钙磷比对钌/磷灰石催化氧化二氯甲烷性能的影响  

Effect of Ca/P ratio on catalytic oxidation of dichloromethane over Ru/hydroxyapatite catalysts

作　　者：万继国 徐力 王钰 WAN Jiguo;XU Li;WANG Yu(College of Resources and Environment Engineering,Wuhan University of Science and Technology,Wuhan 430081,China;Shanwei Innovation Industrial Design&Research Institute,Shanwei 516600,China)

机构地区：[1]武汉科技大学资源与环境工程学院,武汉430081 [2]汕尾市创新工业设计研究院,广东汕尾516600

出　　处：《环境工程》2025年第1期175-184,共10页Environmental Engineering

基　　金：武汉科技大学“十四五”湖北省优势特色学科(群)项目(2023A0302);广东省普通高校重点领域专项(2021ZDZX4094,2023ZDZX3091)。

摘　　要：采用液相沉积法制备了一系列含有不同钙磷摩尔比的羟基磷灰石[HAP(X),X为n(Ca)/n(P)],通过尿素均相沉积沉淀法将钌(Ru)负载于HAP(X)表面,制得Ru/HAP(X)催化剂。由XRD、FT-IR、SEM、TEM、H2-TPR、NH3-TPD等表征结果可知:Ru纳米颗粒在HAP表面呈高度分散状态,Ru/HAP(1.67)表现出最佳的低温氧化还原性能,同时具有最丰富的中、强酸性位点。以二氯甲烷(DCM)为典型含氯挥发性有机物(CVOCs),考察了Ru/HAP(X)对DCM催化氧化活性、选择性和稳定性,结果表明:Ru/HAP(1.67)对DCM催化氧化性能最好,且稳定性良好。钙磷摩尔比对DCM反应副产物的分布有显著影响,Ru/HAP(1.50)由于酸性较强,检测到不完全分解产物CH3Cl,随着钙磷摩尔比增加,Ru/HAP(1.60)和Ru/HAP(1.67)则以CHCl3和CCl4为主要副产物。研究成果可为CVOCs催化氧化工业应用和磷资源高附加值利用提供参考。Catalytic oxidation is the most effective way to treat CVOCs.At present,the core difficulties in making efficient CVOCs catalysts are achieving high activity,resistance to chlorine poisoning and resistance to high temperature sintering.In this experiment,a series of hydroxyapatite(HAP(X),X refers to the Ca/P molar ratio)with different Ca/P molar ratios were prepared by liquid phase deposition method,and then ruthenium(Ru)was loaded on the surface of HAP(X)by urea homogeneous deposition precipitation method to prepare the Ru/HAP(X)catalyst.As shown by the results of XRD,FT-IR,SEM,TEM,H2-TPR,NH3-TPD,etc.,Ru nanoparticles were highly dispersed on the surface of HAP,and Ru/HAP(1.67)exhibited the best low-temperature reducibility,as well as the richest medium and strong acid sites.The catalytic oxidation activity,selectivity,and stability of Ru/HAP(X)for dichloromethane(DCM)were investigated by taking DCM as typical chlorine-containing VOCs.The investigation result indicated that Ru/HAP(1.67)had the best catalytic oxidation performance and good stability for DCM.The Ca/P molar ratio had a significant effect on the distribution of by-products in the DCM reaction.Monochloromethane,an incomplete decomposition product,was detected in Ru/HAP(1.50)because of its strong acidity.With the increase in Ca/P molar ratio,trichloromethane and tetrachloromethane were the main by-products of Ru/HAP(1.60)and Ru/HAP(1.67).The research results provide references for industrial application of CVOCs catalytic oxidation and high value-added utilization of phosphorus resources.

关 键 词：二氯甲烷 羟基磷灰石 催化氧化 钌 酸性位 

分 类 号：TQ426[化学工程] X701[环境科学与工程—环境工程]