炼油废催化剂吸附去除水中硝基苯的特性与机制

doi:10.16085/j.issn.1000-6613.2024-0127

摘要/Abstract

摘要：

以石油炼制过程中产生的废流化催化裂化催化剂（sFCCc）和废加氢裂化催化剂（sHCc）为研究对象，探究了炼油废催化剂对炼化废水特征污染物硝基苯的吸附性能。sFCCc和sHCc保留了新鲜催化剂的Y型分子筛骨架，但具有更大的平均孔径和更高的晶格氧含量。在pH为2~12时，sFCCc经30min对硝基苯达到吸附平衡，吸附容量为18.65mg/g；sHCc经5min达到吸附平衡，吸附容量为20.01mg/g，吸附硝基苯的效果优于sFCCc。两种废催化剂经5次洗脱再生后吸附性能稳定，吸附硝基苯均遵循Freundlich吸附等温模型和拟二级反应动力学模型，表明发生了多层非理想吸附，同时存在物理吸附和化学吸附作用。表征结果显示，炼油废催化剂中的晶格氧和Lewis酸位点均可作为活性位点，通过物理吸附与化学吸附共同去除硝基苯。其中，晶格氧通过电子供体-受体效应与硝基苯的吸电子官能团（—NO₂）结合，而Lewis酸位点易发生羟基化反应通过氢键与硝基苯结合。

关键词: 炼油废催化剂, 吸附, 硝基苯, 动力学

Abstract:

In this study, the waste catalytic cracking catalysts (sFCCc) and waste hydrocracking catalysts (sHCc) produced in the refining process were taken as objects, and their adsorption performance to nitrobenzene and the characteristic pollutant in refining wastewater was investigated. sFCCc and sHCc retained the Y-type zeolite framework of fresh catalysts, but had a larger average pore diameter and a higher lattice oxygen content. In the pH range of 2—12, sFCCc reached the adsorption equilibrium of nitrobenzene after 30min with the adsorption capacity of 18.65mg/g, while sHCc reached the adsorption equilibrium after 5min with the adsorption capacity of 20.01mg/g, better than that of sFCCc. The adsorption properties of the two refinery waste catalysts kept stable after five circles of elution and regeneration, and adsorption processes followed Freundlich isothermal adsorption model and the pseudo-second-order kinetic model, indicating the existence of multilayer non-ideal adsorption with both physical and chemical adsorption processes. Characterization results showed that the lattice oxygen in the waste catalysts and the Lewis acid site-bound hydroxyl groups could combine with the electron-withdrawing functional group (—NO₂) through the electron donor-acceptor interaction and hydrogen bonding, respectively, and were recognized as the active sites for nitrobenzene adsorption. This study would provide data support for the resource utilization of refinery waste catalysts.

Key words: refining waste catalyst, adsorption, nitrobenzene, kinetics

中图分类号:

X705

李琢宇, 余美琪, 陈孝彦, 胡若晖, 王庆宏, 陈春茂, 詹亚力. 炼油废催化剂吸附去除水中硝基苯的特性与机制[J]. 化工进展, 2025, 44(2): 1076-1087.

LI Zhuoyu, YU Meiqi, CHEN Xiaoyan, HU Ruohui, WANG Qinghong, CHEN Chunmao, ZHAN Yali. Effects and mechanism on the removal of nitrobenzene from water by adsorption of refining waste catalysts[J]. Chemical Industry and Engineering Progress, 2025, 44(2): 1076-1087.

图/表 20

图1 新鲜催化剂和炼油废催化剂的XRD谱图

图2 新鲜催化剂和炼油废催化剂的SEM图

表1 新鲜催化剂和炼油废催化剂的表面元素分析结果

催化剂	O		Al		Si		La		Ce		Fe		Ni		W
催化剂	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%	质量分数/%	原子分数/%
FCCc	37.70	51.62	36.39	29.86	22.10	17.42	1.41	0.22	0.89	0.14	0.78	0.31	1.14	0.43	—	—
sFCCc	26.61	41.91	32.64	30.48	24.39	21.88	2.65	0.48	2.92	0.43	4.50	2.03	6.28	2.69	—	—
HCc	40.95	65.00	28.41	26.74	3.05	2.76	—	—	—	—	0.48	0.22	5.20	2.25	21.91	3.03
sHCc	34.70	53.72	41.15	37.78	5.10	4.50	—	—	—	—	0.59	0.26	4.37	1.85	14.08	1.90

表2 新鲜催化剂和炼油废催化剂中O 1s的XPS结果

催化剂	O_latt相对质量分数/%	O_vac相对质量分数/%	O_ads相对质量分数/%
FCCc	16.91	80.51	2.58
HCc	19.40	64.37	16.24
sFCCc	30.93	62.37	6.70
sHCc	39.39	53.62	6.99

