Conversion of waste oils to green diesel by non-precious metal materials
LIU Xiao1, XIA Tao2, ZHANG Jing1, YANG Chun2
1. National Engineering Research Center for Safe Disposal and Resources Recovery of Sludge, School of Environment, Harbin Institute of Technology, Harbin 150000, China; 2. College of Environment and Ecology, Chongqing University, Chongqing 400044, China
Abstract：Varieties of non-noble metal catalysts were prepared and screened by hydrothermal deoxidation of stearic acid for the purpose of efficiently catalyzing the conversion of waste oil into green diesel. The experimental results demonstrated that the nano-Ni-Cu alloy exhibited a significant catalytic effect on stearic acid, with its catalytic performance and product distribution being the most comparable to those of the Pt/C catalyst. Furthermore, the optimization of reaction conditions, stability analysis, catalyst characterization, reaction mechanism exploration and broad-spectrum analysis were carried out for nano Ni-Cu alloy. The characterization results revealed that the structure of nano-Ni-Cu alloy remained stable, and no significant structural changes were observed after continuous cyclic use. Under the optimum reaction conditions of 330℃, 120min, with the addition of 20μL methanol, 30mg catalyst and 80μL water in a 1.67ml micro reactor, stearic acid was primarily converted into heptadecane through catalytic hydrodeoxygenation and decarbonylation. Additionally, the broad-spectrum analysis indicated that the yield of C8-C18 alkanes from various fatty acids and fatty acid esters catalyzed by nano-Ni-Cu alloy could exceed 95%, conforming its excellent catalytic performance.
刘骁, 夏涛, 张静, 阳春. 非贵金属材料催化废弃油脂制备绿色柴油[J]. 中国环境科学, 2025, 45(4): 1889-1900.
LIU Xiao, XIA Tao, ZHANG Jing, YANG Chun. Conversion of waste oils to green diesel by non-precious metal materials. CHINA ENVIRONMENTAL SCIENCECE, 2025, 45(4): 1889-1900.
[1] 李新月,李振京,韩沂杭,等.油脂加氢脱氧生产绿色柴油催化剂的研究进展[J].化工进展, 2024,43(S1):351-364. Li X, Li Z J, Han Y H, et al. Research progress on catalysts for the production of green diesel by hydrodeoxidation of lipid[J]. Chemical Industry and Engineering Progress, 2024,43(S1):351-364. [2] Yani F T, Husin H, Darmadi, et al. Palm oil hydrodeoxygenation into green diesel over NiO/NbOPO4 catalyst:A novel approach of synthesizing NbOPO4 from NbCl5[J]. Journal of Cleaner Production, 2022,354:131704. [3] Chen B S, Zeng Y Y, Liu L, et al. Advances in catalytic decarboxylation of bioderived fatty acids to diesel-range alkanes[J]. Renewable and Sustainable Energy Reviews, 2022,158:112178. [4] Hafriz R S R M, Habib S H, Raof N A, et al. Soybean oil-based green diesel production via catalytic deoxygenation (CDO) technology using low-cost modified dolomite and commercial zeolite-based catalyst[J]. Energy Conversion and Management:X, 2024,24:100749. [5] Peters M A, Onwudili J A, Wang J W. Fuel-range liquid hydrocarbon products from catalytic deoxygenation of mixtures of fatty acids obtained from the hydrolysis of rapeseed oil[J]. Sustainable Energy& Fuels, 2024,8(20):4820-4837. [6] Wu Q, Jia G, Zhang Y, et al. Bifunctional catalysts based on hierarchical SAPO-41nanosheet for Highly-efficient hydroisomerization of n-Hexadecane[J]. Fuel, 2023,352:129066. [7] Cao X, Zhao J, Jia S, et al. Enhanced ruthenium selectivity for the conversion of FAMEs to diesel-range alkanes by surface decoration of FeOx species[J]. Chemical Engineering Journal, 2024,481:148345. [8] Vázquez-Garrido I, Guevara-Lara A, López-Benítez A. Hydroprocessing of new and waste soybean oil for obtaining biodiesel:An operational conditions study[J]. Chemical Engineering Journal, 