Selective Oxidation of 5-Hydroxymethylfurfural to 2，5-Furandicarboxylic Acid over Ru Supported on Magnetic NiFe2O4

doi:10.19894/j.issn.1000-0518.220396

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (6): 879-887.DOI: 10.19894/j.issn.1000-0518.220396

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Selective Oxidation of 5-Hydroxymethylfurfural to 2，5-Furandicarboxylic Acid over Ru Supported on Magnetic NiFe₂O₄

Yu-Wen YANG¹, Jing-Yao QI², Lin LI³, Guo-Ning CHU¹, Sai WANG¹, Yu ZHANG¹, Shuang ZHANG¹()

^1.Institute of Petrochemical Technology，Jilin Institute of Chemical Technology，Jilin 132022，China
^1.Jilin Petrochemical Company Organic Synthesis Plant，Jilin 132021，China
^3.BASF PJPC Neopentylglycol Company Limited，Jilin 132021，China

Received:2022-12-09 Accepted:2023-03-27 Published:2023-06-01 Online:2023-06-27
Contact: Shuang ZHANG
About author:zs3062332@126.com
Supported by:
the Natural Science Foundation of Jilin Provincial Science and Technology Department(YDZJ202101ZYTS163);Jilin Institute of Chemical Technology Doctoral Launch Fund(2020006);the Science and Technology Research Project of Jilin University of Chemical Technology(202020)

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Abstract

Abstract:

The magnetic nickel-iron spinel carrier NiFe₂O₄ is prepared by hydrothermal calcination， and then Ru/NiFe₂O₄ is prepared by impregnation reduction method by loading Ru nanoparticles on the carriers. The catalyst is characterized by X-ray diffraction （XRD），N₂ adsorption-desorption （BET）， NH₃ programmed temperature desorption （NH₃-TPD），H₂ programmed temperature reduction （H₂-TPR）， X-ray photoelectron spectroscopy （XPS） and inductively coupled plasma optical-emission spectrometry （ICP-OES）. The results show that the surface oxygen species of Ru/NiFe₂O₄ catalyst are abundant，and compared with the carriers， the specific surface area and acid amount of the catalyst increases after loading Ru， and Ru interacts with the support， which may be the key to the high activity and stability of the catalyst. The catalyst is used for the selective oxidation of 5-hydroxymethylfurfural （HMF）， and the experimental results show that the catalytic activity of the catalyst is significantly increased after loading Ru. The reaction conditions are optimized， when 0.08 g of KHCO₃ is added， the oxidant O₂ pressure is 1 MPa， the reaction temperature is 80 ℃，and 0.1 g of Ru/NiFe₂O₄ catalyst is used，HMF could be completely converted in water solution for 12 h，and the yield of 2，5-furandicarboxylic acid （FDCA） is 98.1%. Ru/NiFe₂O₄ can still maintain high activity after 5 cycles，and the active component Ru on the catalyst is not easy to leach. The catalyst has magnetic performance， which is convenient for separation from the reaction solution. The research provides valuable reference for the future industrialization of the highly efficient selective oxidation of HMF to synthesize FDCA.

Key words: Ru nanoparticles, NiFe₂O₄, Catalytic oxidation, 5-Hydroxymethylfurfural, 2, 5-Furandicarboxylic acid

CLC Number:

O643.3

Yu-Wen YANG, Jing-Yao QI, Lin LI, Guo-Ning CHU, Sai WANG, Yu ZHANG, Shuang ZHANG. Selective Oxidation of 5-Hydroxymethylfurfural to 2，5-Furandicarboxylic Acid over Ru Supported on Magnetic NiFe₂O₄[J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 879-887.

Figures/Tables 14

Fig.1 XRD pattern of NiFe2O4

Fig.2 N2 adsorption-desorption isotherm curves of NiFe2O4 and Ru/NiFe2O4

Fig.3 NH3-TPD diagrams of NiFe2O4 and Ru/NiFe2O4

Table 1 NH3-TPD acid amount results and catalytic activity before and after loading

Catalyst	Acid amount/（mmol·g^-1）				Conversion/%	Yield/%
Catalyst	Weak acid	Moderate acid	Strong acid	Total	HMF	FDCA	HFCA	FFCA
NiFe₂O₄	0.07	0.11	0.29	0.47	99.5	17.5	3.6	11.1
Ru/NiFe₂O₄	0.25	0.36	0.31	0.92	100	61.3	1.1	1.6

