Synthesis of valerate biofuels on supported Co-based bifunctional catalysts

doi:10.11949/0438-1157.20211319

Abstract

Abstract:

Four types of Co-supported catalysts, HZSM-5, HY, Hβ and MCM-22, were prepared by the impregnation method. In the high-pressure reactor, the prepared catalyst is used as a raw material for one-step hydrodeoxygenation of ethyl levulinate to synthesize ethyl valerate and valeric acid biofuel. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier infrared (FT-IR), NH₃-TPD, H₂-TPR, py-FTIR, ICP-AES and other technologies are used for catalyst characterization. The results show that, because Co is uniformly distributed on HZSM-5, B acidity, total acidity and reduction performance are the best, while maintaining high reactivity, it improves the selectivity of the product. Therefore, the 10Co/HZSM-5 catalyst has higher catalytic performance. The reaction temperature, reaction pressure, etc. are further optimized. When the reaction temperature is 240℃, the pressure is 3 MPa, and the reaction is 3 h, with n-octane as the solvent, the catalyst shows higher catalytic performance, and the conversion rate of ethyl levulinate reaches 100%, the total yield of valerate and valeric acid can reach 90%.

Key words: ethyl levulinate, biofuel, hydrodeoxygenation, cobalt-based catalyst, molecular sieves

摘要：

采用浸渍法制备了HZSM-5、HY、Hβ以及MCM-22四种载体上负载Co的催化剂，在高压反应釜中，开展了以乙酰丙酸乙酯为原料一步法加氢脱氧合成戊酸乙酯以及戊酸生物燃料的研究。采用XRD、XPS、TEM、FT-IR、NH₃-TPD、H₂-TPR、py-FTIR、ICP-AES等对催化剂进行表征。结果表明，10Co/HZSM-5催化剂由于Co在HZSM-5上分布均匀，并且B酸酸性、总酸量以及还原性能最优，在保持较高的反应性能的同时，提高了产物的选择性，具有较高的催化性能。进一步对反应温度、反应压力等进行优化，在反应温度为240℃、压力为3 MPa、反应3 h时，以正辛烷作溶剂，催化剂表现出较高的催化性能，乙酰丙酸乙酯的转化率达到100%，戊酸酯和戊酸的总收率可达90%。

关键词: 乙酰丙酸乙酯, 生物燃料, 加氢脱氧, 钴基催化剂, 分子筛

CLC Number:

TK 6

Wuyu WANG, Yuzhu SHI, Long YAN, Xinghua ZHANG, Longlong MA, Qi ZHANG. Synthesis of valerate biofuels on supported Co-based bifunctional catalysts[J]. CIESC Journal, 2022, 73(2): 689-698.

王吴玉, 史玉竹, 严龙, 张兴华, 马隆龙, 张琦. 负载型Co基双功能催化剂上戊酸酯生物燃料的制备[J]. 化工学报, 2022, 73(2): 689-698.

