改性煤气化渣催化降解双酚A的性能研究

doi:10.11949/0438-1157.20231124

摘要/Abstract

摘要：

以航天炉煤气化细渣为研究对象，以双酚A（BPA）为模型污染物，以过硫酸盐（PMS）为氧化剂，对煤气化渣进行酸、碱、盐改性处理，探究了改性煤气化渣活化PMS降解BPA的性能。研究表明，三种改性方式均可提升煤气化渣活化PMS降解BPA的性能，其中NaOH改性效果最佳。对NaOH改性浓度研究发现，5.5NaOH-FS/PMS/BPA体系中，在30 ℃，催化剂投加量2 g/L，PMS投加量10 mmol/L的条件下，15 mg/L BPA在60 min内可以实现完全去除。XRF/XRD/SEM-EDS/FT-IR分析表明，NaOH改性煤气化渣中保留了活性Fe₂O₃组分，并且碳的百分含量最高，达到52.7%，其存在加速了BPA的降解。自由基淬灭实验证明，5.5NaOH-FS/PMS降解BPA过程中，·O₂^-与¹O₂为主要活性氧物种。研究成果为煤气化渣作为催化剂在污染物去除领域中的应用提供了一定的基础数据。

关键词: 煤气化渣, 改性, 催化剂, 活化, BPA降解

Abstract:

It has a good application potential for coal gasification slag by modifying and regulating the physicochemical properties of it, which can be used to the catalytic removal of organic pollutants, especially electron rich organics. This study focuses on the catalytic application of coal gasification fine slag of space furnace for the removal of bisphenol A by activating persulfate (PMS). Specifically, the coal gasification slag was modified with various concentrations of acid (HCl), alkali (NaOH), and metal salt (ZnCl₂) and used it in the BPA degradation process. The effect of modifier concentration on its catalytic performance was investigated. Besides, the performance of alkali modified coal gasification slag in the degradation of BPA by activating PMS under different reaction conditions was investigated with the active substances that play a dominant role in the catalytic degradation of BPA were further explored through XRF, SEM, XRD, FT-IR, BET characterization and free radical quenching experiments. It was shown that all three modification methods can enhance the catalytic performance of coal gasification slag in degrading BPA, with NaOH modification shown the best performance. For the 5.5NaOH-FS/PMS system, 15 mg/L BPA can be achieved complete removal within 60 minutes under the conditions of 30 °C, catalyst dosage of 2 g/L, and PMS dosage of 10 mmol/L. XRF/XRD/SEM-EDS/FT-IR analysis showed that the active Fe₂O₃ component was retained in the structure of NaOH modified coal gasification slag, as well as the carbon content reached to 52.7% after NaOH modification. It promoted the BPA degradation. The free radical quenching experiment proved that ^·O₂^- and ¹O₂ were the main reactive oxygen species during the degradation of BPA by 5.5NaOH-FS/PMS. Moreover, the presence of carbon defects can directly participate in the oxidative degradation of BPA by forming intermediate complexes with PMS through non-free radical pathways. The research results provide a basis for the resource utilization of coal gasification slag, especially for its application as a catalyst in the field of organic pollutant removal.

Key words: coal gasification slag, modified, catalyst, activation, BPA degradation

中图分类号:

X752

卫月星, 贺子岳, 燕可洲, 李林玉, 秦育红, 贺冲, 焦路畅. 改性煤气化渣催化降解双酚A的性能研究[J]. 化工学报, DOI: 10.11949/0438-1157.20231124.

Yuexing WEI, Ziyue HE, Kezhou YAN, Linyu LI, Yuhong QIN, Chong HE, Luchang JIAO. Catalytic degradation of bisphenol A by modified coal gasification slag[J]. CIESC Journal, DOI: 10.11949/0438-1157.20231124.

