CuO/PSSF复合催化剂的制备及其在苯酚降解中的应用

doi:10.16085/j.issn.1000-6613.2018-0541

摘要/Abstract

摘要：

以纸状不锈钢微纤材料（paper-like sintered stainless steel fibers，PSSF）为载体，采用化学气相沉积法（chemical vapor depositon，CVD）制备CuO/PSSF复合催化剂并在固定床反应器上进行苯酚湿式催化氧化降解研究。采用SEM、XRD、XPS等技术对催化剂的表面形态、物相结构、元素价态进行分析，改变流量及床层高度考察停留时间对湿式催化氧化降解苯酚过程中苯酚转化率、H₂O₂转化率、TOC转化率及Cu²⁺浸出浓度的影响规律。催化剂表征结果表明，活性组分CuO成功负载在PSSF微纤材料上；活性评价测试结果表明，低流量条件对各活性指标变化影响十分明显；随床层高度增加各活性指标均显著提高，4cm床层高度下达到最高苯酚转化率和TOC转化率，分别为96.5%和47.4%，同时没有高毒副产物产生。本文初步探究了复合催化剂与固定床反应器结合的工艺可行性，旨在为工业化含酚废水的降解提供一些思路。

关键词: 废水, 固定床, 复合材料, 苯酚, 湿式催化氧化, 化学气相沉积法

Abstract:

Supported by PSSF (paper-like sintered stainless steel fibers), novel CuO/PSSF composite catalysts were synthesized by chemical vapor deposition(CVD) and applied in the catalytic wet peroxide oxidation (CWPO) of phenol in a fixed-bed reactor. The physical structure, morphology, and element valence state of the catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS), respectively. The influence of residence time has been studied by modifying the feed flow rate and catalyst bed height, while the conversion of phenol, H₂O₂ and TOC as well as the leaching concentration of Cu²⁺ were analyzed to investigate the catalytic activity of the CuO/PSSF composite catalysts. Characterization results indicated that CuO was deposited on PSSF successfully and the activity evaluation results showed that conversion of phenol, H₂O₂ and TOC changed significantly at low feed flow rate but increased as the catalyst bed height increased and the highest phenol and TOC conversion (96.5% and 47.4%, respectively) were obtained with 4cm catalyst bed height, meanwhile the intermediates of high toxicity were not observed. This study preliminarily supported the application of the CuO/PSSF composite catalysts in fixed-bed reactor, and thus provided some new solutions for the degradation of phenol-containing wastewater.

Key words: waste water, fixed-bed, composites, phenol, catalytic wet peroxide oxidation, chemical vapor deposition

中图分类号:

X703

黄浩鑫,张会平,鄢瑛. CuO/PSSF复合催化剂的制备及其在苯酚降解中的应用[J]. 化工进展, 2019, 38(03): 1377-1386.

Haoxin HUANG,Huiping ZHANG,Ying YAN. Synthesis of novel CuO/PSSF composite catalysts for the degradation of phenol[J]. Chemical Industry and Engineering Progress, 2019, 38(03): 1377-1386.

图/表 11

图1 装置流程图

图2 PSSF材料和CuO/PSSF复合催化剂的XRD谱图

图3 PSSF材料和CuO/PSSF复合催化剂SEM图

图4 CuO/PSSF复合催化剂MIP分析曲线图

表1 CuO/PSSF复合催化剂的孔结构特性

总孔面积

/m²·g^-1

中值孔径

(体积)/nm

中值孔径

(面积)/nm

平均孔径

/nm

空隙率

图5 Cu 2p电子能谱

图6 CuO/PSSF复合催化剂O 1s电子能谱

图7 不同流量下苯酚转化率、过氧化氢转化率、TOC转化率随时间变化曲线

图8 不同床层高度下苯酚转化率、过氧化氢转化率、TOC转化率随时间变化曲线

图9 Cu2+浸出浓度及溶液pH

图10 反应1h后样品不同流量及床层高度下的液相色谱图(峰1、峰2为小分子羧酸；峰3为醌)

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