图3 新鲜催化剂和炼油废催化剂的FTIR谱图

图4 新鲜催化剂和炼油废催化剂的py-FTIR谱图

表3 新鲜催化剂和废催化剂的酸位点及酸量

催化剂	Si与Al质量比/%	总酸量 /mmol∙g^-1	B酸量 /mmol∙g^-1	L酸量 /mmol∙g^-1
FCCc	60.73	19.00	5.59	13.42
sFCCc	74.72	8.54	1.28	7.26
HCc	10.74	32.19	2.77	29.42
sHCc	11.91	18.20	1.75	16.46

表4 新鲜催化剂和炼油废催化剂的比表面积和孔结构参数

催化剂	总比表面积/m²∙g^-1	微孔比表面积/m²∙g^-1	外比表面积/m²∙g^-1	总孔体积/cm³∙g^-1	微孔体积/cm³∙g^-1	平均孔径/nm
FCCc	219.44	134.91	84.53	0.18	0.066	3.36
sFCCc	116.91	72.00	44.91	0.16	0.035	5.40
HCc	272.14	127.89	144.25	0.35	0.062	5.17
sHCc	236.56	106.86	129.69	0.47	0.051	7.96

图5 不同反应工况对炼油废催化剂吸附硝基苯的影响去除率为柱状图；吸附容量为折线图

图6 不同催化剂对硝基苯的去除率和吸附容量

图7 炼油废催化剂对硝基苯的吸附等温线拟合结果

表5 炼油废催化剂吸附硝基苯的等温线参数

催化剂	Langmuir模型				Freundlich模型			Temkin模型
催化剂	K_L	q_m/mg∙g^-1	R_L	R²	K_F	1/n	R²	K_T	R²
sFCCc	0.1580	25.38	0.11	0.9527	5.3411	0.430	0.9946	0.9416	0.9666
sHCc	0.1780	26.68	0.10	0.9745	6.3256	0.398	0.9921	1.2475	0.9560

图8 炼油废催化剂吸附硝基苯的动力学拟合结果

表6 炼油废催化剂吸附硝基苯的动力学参数

催化剂

拟一级动力学模型

拟二级动力学模型

Morris-web

粒子内扩散模型

q_e/mg∙g^-1

q_cal/mg∙g^-1

k₁/min^-1

R²

R²

m i n^{- \frac{1}{2}}

R²

表6 炼油废催化剂吸附硝基苯的动力学参数

催化剂

拟一级动力学模型

拟二级动力学模型

Morris-web

粒子内扩散模型

q_e/mg∙g^-1

q_cal/mg∙g^-1

k₁/min^-1

R²

q_cal/mg∙g^-1

H/mg∙g^-1∙min^-1

k₂/mg∙g^-1∙min^-1

R²

k₃/mg∙g^-1∙

m i n^{- \frac{1}{2}}

R²

sFCCc

15.54

7.06

0.408

0.9975

16.31

0.43

0.206

0.9999

0.9395

0.9669

sHCc

18.76

1.01

0.408

0.9790

18.87

6.54

0.347

0.9999

1.2493

0.9566

表7 炼油废催化剂吸附硝基苯的热力学参数

催化剂	温度/K	ΔG/kJ∙mol^-1	ΔH/kJ∙mol^-1	ΔS/J·mol^-1∙K^-1
sFCCc	298	0.36	5.19	16.20
	308	0.20
	318	0.04
	328	0.03
sHCc	298	-3.87	-20.97	-57.39
	308	-3.29
	318	-2.72
	328	-2.15

图9 炼油废催化剂吸附硝基苯后的SEM图

图10 炼油废催化剂吸附硝基苯前后的FTIR图谱

图11 炼油废催化剂吸附前后的O 1s图

表8 不同吸附剂对硝基苯废水的处理效果比较

吸附剂种类	最优条件	去除率/%	参考文献
炼油废催化剂	投加量2.5g/L，温度55℃（sFCCc）、25℃（sHCc），吸附平衡时间30min（sFCCc）、5min（sHCc）	72.25（sFCCc），92.19（sHCc）	本研究
大孔树脂	pH=1，投加量70g/L，吸附平衡时间3.5h	98.8	[29]
活性炭纤维毡	投加量22.9g/L，吸附平衡时间110~120min	>46	[30]
粉状活性炭	投加量14.2g/L，吸附平衡时间60~70min	>80	[30]
颗粒活性炭	投加量3.14g/L，吸附平衡时间40~50min	>94	[30]
碳纳米管/聚氨酯复合材料	pH=5.4，投加量2mg/L，吸附平衡时间24h	>60	[31]
膨胀石墨	投加量0.4g/L，温度70℃，吸附平衡时间120min	>50	[32]
改性硅藻土	pH=5，温度50℃，投加量4g/L，吸附平衡时间2h	99.5	[33]
有机改性膨润土	投加量20g/L，吸附平衡时间80min	62.4	[34]
SiO₂气凝胶	pH=8.35，温度25℃，投加量3.33g/L，吸附平衡时间30min	62.4	[35]

图12 炼油废催化剂稳定性实验性能

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