稻壳白炭黑负载Fe2O3的气相芬顿反应NO预氧化

doi:10.16085/j.issn.1000-6613.2020-1542

摘要/Abstract

摘要：

以稻壳为硅源，采用直接煅烧法制备白炭黑，以其为载体，采用共浸渍法制备Fe₂O₃/SiO₂催化剂；并采用同样方法以商用二氧化硅为载体制备Fe₂O₃/C-SiO₂催化剂，将二者用于催化H₂O₂预氧化NO的实验。探究不同工况（负载量、催化温度、H₂O₂汽化温度、H₂O₂流量和水汽浓度）对NO预氧化的影响，并对催化剂进行表征，分析其物理化学性质对催化性能的影响。结果表明，在负载量为50%、催化温度为140℃、H₂O₂汽化温度为120℃、H₂O₂流量为2.5mL/h时，达到最佳工况，NO氧化度能达到73%；在相同实验条件下Fe₂O₃/SiO₂催化剂的预氧化效果要比Fe₂O₃/C-SiO₂催化剂高20%左右。TPR结果表明载体可以降低活性组分的还原温度，减少活性组分的团聚；催化剂的晶相结构稳定，机械强度及热稳定性良好；ESR和XPS结果显示Fe₂O₃/SiO₂催化剂的催化性能优于Fe₂O₃/C-SiO₂催化剂，能够更好地催化分解H₂O₂产生·OH。

关键词: 稻壳, 二氧化硅, 铁基催化剂, 气相双氧水, 脱硝

Abstract:

With rice husk as silicon source, silica was firstly prepared by the direct calcination method, and then the Fe₂O₃/SiO₂ catalyst was prepared by co-impregnation method with the silica as the carrier. As a comparison, the Fe₂O₃/C-SiO₂ catalyst supported on commercial silica was prepared by the same method. Both catalysts were used in catalyzing H₂O₂ to pre-oxidize NO. The effects of different operating conditions (loading, catalysis temperature, vaporization temperature of H₂O₂, flow rate of H₂O₂ and vapor concentration) on the pre-oxidation of NO were systematically investigated. In addition, the physicochemical properties of the catalysts were characterized and attempts were made to correlate them with their catalytic performance. The experimental results indicated that a NO oxidation efficiency of 73% could be achieved when the loading was 50%, catalysis temperature was 140℃, vaporization temperature of H₂O₂ was 120℃, and the flow rate of H₂O₂ was 2.5mL/h. Under the same experiment conditions, the NO pre-oxidation efficiency of Fe₂O₃/SiO₂ catalyst was about 20% higher than that of Fe₂O₃/C-SiO₂ catalyst. TPR result showed that the carrier could lower the reduction temperature of active components and further reduce their agglomeration. The catalyst has a stable crystal structure, and good mechanical strength and thermal stability. ESR and XPS results indicated that the catalytic performance of Fe₂O₃/SiO₂ catalyst was better than that of Fe₂O₃/C-SiO₂ catalyst, which better catalyzed the decomposition of H₂O₂ to produce ·OH.

Key words: rice husk, silica, iron-based catalyst, gas phase H₂O₂, denitrification

中图分类号:

X 511

闫文杰, 熊源泉, 杨思源, 何珊珊. 稻壳白炭黑负载Fe₂O₃的气相芬顿反应NO预氧化[J]. 化工进展, 2021, 40(7): 4027-4035.

YAN Wenjie, XIONG Yuanquan, YANG Siyuan, HE Shanshan. NO preoxidation by gas phase Fenton reaction with Fe₂O₃ over rice husk-based silica carrier[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 4027-4035.

图/表 16

图1 实验装置1—质量流量计；2—缓冲罐；3—三通阀；4—烟气预热器；5—温度控制单元；6—注射泵；7—催化反应器；8—冷却装置；9—干燥装置；10—烟气分析仪；11—KMnO4/NaOH溶液；12—活性炭

图2 催化剂H2-TPR图谱

图3 催化剂XRD图谱

图4 催化剂N2-吸附/脱附等温线

表1 催化剂的BET数据

样品	比表面积/m²·g^-1	孔体积/m³·g^-1	孔径/nm
30% Fe₂O₃/SiO₂	123.69	0.208	6.73
40% Fe₂O₃/SiO₂	97.64	0.193	7.89
50% Fe₂O₃/SiO₂	90.45	0.232	10.27
60% Fe₂O₃/SiO₂	83.82	0.174	11.29
70% Fe₂O₃/SiO₂	57.99	0.141	13.35
Fe₂O₃	12.17	0.135	44.51
50%Fe₂O₃/C-SiO₂	146.71	0.748	20.55

图5 催化剂XPS图谱

表2 铁元素的结合能和原子分数（Fe 2p光谱）

催化剂	Fe²⁺	Fe_octa³⁺	Fe_tet³⁺	Fe²⁺/Fe³⁺
Fe₂O₃/SiO₂
结合能/eV	709.3	710.2	711.8	0.212
原子分数/%	17.48	26.41	56.11
Fe₂O₃/C-SiO₂
结合能/eV	709.2	710.2	711.3	0.09
原子分数/%	8.22	47.31	44.47

表3 氧元素的结合能和原子分数（O 1s光谱）

催化剂	O_ad	O_lat	$O H 2 O$	O_ad/（O_ad+O_lat）
Fe₂O₃/SiO₂
结合能/eV	530.2	529.5	532.8	0.486
原子分数/%	24.78	26.17	49.05
Fe₂O₃/C-SiO₂
结合能/eV	530.6	529.5	532.4	0.193
原子分数/%	2	8.36	89.64

表3 氧元素的结合能和原子分数（O 1s光谱）

催化剂	O_ad	O_lat	$O H 2 O$	O_ad/（O_ad+O_lat）
Fe₂O₃/SiO₂
结合能/eV	530.2	529.5	532.8	0.486
原子分数/%	24.78	26.17	49.05
Fe₂O₃/C-SiO₂
结合能/eV	530.6	529.5	532.4	0.193
原子分数/%	2	8.36	89.64

图6 催化剂ESR图谱

图7 催化剂负载量对NO预氧化的影响（实验条件：H2O2浓度10mol·L-1，催化反应温度140℃，H2O2汽化温度120℃，H2O2流量2.5mL·h-1）

图8 催化温度对NO预氧化的影响（实验条件：H2O2浓度10mol·L-1，H2O2汽化温度120℃，H2O2流量2.5mL·h-1，负载量50%）

图9 H2O2汽化温度对NO预氧化的影响（实验条件：H2O2浓度10mol·L-1，催化反应温度140℃，H2O2流量2.5mL·h-1，负载量50%）

H2O2→H2O+O2? (6)

图10 烟气水汽浓度对NO预氧化的影响（实验条件：催化反应温度140℃，H2O2汽化温度120℃，负载量50%）

表4 H2O2溶液参数

H₂O₂流量/mL·h^-1	H₂O₂浓度/mol·L^-1
10	2.5
7.5	3.3
5	5
3.3	7.5
2.5	10

图11 H2O2流量对NO预氧化的影响（实验条件：H2O2浓度10mol·L-1，催化反应温度140℃，H2O2汽化温度120℃，负载量50%）

图12 催化温度对两种催化剂预氧化NO的影响（实验条件：H2O2浓度10mol·L-1，H2O2汽化温度120℃，H2O2流量2.5mL·h-1，负载量均为50%）

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稻壳白炭黑负载Fe₂O₃的气相芬顿反应NO预氧化

NO preoxidation by gas phase Fenton reaction with Fe₂O₃ over rice husk-based silica carrier

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