Fig.4 H2-TPR diagrams for Ru/NiFe2O4 （a） and NiFe2O4 （b）

Fig.5 XPS spectra of Ru/NiFe2O4

Fig.6 Effect of alkali amount on the oxidation of HMF

Fig.7 Effect of reaction temperature on the oxidation of HMF

Fig.8 Effect of reaction time on the oxidation of HMF

Fig.9 Effect of oxygen pressure on the oxidation of HMF

Fig.10 Effect of catalyst amount on the oxidation of HMF

Fig.11 Magnetic separation of Ru/NiFe2O4

Fig.12 Reuse of Ru/NiFe2O4

Table 2 Mass concentration of Ru in the reaction（mg/L）

Element	Run-1	Run-2	Run-3	Run-4	Run-5
Ru	0.00	0.00	0.00	0.00	0.00

References 25

1	BEASSON M， GALLEZOT P， PINEL C. Conversion of biomass into chemicals over metal catalysts［J］. Chem Rev， 2014， 114（3）： 1827-1870.
2	XU C， PAONE E， RODRÍGUEZ-PADRÓN D， et al. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural［J］. Chem Soc Rev， 2020， 49（13）： 4273-4306.
3	HAYASHI E， YAMAGUCHI Y， KAMATA K， et al. Effect of MnO₂ crystal structure on aerobic oxidation of 5-hydroxymethylfurfural to 2， 5-furandicarboxylic acid［J］. J Am Chem Soc， 2019， 141（2）： 890-900.
4	陈英，姜敏，孙长江，等. 聚2， 5-呋喃二甲酸乙二醇酯/聚丁二酸丁二醇酯共混物的制备与表征［J］. 应用化学， 2015， 32（9）： 1022-1027.
	CHEN Y， JIANG M， SUN C J， et al. Preparation and characterization of poly（ethylene 2， 5-furandicarboxylate）/poly（butylene succinate） blends［J］. Chin J Appl Chem， 2015， 32（9）： 1022-1027.
5	ADVANI J H， MORE G S， SRIVASTAVA R. Spinel-based catalysts for the biomass valorisation of platform molecules via oxidative and reductive transformations［J］. Green Chem， 2022， 24（9）： 3574-3604.
6	WAN X， TANG N， XIE Q， et al. A CuMn₂O₄ spinel oxide as a superior catalyst for the aerobic oxidation of 5-hydroxymethylfurfural toward 2， 5-furandicarboxylic acid in aqueous solvent［J］. Catal Sci Technol， 2021， 11（4）： 1497-1509.
7	ZHANG S， SUN X， ZHENG Z， et al. Nanoscale center-hollowed hexagon MnCo₂O₄ spinel catalyzed aerobic oxidation of 5-hydroxymethylfurfural to 2，5-furandicarboxylic acid［J］. Catal Commun， 2018， 113： 19-22.
8	MISHRA D K， LEE H J， KIM J， et al. MnCo₂O₄ spinel supported ruthenium catalyst for air-oxidation of HMF to FDCA under aqueous phase and base-free conditions［J］. Green Chem， 2017， 19（7）： 1619-1623.
9	GAWADE A B， NAKHATE A V， YADAV G D. Selective synthesis of 2， 5-furandicarboxylic acid by oxidation 5-hydroxymethylfurfural over MnFe₂O₄ catalyst［J］. Catal Today， 2018， 309： 119-125.
10	陈文龙. 碳纳米管负载铂、钌催化剂的制备及其催化羰基化合物加氢性能研究［D］. 兰州：西北师范大学， 2016.
	CHEN W L. Preparation and catalytic properties of carbon nanotubes supported platinum and ruthenium catalysts in the hydrogenation of carbonyl compounds［D］. Lanzhou： Northwest Normal University， 2016.
11	刘帅，黄振，何方，等. NiFe₂O₄为载氧体的生物质半焦化学链燃烧热力学模拟研究［J］. 新能源进展， 2016， 4（3）： 172-178.
	LIU S， HUANG Z， HE F， et al. Thermodynamic simulation of chemical chain combustion of biomass char with NiFe₂O₄ as oxygen carrier［J］. Adv New Renew Energy， 2016， 4（3）： 172-178.
12	陈康伟，熊文婷，符继乐，等. 合成气费托合成制重质烃Ru-Co/SiC催化剂的制备及性能［J］. 化工学报， 2021， 72（7）： 3648-3657.
