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Oxidation of Furfural to Maleic Acid and Fumaric Acid in Deep Eutectic Solvent (DES) under Vanadium Pentoxide Catalysis

  • Furfural is an alternative feedstock and has been used for the production of maleic acid (MA) and fumaric acid (FA) by an oxidation process. Deep eutectic solvents (DESs) were used as the green solvents while sodium chlorate was used as an oxidant and vanadium pentoxide was used as the catalyst at 70–90 ℃ under atmospheric pressure. It was found that several acidic DESs are valid, such as acetic acid/choline chloride (AA/ChCl) and propionic acid/choline chloride (PA/ChCl), and AA/ChCl DES was selected as the solvent for the conversion. The optimal DES is AA/ChCl, and the effect of the amount of oxidant, time, and temperature on the yield of the MA and FA has been systematically studied, and the conversion of furfural can reach 100% while the yield of the MA and FA reached 66.5% under reaction temperature of 80 ℃ for 12 h, which provides a new green route to synthesis valuable monomers from furfural.
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  • [1]

    Abbott, A. P. , Boothby, D. , Capper, G. , Davies, D. L. , Rasheed, R. K. , 2004. Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids. J. Am. Chem. Soc. 126, 9142-9147. doi: 10.1021/ja048266j
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    Abbott, A. P. , Capper, G. , Davies, D. L. , Rasheed, R. K. , Tambyrajah, V. , 2003. Novel solvent properties of choline chloride/urea mixtures. Chem. Commun. 1, 70-71.
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    Alonso-Fagúndez, N. , Agirrezabal-Telleria, I. , Arias, P. L. , Fierro, J. L. G. , Mariscal, R. , Granados, M. L. , 2014. Aqueous-phase catalytic oxidation of furfural with H2O2: high yield of maleic acid by using titanium silicalite-1. RSC Adv. 4, 54960-54972. doi: 10.1039/C4RA11563E
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    Araji, N. , Madjinza, D. D. , Chatel, G. , Moores, A. , Jérôme, F. , de Oliveira Vigier, K. , 2017. Synthesis of maleic and fumaric acids from furfural in the presence of betaine hydrochloride and hydrogen peroxide. Green Chem. 19, 98-101. doi: 10.1039/C6GC02620F
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    Badovskaya, L. A. , Povarova, L. V. , 2009. Oxidation of furans (Review). Chem. Heterocycl. Compd. 45, 1023-1034. doi: 10.1007/s10593-009-0390-8
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    Li, X. D. , Jia, P. , Wang, T. F. , 2016a. Furfural: a promising platform compound for sustainable production of C4 and C5 chemicals. ACS Catal. 6, 7621-7640. doi: 10.1021/acscatal.6b01838
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    Li, X. K. , Ho, B. , Lim, D. S. W. , Zhang, Y. G. , 2017. Highly efficient formic acid-mediated oxidation of renewable furfural to maleic acid with H2O2. Green Chem. 19, 914-918. doi: 10.1039/C6GC03020C
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    Li, X. K. , Ho, B. , Zhang, Y. G. , 2016b. Selective aerobic oxidation of furfural to maleic anhydride with heterogeneous Mo-V-O catalysts. Green Chem. 18, 2976-2980. doi: 10.1039/C6GC00508J
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    Mao, L. Y. , Zhang, L. , Gao, N. B. , Li, A. M. , 2012. FeCl3 and acetic acid co-catalyzed hydrolysis of corncob for improving furfural production and lignin removal from residue. Bioresour. Technol. 123, 324-331. doi: 10.1016/j.biortech.2012.07.058
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    Milas, N. A. , 1928. Catalytic oxidations in aqueous solutions. ii. The oxidation of primary alcohols. J. Am. Chem. Soc. 50, 493-499. doi: 10.1021/ja01389a037
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    Murthy, M. S. , Rajamani, K. , 1974. Kinetics of vapour phase oxidation of furfural on vanadium catalyst. Chem. Eng. Sci. 29, 601-609. doi: 10.1016/0009-2509(74)80071-0
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    Ni, Y. , Bi, Z. H. , Su, H. , Yan, L. F. , 2019. Deep eutectic solvent (DES) as both solvent and catalyst for oxidation of furfural to maleic acid and fumaric acid. Green Chem. 21, 1075-1079. doi: 10.1039/C8GC04022B
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    Tang, X. , Zuo, M. , Li, Z. , Liu, H. , Xiong, C. , Zeng, X. , Sun, Y. , Hu, L. , Liu, S. , Lei, T. , Lin, L. , 2017. Green processing of lignocellulosic biomass and its derivatives in deep eutectic solvents. ChemSusChem 10, 2696-2706. doi: 10.1002/cssc.201700457
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Oxidation of Furfural to Maleic Acid and Fumaric Acid in Deep Eutectic Solvent (DES) under Vanadium Pentoxide Catalysis

