CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究

doi:10.11949/0438-1157.20191050

化工学报 ›› 2020, Vol. 71 ›› Issue (4): 1646-1656.DOI: 10.11949/0438-1157.20191050

• 催化、动力学与反应器 • 上一篇下一篇

CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究

焦昭杰¹(),陈立功¹,柳云骐²,张贤明¹,龚海峰¹,高旭³()

^1.重庆工商大学废油资源化技术与装备教育部工程研究中心，重庆 400067
^2.中国石油大学（华东）重质油国家重点实验室，山东青岛 266580
^3.重庆工商大学智能制造服务国际科技合作基地，重庆 400067

收稿日期:2019-09-23 修回日期:2019-12-09 出版日期:2020-04-05 发布日期:2020-04-05
通讯作者: 高旭
作者简介:焦昭杰（1981—），男，博士，助理研究员，jiaozhaojie2001@ctbu.edu.cn
基金资助:
中泰战略国际科技创新合作重点专项(2016YFE0205600);重庆市教委项目(KJQN201900823);重庆工商大学项目(1956004)

Preparation of CuCe oxide catalyst for CWPO degradation of bisphenol A

Zhaojie JIAO¹(),Ligong CHEN¹,Yunqi LIU²,Xianming ZHANG¹,Haifeng GONG¹,Xu GAO³()

^1.Engineering Research Center for Waste Oil Recovery Technology and Equipment, Ministry of Education, Chongqing Technology and Business University, Chongqing 400067, China
^2.State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, Shandong, China
^3.National Research Base of Intelligent Manufacturing Service, Chongqing Technology and Business University, Chongqing 400067, China

Received:2019-09-23 Revised:2019-12-09 Online:2020-04-05 Published:2020-04-05
Contact: Xu GAO

摘要/Abstract

摘要：

为解决Fenton法存在活性组分流失及通常在pH 2～3条件下运行的局限性，采用柠檬酸络合法制备了CuCe氧化物催化剂，建立了双酚A非均相催化湿式过氧化氢氧化（CWPO）反应体系。考察了焙烧温度、Cu/Ce摩尔比、H₂O₂用量、双酚A初始浓度和pH对催化剂物化结构和CWPO性能的影响。并分析了可能的降解路径。结果表明：催化剂具有良好的高温稳定性和pH适应性，在pH 1.6～7.9范围内对双酚A都具有较高的降解性能，不需要调节pH。在焙烧温度450℃、Cu/Ce摩尔比1.0、催化剂用量1 g·L^-1、H₂O₂用量196 mmol·L^-1、BPA浓度152 mg·L^-1、pH 6.6、反应温度75℃、反应95 min后，BPA和TOC去除率分别为91.8%和84.5%,Cu²⁺析出浓度为19.3 mg·L^-1。推测了双酚A可能的降解路径。

关键词: 催化湿式过氧化氢氧化, CuCe氧化物催化剂, ·OH自由基, 双酚A, 降解

Abstract:

In order to overcome the limitation to loss of active components of Fenton as well as operation only under pH 2—3, a CuCe oxide catalyst was prepared by a citric acid complex method. A catalytic wet peroxide oxidation (CWPO) reaction system was also established, which aimed at degradation bisphenol A. The effects of calcination temperature, Cu/Ce molar ratio, H₂O₂ dosage, initial concentration of bisphenol A and pH on the structure of the catalyst and the performance of the CWPO were investigated. Possible degradation pathways were also analyzed.The results show that the catalyst has good high temperature stability and pH adaptability, and has high degradation performance for bisphenol A in the range of pH 1.6 to 7.9, and does not need to adjust the pH. The removal rates of BPA and TOC were 91.8% and 84.5%, respectively, with the concentration of Cu²⁺ at 19.3 mg·L^-1 after calcination of 450℃, Cu/Ce molar ratio at 1.0, catalyst dosage at 1 g·L^-1, hydrogen peroxide dosage at 196 mmol·L^-1, BPA concentration at 152 mg·L^-1, pH at 6.6, reaction temperature at 75℃ and reaction for 95 min. The possible degradation pathways of bisphenol A were proposed.

Key words: catalytic wet peroxide oxidation (CWPO), CuCe oxide catalyst, ·OH radical, bisphenol A, degradation

中图分类号:

X 703

焦昭杰, 陈立功, 柳云骐, 张贤明, 龚海峰, 高旭. CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究[J]. 化工学报, 2020, 71(4): 1646-1656.

