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浙江大学学报（理学版）
Journal of Zhejiang University (Science Edition)  2023, Vol. 50 Issue (2): 174-184    DOI: 10.3785/j.issn.1008-9497.2023.02.007
Chemistry     
Preparation of modified walnut shell char supported Molybdenum carbide catalyst and its application in hydrodeoxidation of corn oil
Fang CHEN,Huijun GUO,Yumeng SONG,Hui LOU()
Department of Chemistry，Zhejiang University，Hangzhou 310028，China
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Abstract  

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 cm2·g-1 to 377 cm2·g-1 and the pore volume increased from 0.004 6 cm3·g-1 to 0.074 cm3·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.

Key words： walnut shell char      activation with FeCl3      catalytic activity      stability     
Received: 10 December 2021      Published: 21 March 2023
CLC:  O 643  
Corresponding Authors: Hui LOU     E-mail: hx215@zju.edu.cn
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Fang CHEN
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Cite this article:

Fang CHEN, Huijun GUO, Yumeng SONG, Hui LOU. Preparation of modified walnut shell char supported Molybdenum carbide catalyst and its application in hydrodeoxidation of corn oil. Journal of Zhejiang University (Science Edition), 2023, 50(2): 174-184.

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https://www.zjujournals.com/sci/EN/Y2023/V50/I2/174


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

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 cm2·g-1提高至377 cm2·g-1，孔容由0.004 6 cm3·g-1提高至0.074 cm3·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。


关键词： 核桃壳炭,  FeCl3改性,  催化活性,  稳定性 
Fig.1 SEM and TEM images of WSC
Fig.2 XRD spectrums of WSC
Fig.3 N2 adsorption-desorption isotherms and pore size distributions of WSC
样品

比表面积/

（m2·g-1）

孔容/（cm3·g-1）峰位/cm-1aID/IGb元素组成/%c

收率/

%e

DGCHN其他d
WSC-O1.60.004 61 3421 5940.9673.92.90.422.8-
WSC-C7.60.007 11 3411 5940.9476.32.40.420.971.5
WSC-K1 5150.881 3401 5960.8881.21.90.616.335.8
WSC-13770.0741 3421 5960.8177.51.81.119.665.4
WSC-104180.131 3391 5960.7481.01.41.216.461.2
WSC-504270.171 3521 5850.6386.01.21.411.450.7
ACf8830.271 3491 5790.9254.91.50.543.1-
Table 1 Textural parameters， Raman spectra data， element contents， and yield of differently activated WSC
催化剂

比表面积/

（m2·g-1）

孔容/（cm3·g-1）峰位/cm-1ID/IG转化率/%a收率/%b
DG
Mo2C/WSC-12310.0361 3471 5940.7875.167.6
Mo2C/WSC-103050.0921 3431 5950.7189.787.2
Mo2C/WSC-503240.111 3481 5870.6291.188.3
Mo2C/WSC-K7860.311 3421 5940.8668.466.3
Mo2C/AC4100.141 3511 5820.8869.459.1
Table 2 Textual parameters， Raman spectra data and reaction results of supported Mo2C catalysts
Fig.4 XRD patterns of modified WSC supported Mo2C catalysts
Fig.5 XPS spectrum of Mo2C/WSC-10
Fig.6 Mo 3d and C 1s XPS spectrum of modified WSC supported Mo2C catalysts
催化剂结合能/eV （原子百分比/%）
Mo2+Mo2+~4+Mo4+Mo4+~6+Mo6+
Mo2C/WSC-1228.29 （11.3）228.68 （18.5）229.42 （22.7）231.17 （10.1）232.41 （37.4）
Mo2C/WSC-10228.38 （17.5）228.69 （16.3）229.38 （25.7）231.19 （16.8）232.41 （23.7）
Mo2C/WSC-50228.42 （21.8）228.70 （14.8）229.28 （23.6）231.20 （18.1）232.41 （21.7）
Mo2C/WSC-K228.17 （10.7）228.70 （12.3）229.40 （23.6）231.19 （18.3）232.39 （35.1）
Table 3 XPS results of the Mo 3d spectra of different catalysts
催化剂结合能/eV （原子百分比/%）
C—Mo平面内C—C缺键位C—CC—OC=O
Mo2C/WSC-1284.20 （10.3）284.59 （41.4）285.52 （28.5）286.70 （11.5）288.68 （8.3）
Mo2C/WSC-10284.14 （11.3）284.59 （53.2）285.48 （18.6）286.69 （10.1）288.70 （6.8）
Mo2C/WSC-50284.12 （12.4）284.60 （63.7）285.51 （11.5）286.71 （6.5）288.65 （5.9）
Mo2C/WSC-K284.22 （9.1）284.61 （56.3）285.50 （15.8）286.69 （9.6）288.69 （9.2）
Table 4 XPS results of the C 1s spectra of different catalysts.
Fig.7 Reaction results of Mo2C catalysts supported on different carriers
Fig.8 Cycling tests of Mo2C/WSC-10 and Mo2C/WSC-K
Fig.9 SEM images of Mo2C/WSC-10 and Mo2C/WSC-K before and after the recycling
Fig.10 XRD patterns of Mo2C/WSC-10 and Mo2C/WSC-K before and after the recycling
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