2023,452:139508. [9] Lei X, Xin H, Du X, et al. Efficiency conversion of jatropha oil into high-quality biofuel over the innovative Ni-Mo2 N based catalyst[J]. Fuel, 2022,324:124548. [10] Wijaya K, Ramadhani S, Saviola A J, et al. Efficient conversion of used palm cooking oil into biogasoline over hydrothermally prepared sulfated mesoporous silica loaded with NiMo catalyst[J]. Results in Engineering, 2024,24:103185. [11] Racha A, Kumar L, Pai S, et al. Highly selective hydrodeoxygenation catalyst for sustainable aviation fuel production from used cooking oil[J]. Catalysis Today, 2024,442:114895. [12] Bosoy S, Intachai S, Sumanatrakul P, et al. Novel magnetic composite:NiFe-layered double oxide/ferric oxyhydroxide/activated carbon for optimizing biodiesel production from used cooking oil[J]. Biomass and Bioenergy, 2024,183:107096. [13] Goh B H H, Chong C T, Milano J, et al. Response optimisation of TiO2-supported bimetallic NiCo catalyst for the cracking and deoxygenation of waste cooking oil into jet-fuel range hydrocarbon fuels under non-hydrogen environment[J]. Energy, 2024,309:133057. [14] Hatefirad P, Hosseini M, Tavasoli A. Effect of Fe/Cu catalysts supported on zeolite/active carbon hybrid on bio-oil quality derived from catalytic pyrolysis of granular bacteria biomass[J]. Fuel, 2022,312:122870. [15] Zeng D F, Li Y L, Xia T, et al. MOF-derived Co3O4 Nanoparticles catalyzing hydrothermal deoxygenation of fatty acids for alkane production[J]. ACS OMEGA, 2022,7(37):33482-90. [16] Zhang Z, Yang Q, Chen H, et al. In situ hydrogenation and decarboxylation of oleic acid into heptadecane over a Cu-Ni alloy catalyst using methanol as a hydrogen carrier[J]. Green Chemistry, 2018,20(1):197-205. [17] Yao X Y, Strathmann T J, Li Y L, et al. Catalytic hydrothermal deoxygenation of lipids and fatty acids to diesel-like hydrocarbons:a review[J]. Green Chemistry, 2021,23(3):1114-29. [18] Rahmawati Z, Anderson J A, McCue A J. Selective hydrogenation of stearic acid to stearyl alcohol over cobalt alumina catalysts[J]. Applied Catalysis A:General, 2023,666:119437. [19] Huang Z, Zhao Z, Zhang C, et al. Enhanced photocatalytic alkane production from fatty acid decarboxylation via inhibition of radical oligomerization[J]. Nature Catalysis, 2020,3(2):170-8. [20] Liu L, Corma A. Structural transformations of solid electrocatalysts and photocatalysts[J]. Nature Reviews Chemistry, 2021,5(4):256-76. [21] Fang W T, Liu S H, Steffensen A K, et al. On the role of Cu+ and CuNi alloy phases in mesoporous CuNi catalyst for furfural hydrogenation[J]. ACS Catalysis, 2023,13(13):8437-44. [22] Ferraz C P, Kiméné A, Silva Vargas K, et al. Efficient non-noble Ni-Cu based catalysts for the valorization of palmitic acid through a decarboxylation reaction[J]. Catalysis Science& Technology, 2021, 11(9):3025-38. [23] Reangchim P, Saelee T, Itthibenchapong V, et al. Role of Sn promoter in Ni/Al2O3 catalyst for the deoxygenation of stearic acid and coke formation:experimental and theoretical studies[J]. Catalysis Science& Technology, 2019,9(13):3361-72. [24] Zheng D, Guo D, Wang Z, et al. Synergistic effect of CoOx and Ni-Co alloy in Ni-Co/SAPO-11 catalysts for the deoxygenation of stearic acids[J]. Chemical Engineering Journal, 2023,451:138929. [25] Chen B, Zhou Z, Li Y, et al. Catalytic pyrolysis of fatty acids and oils into liquid biofuels and chemicals over supported Ni catalysts on biomass-derived carbon[J]. Applied Catalysis B:Environmental, 2023,338:123067. [26] Li M, Fu J, Xing S, et al. A novel catalyst with variable active sites for the direct hydrogenation of waste oils into jet fuel[J]. Applied Catalysis B:Environmental, 2020,260:118114.