图/表 16

图1 BPA浓度的标准曲线

Fig. 1 Standard curve of the BPA concentration

表1 煤气化渣元素含量及化学组成

Tab. 1 Element content and Chemical composition of coal gasification slag

元素	元素含量/%（mass）		化学组成
O	41.03	/	/
Si	14.62	SiO₂	31.28
Fe	19.69	Fe₂O₃	28.15
Al	9.76	Al₂O₃	15.84
Ca	8.34	CaO	13.65
S	1.62	SO₃	4.04
K	1.44	TiO₂	1.73
Ti	1.04	K₂O	1.73
Cl	0.64	P₂O₅	1.06
Na	0.58	Na₂O	0.87
P	0.46	Cl	0.58
Mg	0.35	MgO	0.59
Zr	0.13	ZrO₂	0.18
Sr	0.12	SrO	0.14
Mn	0.07	MnO	0.09
Zn	0.05	ZnO	0.06
Rb	0.01	Rb₂O	0.01

表2 煤气化渣的有机元素分析

Tab. 2 Organic elemental analysis of coal gasification slags

样品	N/%	C/%	H/%	S/%	O/%
FS	0.21	21.02	0.24	3.44	75.09

图2 不同改性煤气化渣放大5000倍的SEM图

Fig. 2 SEM images of the four different modified coal gasification slag magnified by 5000 times

图3 不同改性煤气化渣的EDS面扫图

Fig.3 EDS mapping images of the different modified coal gasification slag

表3 不同改性煤气化渣的EDS面扫元素含量

Tab. 3 Element distribution table of the different modified coal gasification slag

含量/wt%	C	O	Fe	Si	Al	其他
3.3HCl-FS	3.8	43.8	5.5	21.8	16	9.1
5.5NaOH-FS	87.5	7.9	2.4	0.7	0.5	1
0.6ZnCl₂-FS	35.4	27.4	2.3	8.7	4	22.2

表4 不同改性方式所制备煤气化渣的有机元素分析结果

Table 4 Organic elements analysis data of different modified coal gasification slags

样品		N/%	C/%	H/%	S/%
FS	0.21	21.02	0.24	3.44	75.09
3.3HCl-FS	0.27	30.07	0.87	3.46	65.6
5.5NaOH-FS	0.31	52.7	0.75	4.99	41.25
0.6ZnCl₂-FS	0.05	21.1	0.06	3.47	75.32

图4 不同改性煤气化渣的XRD图

Fig.4 XRD patterns of the different modified coal gasification slag

表5 不同改性煤气化渣的比表面积、孔结构和孔径

Table 5 Specific surface area， pore structure and aperture of different modified coal gasification slag

样品	S_BET/m²·g^-1	孔体积/cm³·g^-1	平均孔径/nm
FS	1.69	0	2.7
3.3HCl-FS	0	0	0
5.5NaOH-FS	27.95	0.04	5.1
0.6ZnCl₂-FS	9.2	0.04	17

图 5 几种改性煤气化渣的孔径分布

Fig. 5 Diagrams of pore size distribution of the FS and modified FS

图 6 不同改性FS的FT-IR图

Fig. 6 FT-IR patterns of different modified FS

图 7 不同改性煤气化渣对BPA的降解性能

Fig.7 BPA degradation performance of coal gasification slag modified with various concentrations of modifiers

图 8 不同反应条件对5.5NaOH-FS活化PMS降解BPA的影响

Fig. 8 Effect of different reaction conditions (a) catalyst dosage;(b) BPA concentration;(c) pH;(d) PMS dosage on the BPA degradation of 5.5NaOH-FS

表6 本研究所用改性煤气化渣与部分文献中所制备材料活化PMS降解BPA的性能对比

Tab. 6 The BPA degradation performance of 5.5NaOH-FS via PMS activation compared to other synthesized catalysts

催化剂	污染物	污染物浓度	催化剂用量	时间	降解率	文献
5.5NaOH-FS	BPA	20 mg/L	1 g/L	60 min	95%	本文
生物炭	BPA	20 mg/L	1 g/L	150 min	97%	^[35]
CF@MWCNT	BPA	40 mg/L	0.3 g/L	60 min	44%	^[36]
S-氮化碳	BPA	50 mg/L	0.3 g/L	120 min	60%	^[37]
MnFe₂O₄	BPA	5 mg/L	0.2g/L	30 min	88.44%	^[38]
污泥碳	BPA	0.1 mmol/L	0.5 g/L	60 min	94.5%	^[39]
MnO₂	BPA	40 umol/L	17.4mg/L	60 min	94%	^[40]
Ca(OH)₂	BPA	0.02 mmol/L	1.5 mmol/L	80 min	90.81%	^[41]

图9 自由基淬灭实验

Fig. 9 Free radical quenching experiment

图 10 5.5NaOH-FS活化PMS降解BPA的机制图

Fig. 10 Mechanism diagram of 5.5NaOH-FS activated PMS degradation of BPA

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