Figures/Tables 13

References 40

1	Sun P, Gao G, Zhao Z L, et al. Acidity-regulation for enhancing the stability of Ni/HZSM-5 catalyst for valeric biofuel production[J]. Applied Catalysis B: Environmental, 2016, 189: 19-25.
2	Yan K, Lafleur T, Wu X, et al. Cascade upgrading of γ-valerolactone to biofuels[J]. Chemical Communications (Cambridge, England), 2015, 51(32): 6984-6987.
3	Cai T M, Deng Q, Peng H L, et al. Synthesis of renewable C-C cyclic compounds and high-density biofuels using 5-hydromethylfurfural as a reactant[J]. Green Chemistry, 2020, 22(8): 2468-2473.
4	张琦, 马隆龙, 张兴华. 生物质转化为高品位烃类燃料研究进展[J]. 农业机械学报, 2015, 46(1): 170-179.
	Zhang Q, Ma L L, Zhang X H. Progress in production of high-quality hydrocarbon fuels from biomass[J]. Transactions of the Chinese Society for Agricultural Machinery, 2015, 46(1): 170-179.
5	Yu Z H, Lu X B, Xiong J, et al. Transformation of levulinic acid to valeric biofuels: a review on heterogeneous bifunctional catalytic systems[J]. ChemSusChem, 2019, 12(17): 3915-3930.
6	Bozell J J, Moens L, Elliott D C, et al. Production of levulinic acid and use as a platform chemical for derived products[J]. Resources, Conservation and Recycling, 2000, 28(3/4): 227-239.
7	Buitrago-Sierra R, Serrano-Ruiz J C, Rodríguez-Reinoso F, et al. Ce promoted Pd-Nb catalysts for γ-valerolactone ring-opening and hydrogenation[J]. Green Chemistry, 2012, 14(12): 3318.
8	Pan T, Deng J, Xu Q, et al. Catalytic conversion of biomass-derived levulinic acid to valerate esters as oxygenated fuels using supported ruthenium catalysts[J]. Green Chemistry, 2013, 15(10): 2967.
9	Vennestrøm P N R, Osmundsen C M, Christensen C H, et al. Beyond petrochemicals: the renewable chemicals industry[J]. Angewandte Chemie International Edition, 2011, 50(45): 10502-10509.
10	Wang D L, Chen Z H, Yu J, et al. Effect of Si/Al ratio of HZSM-5 zeolites on catalytic upgrading of coal pyrolysis volatiles[J]. Journal of Fuel Chemistry and Technology, 2021, 49(5): 634-641.
11	Zhang Z Z, Liu N, An C X, et al. Effect of hierarchical ZSM-5 zeolites on product distribution of low rank coal fast pyrolysis in a fluidized bed[J]. Journal of Fuel Chemistry and Technology, 2021, 49(4): 407-414.
12	王磊, 徐天晓, 韩燕絮, 等. Ru/有机改性蛭石催化乙酰丙酸甲酯加氢性能的研究[J]. 燃料化学学报, 2020, 48(1): 100-107.
	Wang L, Xu T X, Han Y X, et al. Study on the catalytic hydrogenation of methyl levulinate over Ru/organic modified vermiculite[J]. Journal of Fuel Chemistry and Technology, 2020, 48(1): 100-107.
13	Lange J P, Price R, Ayoub P, et al. Valeric biofuels: a platform of cellulosic transportation fuels[J]. Angewandte Chemie, 2010, 122(26): 4581-4585.
14	Gu X M, Zhang B, Liang H J, et al. Pt/HZSM-5 catalyst synthesized by atomic layer deposition for aqueous-phase hydrogenation of levulinic acid to valeric acid[J]. Journal of Fuel Chemistry and Technology, 2017, 45(6): 714-722.
15	Pham H N, Pagan-Torres Y J, Serrano-Ruiz J C, et al. Improved hydrothermal stability of niobia-supported Pd catalysts[J]. Applied Catalysis A: General, 2011, 397(1/2): 153-162.
16	Hou M Y, Li G, Jin L J, et al. Pyrolysis behaviors of coal-related model compounds catalyzed by Ni-modified HZSM-5 zeolite[J]. Journal of Fuel Chemistry and Technology, 2021, 49(5): 582-588.
17	He J, Wu Z J, Gu Q Q, et al. Zeolite-tailored active site proximity for the efficient production of pentanoic biofuels[J]. Angewandte Chemie International Edition, 2021, 60(44): 23713-23721.
18	Li C, Ni X J, Di X, et al. Aqueous phase hydrogenation of levulinic acid to γ-valerolactone on supported Ru catalysts prepared by microwave-assisted thermolytic method[J]. Journal of Fuel Chemistry and Technology, 2018, 46(2): 161-170.
19	Dai N, Shang R, Fu M C, et al. Transfer hydrogenation of ethyl levulinate to γ-valerolactone catalyzed by iron complexes[J]. Chinese Journal of Chemistry, 2015, 33(4): 405-408.
20	Démolis A, Essayem N, Rataboul F. Synthesis and applications of alkyl levulinates[J]. ACS Sustainable Chemistry & Engineering, 2014, 2(6): 1338-1352.
21	Sun P, Gao G, Zhao Z L, et al. Stabilization of cobalt catalysts by embedment for efficient production of valeric biofuel[J]. ACS Catalysis, 2014, 4(11): 4136-4142.
22	Bermudez J M, Menéndez J A, Romero A A, et al. Continuous flow nanocatalysis: reaction pathways in the conversion of levulinic acid to valuable chemicals[J]. Green Chemistry, 2013, 15(10): 2786.
23	Serrano-Ruiz J C, Wang D, Dumesic J A. Catalytic upgrading of levulinic acid to 5-nonanone[J]. Green Chemistry, 2010, 12(4): 574.
24	Díaz U, Corma A. Layered zeolitic materials: an approach to designing versatile functional solids[J]. Dalton Transactions (Cambridge, England), 2014, 43(27): 10292-10316.
25	Corma A, Corell C, Pérez-Pariente J. Synthesis and characterization of the MCM-22 zeolite[J]. Zeolites, 1995, 15(1): 2-8.
26	Marlinda L, Al Muttaqii M, Roesyadi A, et al. Production of biofuel by hydrocracking of cerbera manghas oil using Co-Ni/HZSM-5 catalyst: effect of reaction temperature[J]. The Journal of Pure and Applied Chemistry Research, 2016, 5(3): 189-195.
27	Wang S R, Yin Q Q, Guo J F, et al. Improved Fischer-Tropsch synthesis for gasoline over Ru, Ni promoted Co/HZSM-5 catalysts[J]. Fuel, 2013, 108: 597-603.
28	Zhu Z Z, Lu G Z, Zhang Z G, et al. Highly active and stable Co₃O₄/ZSM-5 catalyst for propane oxidation: effect of the preparation method[J]. ACS Catalysis, 2013, 3(6): 1154-1164.
29	Feng X B, Tian M J, He C, et al. Yolk-shell-like mesoporous CoCrO_x with superior activity and chlorine resistance in dichloromethane destruction[J]. Applied Catalysis B: Environmental, 2020, 264: 118493.
30	Su Y, Fu K X, Zheng Y F, et al. Catalytic oxidation of dichloromethane over Pt-Co/HZSM-5 catalyst: synergistic effect of single-atom Pt, Co₃O₄, and HZSM-5[J]. Applied Catalysis B: Environmental, 2021, 288: 119980.
31	Fei X Q, Cao S, Ouyang W L, et al. A convenient synthesis of core-shell Co₃O₄@ZSM-5 catalysts for the total oxidation of dichloromethane (CH₂Cl₂)[J]. Chemical Engineering Journal, 2020, 387: 123411.
32	Wang H T, Wu Y S, Li Y Z, et al. One-step synthesis of pentane fuel from γ-valerolactone with high selectivity over a Co/HZSM-5 bifunctional catalyst[J]. Green Chemistry, 2021, 23(13): 4780-4789.
33	Ren X Y, Cao J P, Zhao X Y, et al. Increasing light aromatic products during upgrading of lignite pyrolysis vapor over Co-modified HZSM-5[J]. Journal of Analytical and Applied Pyrolysis, 2018, 130: 190-197.
34	Furusawa T, Seshan K, Lefferts L, et al. Selective reduction of NO with propylene in the presence of oxygen over Co- and Pt-Co promoted HY[J]. Applied Catalysis B: Environmental, 2002, 39(3): 233-246.
35	Sabarish R, Unnikrishnan G. Polyvinyl alcohol/carboxymethyl cellulose/ZSM-5 zeolite biocomposite membranes for dye adsorption applications[J]. Carbohydrate Polymers, 2018, 199: 129-140.
36	Yu K, Kumar N, Roine J, et al. Synthesis and characterization of polypyrrole/H-beta zeolite nanocomposites[J]. RSC Adv., 2014, 4(62): 33120-33126.
37	田丙伦, 舒玉瑛, 刘红梅, 等. Co-Mo/HZSM-5甲烷无氧芳构化催化剂上的积炭[J]. 催化学报, 2000, 21(3): 255-258.
	Tian B L, Shu Y Y, Liu H M, et al. Characterization of coke on Co-Mo/HZSM-5 catalyst for methane dehydro aromatization in the absence of oxygen[J]. Chinese Journal of Catalysis, 2000, 21(3): 255-258.
38	方辉煌, 吴历洁, 陈伟坤, 等. 生物质基含氧化合物在过渡金属碳化物上加氢脱氧研究进展[J]. 化工学报, 2021, 72(7): 3562-3575.
	Fang H H, Wu L J, Chen W K, et al. Recent progress on hydrodeoxygenation of biomass-derived oxygenates over transition metal carbides[J]. CIESC Journal, 2021, 72(7): 3562-3575.
39	马会霞, 周峰, 武光, 等. 多级孔HZSM-5分子筛催化快速热解生物质制芳烃[J]. 化工学报, 2020, 71(11): 5200-5207.
	Ma H X, Zhou F, Wu G, et al. Catalytic fast pyrolysis of biomass to aromatics over hierarchical HZSM-5[J]. CIESC Journal, 2020, 71(11): 5200-5207.
40	方书起, 石崇, 李攀, 等. Fe-Zn共改性ZSM-5催化作用下生物质快速热解特性研究[J]. 化工学报, 2020, 71(4): 1637-1645.
	Fang S Q, Shi C, Li P, et al. Study on rapid pyrolysis characteristics of biomass catalyzed by Fe-Zn co-modified ZSM-5[J]. CIESC Journal, 2020, 71(4): 1637-1645.

