Mn-Ce-Co-Ox/PPS催化滤料催化降解气相二英的研究

doi:10.11949/0438-1157.20201294

摘要/Abstract

摘要：

通过原位氧化法一步制备得到Mn-Ce-Co-O_x/PPS催化滤料，研究了催化剂负载量对Mn-Ce-Co-O_x/PPS催化降解呋喃的影响，进而分析了最优负载量的Mn-Ce-Co-O_x/PPS催化滤料在140~200℃对二英的催化降解规律，同时采用SEM、EDS和XRD等表征手段对复合催化滤料的结构及性能进行表征。结果如下：催化剂负载量由81.8 g/m²增加到154.2 g/m²，Mn-Ce-Co-O_x/PPS对呋喃的降解效率呈增加趋势，催化剂单层饱和负载量为120.5 g/m²。Mn-Ce-Co-O_x/PPS催化滤料在140~200℃对二英的脱除效率高达90%以上，降解效率随着反应温度升高而快速提升，200℃降解效率达到最高，为78.01%，表现出良好的催化降解性能。对17种二英同系物的降解效率进行分析，发现Mn-Ce-Co-O_x/PPS对低氯代二英同系物的降解率高于高氯代同系物的降解率。

关键词: 原位氧化法, 催化滤料, 二英, 降解, 污染, 废物处理

Abstract:

To decompose PCDD/Fs(polychlorinated dibenzo-p-dioxins and dibenzofurans) in flue gas, Mn-Ce-Co-O_x/PPS catalytic filter was prepared by in-situ oxidation method. The effect of catalyst loading on catalytic degradation of furan by Mn-Ce-Co-O_x/PPS catalytic filter was investigated. Furthermore, effect of operating temperature in the range of 140—200℃ on catalytic degradation of PCDD/Fs by Mn-Ce-Co-O_x/PPS catalytic filter was studied. Several physicochemical methods, including SEM(scanning electron microscope), EDS(energy dispersive spectroscopy) and XRD(X-ray diffraction) were employed to characterize the structure and properties of the composite catalytic filter. With the increase of catalyst loading from 81.8 g/m² to 154.2 g/m², degradation efficiency of furan by Mn-Ce-Co-O_x/PPS kept increasing, and the monolayer saturated loading of Mn-Ce-Co-O_x/PPS was 120.5 g/m². Mn-Ce-Co-O_x/PPS catalytic filter can remove more than 90% of PCDD/Fs at 140—200℃. Degradation efficiencies of PCDD/Fs over Mn-Ce-Co-O_x/PPS showed a rapid growth with the increase of reaction temperature, achieving the highest of 78.01% at 200℃. The degradation efficiency of 17 dioxin homologs was analyzed, and it was found that the degradation rate of Mn-Ce-Co-O_x /PPS to low-chlorinated dioxin homologs was higher than that of high-chlorinated homologs.

Key words: in situ oxidation, catalytic filter, PCDD/Fs, degradation, pollution, waste management

中图分类号:

X 592

刘红蕾, 彭亚旗, 陶鋆奕, 汤明慧, 陆胜勇. Mn-Ce-Co-O_x/PPS催化滤料催化降解气相二英的研究[J]. 化工学报, 2021, 72(2): 1018-1025.

LIU Honglei, PENG Yaqi, TAO Junyi, TANG Minghui, LU Shengyong. Study on catalytic degradation of PCDD/Fs over Mn-Ce-Co-O_x/PPS catalytic filter[J]. CIESC Journal, 2021, 72(2): 1018-1025.

图/表 10

图1 SEM图

Fig.1 SEM images

图2 Mn-Ce-Co-Ox/PPS催化滤料的EDS能谱及元素分布图

Fig.2 EDS spectrum of Mn-Ce-Co-Ox/PPS catalytic filter

图3 Mn-Ce-Co-Ox催化剂粉末、聚苯硫醚滤料和Mn-Ce-Co-Ox/PPS催化滤料的XRD谱图

Fig.3 XRD patterns of Mn-Ce-Co-Ox catalyst powder, raw PPS filter and Mn-Ce-Co-Ox/PPS catalytic filter

图4 空白测试

Fig.4 Blank test

图5 温度对催化滤料降解呋喃的影响

Fig.5 Effects of temperature on furan degradation of Mn-Ce-Co-Ox/PPS catalytic filter

图6 负载量对催化滤料降解呋喃的影响

Fig.6 Effects of catalyst loading on furan degradation of Mn-Ce-Co-Ox/PPS catalytic filter

图7 Mn-Ce-Co-Ox/PPS催化滤料降解呋喃的稳定性

Fig.7 Stability of Mn-Ce-Co-Ox/PPS catalytic filter performance on catalytic conversion of furan

表1 17种有毒二英的初始浓度

Table 1 Initial concentration of seventeen 2, 3, 7, 8-substituted PCDD/F congeners

同系物	初始浓度/(ng I-TEQ/m³)			平均值/(ng I-TEQ/m³)	相对标准偏差/%
同系物	1	2	3	平均值/(ng I-TEQ/m³)	相对标准偏差/%
2,3,7,8-TCDD	0.3366	0.3439	0.3095	0.3300	5.50
1,2,3,7,8-PeCDD	0.4259	0.4487	0.4744	0.4497	5.39
1,2,3,4,7,8-HxCDD	0.0818	0.0916	0.0880	0.0871	5.71
1,2,3,6,7,8-HxCDD	0.1120	0.1423	0.1386	0.1310	12.64
1,2,3,7,8,9-HxCDD	0.1056	0.1230	0.1210	0.1165	8.20
1,2,3,4,6,7,8-HpCDD	0.0722	0.0921	0.0918	0.0854	13.32
OCDD	0.0083	0.0103	0.0117	0.0101	16.77
2,3,7,8-TCDF	0.2024	0.2035	0.2034	0.2031	0.30
1,2,3,7,8-PeCDF	0.1115	0.1282	0.1133	0.1177	7.83
2,3,4,7,8-PeCDF	2.4160	2.8840	2.4885	2.5962	9.70
1,2,3,4,7,8-HxCDF	0.2679	0.3190	0.2832	0.2900	9.05
1,2,3,6,7,8-HxCDF	0.3241	0.3553	0.3254	0.3350	5.27
2,3,4,6,7,8-HxCDF	0.1532	0.1684	0.1542	0.1586	5.36
1,2,3,7,8,9-HxCDF	0.4765	0.5562	0.5077	0.5135	7.82
1,2,3,4,6,7,8-HpCDF	0.0594	0.0714	0.0679	0.0662	9.32
1,2,3,4,7,8,9-HpCDF	0.0116	0.0139	0.0134	0.0130	9.30
OCDF	0.0019	0.0020	0.0022	0.0021	7.92
PCDDs	1.1424	1.2519	1.2350	1.2098	4.87
PCDFs	4.0245	4.7021	4.1593	4.2953	8.35
PCDD/Fs	5.1670	5.9540	5.3943	5.5051	7.36

图8 Mn-Ce-Co-Ox/PPS在不同温度催化降解二英的脱除效率和降解效率

Fig.8 Effect of operating temperature in PCDD/Fs degradation performance of Mn-Ce-Co-Ox/PPS catalytic filter

图9 17种二英同系物的降解效率

Fig.9 Degradation efficiencies of the 17 toxic PCDDs and PCDFs congeners

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