	CHEN K W， XIONG W T， FU J L， et al. Preparation and performance of Ru-Co/SiC catalyst for Fischer-Tropsch synthesis of syngas to heavy hydrocarbons［J］. CIESC J， 2021， 72（7）： 3648-3657.
13	孙景玉. 直接甲醇燃料电池碳纳米管负载的阳极催化剂研究［D］. 乌鲁木齐：新疆大学， 2007.
	SUN J Y. Studies on anode catalysts supported on carbon nanotubes for direct methanol fuel Cell［D］. Urumqi： Xinjiang University， 2007.
14	SEEKHIAW P， PINTHONG P， PRASERTHDAM P， et al. Optimal conditions for butanol production from ethanol over MgAlO catalyst derived from Mg-Al layer double hydroxides［J］. J Oleo Sci， 2022， 71（1）： 141-149.
15	LIU M， ZHANG J， LIU J， et al. Synthesis of PVP-stabilized Pt/Ru colloidal nanoparticles by ethanol reduction and their catalytic properties for selective hydrogenation of ortho-chloronitrobenzene［J］. J Catal， 2011， 278（1）： 1-7.
16	YANG Y J， FENG Z， LI X， et al. One step synthesis of 2， 5-furandicarboxylic acid from fructose catalyzed by Ce modified Ru/HAP［J］. J Fuel Chem Technol， 2020， 48（8）： 942-948.
17	BENRABAA R， BOUKHLOUF H， LÖFBERG A， et al. Nickel ferrite spinel as catalyst precursor in the dry reforming of methane： synthesis， characterization and catalytic properties［J］. J Nat Gas Chem， 2012， 21（5）： 595-604.
18	张丹，尚润梅，赵振涛，等. V/Ce-Al₂O₃催化甲醇选择性氧化制备二甲氧基甲烷［J］. 应用化学， 2022， 39（9）： 1429-1436.
	ZHANG D， SHANG R M， ZHAO Z T， et al. Selective oxidation of methanol to dimethoxymethane over V/Ce-Al₂O₃［J］. Chin J Appl Chem， 2022， 39（9）： 1429-1436.
19	DAS S， THAKUR S， BAG A， et al. Support interaction of Ni nanocluster based catalysts applied in CO₂ reforming［J］. J Catal， 2015， 330： 46-60.
20	REDDY G K，BOOLCHAND P，SMIRNIOTIS P G. Unexpected behavior of copper in modified ferrites during high temperature WGS reaction aspects of Fe³⁺↔Fe²⁺ redox chemistry from mössbauer and XPS studies［J］. J Phys Chem C， 2012， 116（20）： 11019-11031.
21	GAO T， YIN Y， ZHU G， et al. Co₃O₄ NPs decorated Mn-Co-O solid solution as highly selective catalyst for aerobic base-free oxidation of 5-HMF to 2， 5-FDCA in water［J］. Catal Today， 2020， 355： 252-262.
22	GAO T， YIN Y， FANG W， et al. Highly dispersed ruthenium nanoparticles on hydroxyapatite as selective and reusable catalyst for aerobic oxidation of 5-hydroxymethylfurfural to 2，5-furandicarboxylic acid under base-free conditions［J］. Mol Catal， 2018， 450： 55-64.
23	ZHU M M， DU X L， ZHAO Y， et al. Ring-opening transformation of 5-hydroxymethylfurfural using a golden single-atomic-site palladium catalyst［J］. ACS Catal， 2019， 9（7）： 6212-6222.
24	VANDARKUZHALI S A A， KARTHIKEYAN G， PACHAMUTHU M P. Efficient oxidation of 5-hydroxymethylfurfural to 2， 5-furandicarboxylic acid over FeNPs@NH₂-SBA-15 catalyst in water［J］. Mol Catal， 2021， 16： 111951.
25	KANDASAMY P， GOGOI P， VENUGOPALAN A T， et al. A highly efficient and reusable Ru-NaY catalyst for the base free oxidation of 5-hydroxymethylfurfural to 2，5-furandicarboxylic acid［J］. Catal Today， 2021， 375： 145-154.

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Selective Oxidation of 5-Hydroxymethylfurfural to 2，5-Furandicarboxylic Acid over Ru Supported on Magnetic NiFe₂O₄

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