Catalyst	Si/Al molar ratio	Conversion/%	Yield(C molar fraction)/%
Catalyst	Si/Al molar ratio	Conversion/%	GVL	PA	EP
10Co/HZSM-5	21	98.70	41.91	12.97	20.32
10Co/Hβ	25	97.65	55.95	8.52	16.29
10Co/MCM-22	30	92.37	57.72	8.67	12.80
10Co/HY	26	90.06	62.28	6.34	10.96

Catalyst	Si/Al molar ratio	Conversion/%	Yield(C molar fraction)/%
Catalyst	Si/Al molar ratio	Conversion/%	GVL	PA	EP
10Co/HZSM-5	21	98.70	41.91	12.97	20.32
10Co/Hβ	25	97.65	55.95	8.52	16.29
10Co/MCM-22	30	92.37	57.72	8.67	12.80
10Co/HY	26	90.06	62.28	6.34	10.96

催化剂	温度区间/℃	峰顶温度/℃	酸量/(μmol/g)
10Co/HZSM-5	100~390	242	771
10Co/Hβ	100~410	231	579
10Co/MCM-22	100~390	239	711
10Co/HY	100~450	231	421

催化剂	温度区间/℃	峰顶温度/℃	酸量/(μmol/g)
10Co/HZSM-5	100~390	242	771
10Co/Hβ	100~410	231	579
10Co/MCM-22	100~390	239	711
10Co/HY	100~450	231	421

催化剂	温度区间/℃	峰顶温度/℃	酸量/(μmol/g)
10Co/HZSM-5	390~650	491	623
10Co/Hβ	410~650	494	504
10Co/MCM-22	390~600	456	339
10Co/HY	450~600	531	130