改性核桃壳炭负载的碳化钼催化剂的制备及其在玉米油加氢脱氧反应中的应用  

Preparation of modified walnut shell char supported Molybdenum carbide catalyst and its application in hydrodeoxidation of corn oil

作　　者：陈芳[1] 郭慧君 宋雨濛 楼辉[1] CHEN Fang;GUO Huijun;SONG Yumeng;LOU Hui(Department of Chemistry,Zhejiang University,Hangzhou 310028,China)

机构地区：[1]浙江大学化学系,浙江杭州310028

出　　处：《浙江大学学报（理学版）》2023年第2期174-184,194,共12页Journal of Zhejiang University（Science Edition）

基　　金：浙江省基础公益项目(LGC22B050001).

摘　　要：将核桃壳等可再生资源转化为能源或化工产品,是双碳目标的指引方向之一。核桃壳炭是核桃壳快速热解制备生物油的固体残渣,由于其低比表面积和较差的孔隙率,难以直接使用。用FeCl3活化剂对核桃壳炭进行改性,并将其与常用的KOH改性做对比,通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、BET方法、拉曼光谱、N2等温吸脱附曲线等系列表征,发现相较核桃壳炭,改性核桃壳炭的石墨化程度有所提高,其中,用FeCl3改性的核桃壳炭的比表面积由1.6 cm^(2)·g^(-1)提高至377 cm^(2)·g^(-1),孔容由0.0046 cm^(3)·g^(-1)提高至0.074 cm^(3)·g^(-1),呈现丰富的海绵状孔结构,且收率(61.2%)高于用KOH改性的核桃壳炭(35.8%)。将用FeCl3改性的核桃壳炭负载的碳化钼催化剂用于玉米油加氢脱氧反应,玉米油转化率和烃类产率分别达89.7%和87.2%,循环8次后,玉米油转化率和烃类收率均无明显下降,具有良好的稳定性。因此用FeCl3改性的核桃壳炭经济、高效和环境友好,有一定的推广应用价值。Converting renewable resources such as walnut shells into energy or chemical products is one of the targets for peak carbon dioxide emission and carbon neutrality.Walnut shell char is a solid byproduct of the rapid pyrolysis of walnut shells to create biological oil.Due to its limited porosity and low specific surface area,it is difficult to be used directly as carbon material.FeCl3 was utilized to activate carbon extracted from walnut shells,whereas KOH was used as a reference.Through SEM,TEM,BET,Raman,N2-adsorption,and other series of characterization,it was found that activation improves the degree of graphitization compared to that without activation.The specific surface area increased from 1.6 cm^(2)·g^(-1)to 377 cm^(2)·g^(-1)and the pore volume increased from 0.0046 cm^(3)·g^(-1)to 0.074 cm^(3)·g^(-1)when the FeCl3/WSC mass ratio was 10%.The structure of pores was abundant,and the carbon yield(61.2%)was higher than that by using the KOH activation method(35.8%).As a support for the corn oil hydrodeoxidation reaction,carbon derived from walnut shells was treated with FeCl3 to produce the molybdenum carbide catalyst.The corn oil conversion rate and the yield of hydrocarbon were 89.7%and 87.2%,respectively.After 8 cycles,neither the corn oil conversion rate nor the yield of hydrocarbon decreased,and the catalyst remained stable.This method of modifying FeCl3 has the advantages of cost-effectiveness,high efficiency,and environmental friendliness,as well as the potential for extensive use.

关 键 词：核桃壳炭 FeCl3改性 催化活性 稳定性 

分 类 号：O643[理学—物理化学]