数								RI
项目	Cu	Pb	Zn	Ni	Hg	Cd	Cr	As	RI
焦油渣	1.87	28.42	6.14	0.71	600.00	700.00	0.24	0.65	1 338.04
煤焦油	0.12	8.82	0.68	—	430.00	180.00	0.02	0.42	620.06
硫铵酸焦油	1.65	—	0.06	3.62	1 750.00	20.00	0.42	38.08	1 813.83
焦粉	5.92	6.43	1.78	2.39	600.00	40.00	0.88	6.00	663.40
剩余污泥	5.34	1.02	1.32	1.33	1 270.00	—	0.69	3.12	1 282.80
毒性系数	5	5	1	5	40	30	2	10
注：—表示未检出。

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