Zhaojie JIAO, Ligong CHEN, Yunqi LIU, Xianming ZHANG, Haifeng GONG, Xu GAO. Preparation of CuCe oxide catalyst for CWPO degradation of bisphenol A[J]. CIESC Journal, 2020, 71(4): 1646-1656.

图/表 13

图1 制备的CuCe氧化物催化剂XRD谱图

Fig.1 XRD patterns of CuCe oxide catalysts

表1 制得的CuCe氧化物催化剂参数

Table 1 Parameters of CuCe oxide catalysts

CuCe 催化剂	结晶度^①/%	平均晶粒尺寸/nm	晶胞参数
CuCe 催化剂	结晶度^①/%	平均晶粒尺寸/nm	a (α=90°)/?	b (β=90°)/?	c (γ=90°)/?
CC450	42.55	8.0	5.4045	5.4001	5.3241
CC550	45.43	9.6	5.4054	5.4219	5.4065
CC650	62.17	17.9	5.4032	5.4111	5.4071
CC750	63.14	32.5	5.4095	5.4096	5.4096
Cu₂Ce₁	63.81	20.7	5.3988	5.4100	5.4003
Cu₁Ce₂	56.57	15.8	5.4031	5.4167	5.4085
Cu₁Ce₃	52.58	12.5	5.4097	5.4133	5.4081

图2 制备的CuCe氧化物催化剂的SEM图

Fig.2 SEM images of CuCe oxide catalysts

图3 制备的CuCe氧化物催化剂的H2-TPR谱图

Fig.3 H2-TPR profiles of CuCe oxide catalysts

图4 制备的CuCe氧化物催化剂Ce 3d、Cu 2p和O 1s的XPS谱图

Fig.4 Ce 3d, Cu 2p and O 1s XPS spectra of CuCe oxide catalysts

表2 制备的CuCe氧化物催化剂XPS参数

Table 2 XPS parameters of CuCe oxide catalysts

CuCe催化剂	晶格氧/%	吸附氧/%	羟基氧/%	Ce/%(质量分数)	Cu/%(质量分数)	O/%(质量分数)
Cu₁Ce₃	62.71	28.04	9.25	23.68	8.92	67.39
Cu₁Ce₂	69.16	18.07	12.77	25.22	8.49	66.30
Cu₂Ce₁	64.10	22.75	13.14	2.44	18.90	78.67
CC450	68.32	20.00	11.69	23.54	12.02	64.44
CC550	66.44	20.56	13.00	21.62	12.83	65.55
CC650	65.49	20.38	14.13	19.75	13.95	66.31
CC750	68.73	18.47	12.80	19.78	14.14	66.08

图5 制备条件对CWPO性能的影响

Fig.5 Effects of preparations on heterogeneous CWPO performance of bisphenol A (催化剂=1 g·L-1, BPA=152 mg·L-1, H2O2=196 mmol·L-1, pH=6.6, t=95 min, T=75℃)

图6 H2O2 用量对CWPO性能的影响

Fig.6 Effect of H2O2 dosage on BPA degradation by CWPO (催化剂=1 g·L-1, BPA=152 mg·L-1, pH=6.6, T=75℃)

图7 BPA初始浓度对CWPO性能的影响

Fig.7 Effect of initial concentrations on BPA degradation by CWPO(催化剂=1 g·L-1, H2O2=196 mmol·L-1, pH=6.6, T=75℃)

图8 初始pH对CWPO性能的影响

Fig.8 Effect of pH on BPA degradation by CWPO(催化剂=1 g·L-1, H2O2 =196 mmol·L-1, BPA=152 mg·L-1)

图9 CWPO反应过程中·OH自由基浓度的变化

Fig.9 Variations of ·OH concentration in CWPO system(催化剂=1 g·L-1, H2O2=196 mmol·L-1, BPA=152 mg·L-1, T=75℃)

表3 BPA降解过程中可能的主要中间产物

Table 3 Possible major intermediates in BPA degradation process

Compound	Molecular weight	Tentative structure
benzaldehyde, 4-ethyl-	134
p-benzoquinone	108
phenol	94
styrene	104
p-isopropenylphenol	134
p-xylene	106
p-hydroxytoluene	108
o-cresol	108
phenol,-2,4-bis(1,1-dimethylethyl)-	206
phenol, 2,5-bis(1,1-dimethylethyl)-	206

图10 可能的BPA降解路径

Fig.10 Probable degradation pathway of BPA

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CuCe氧化物催化剂的制备及CWPO降解双酚A废水研究

Preparation of CuCe oxide catalyst for CWPO degradation of bisphenol A

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