    Corresponding author: Lifeng Yan, lfyan@ustc.edu.cn
  • CAS Key Laboratory of Soft Matter Chemistry, Hefei National Laboratory for Physical Sciences at the Microscale, and Department of Chemical Physics, iCHEM, University of Science and Technology of China, Hefei 230026, China

Abstract: Furfural is an alternative feedstock and has been used for the production of maleic acid (MA) and fumaric acid (FA) by an oxidation process. Deep eutectic solvents (DESs) were used as the green solvents while sodium chlorate was used as an oxidant and vanadium pentoxide was used as the catalyst at 70–90 ℃ under atmospheric pressure. It was found that several acidic DESs are valid, such as acetic acid/choline chloride (AA/ChCl) and propionic acid/choline chloride (PA/ChCl), and AA/ChCl DES was selected as the solvent for the conversion. The optimal DES is AA/ChCl, and the effect of the amount of oxidant, time, and temperature on the yield of the MA and FA has been systematically studied, and the conversion of furfural can reach 100% while the yield of the MA and FA reached 66.5% under reaction temperature of 80 ℃ for 12 h, which provides a new green route to synthesis valuable monomers from furfural.

1.   Introduction
  • Biomass-based chemicals and materials are attracting topic for sustainable development. Furfural is an ideal biomass resource which has been produced from cellulosic and waste biomass such as corncob, corn stock, and rice hull with a global output of about one million ton per year (Mao et al., 2012). Furfural has been utilized as feedstock for synthesis of maleic acid (MA) and fumaric acid (FA), and the MA/FA and their anhydride are important chemical intermediates that have been applied in multiple fields of the chemical industry, such as synthesis of unsaturated polyester resins, vinyl copolymers, terephthalic acid, coatings, lubricant additives, copolymers, agrochemicals, and pharmaceuticals (Badovskaya and Povarova, 2009; Tachibana et al., 2015). It is attractive to prepare the MA and FA in green and low-cost method for the production of them is about two million ton per year. Today, the MA is mainly produced in the industry by the aerobic oxidation of butane, benzene, or butadiene while the FA is manufactured by hydrolysis conversion of maleic anhydride or biological conversion by fungi (Zhou et al., 2011).

    Furfural or 5-hydroxymethylfurfural (HFM) is the most important bio-based chemical platforms that can be obtained from hemicellulose or cellulose, and they can be used to prepare the MA and FA via an oxidation process under the assistant of catalysts (Li et al., 2016a). Various catalytic systems have been developed for the conversion of furfural/HMF to MA/FA in the presence of potassium permanganate, chlorate, molecular oxygen or hydrogen peroxide as oxidants, such as vanadium-oxide-based catalysis in gas-phase oxidation of furfural with an up to 70% MA (Milas, 1928; Murthy and Rajamani, 1974), liquid phase oxidations of furfural under titanium silicate-1 (TS-1) catalysis gave 78% yield of MA (Alonso-Fagúndez et al., 2014), and Mo-V-O catalyst was also used as the heterogeneous catalyst to convert furfural to anhydride of MA and FA using acetic acid as the solvent (Li et al., 2016b). Else, using an aqueous solution of betaine hydrochloride (BHC) in the presence of hydrogen peroxide can get over 90% yield of MA and FA (Araji et al., 2017). Li et al. (2017) found that furfural can be efficiently oxidized by H2O2 in formic acids as both solvent and catalyst in the presence of H2O2. Interestingly, they found that the acidity of organic acid is a key parameter, and the yield of the MA increased when the pKa of organic acids increase. Is it possible to use a much strong organic acid to get the oxidation reaction more quick and efficient? Such as oxalic acid with pKa of 1.23. However, the molten point of oxalic acid is 189 ℃, and a solvent should be added if oxalic acid was used. Recently, we found that an oxalic acid-based deep eutectic solvent (DES) of oxalic acid/choline chloride (OA/ChCl) can work as both the solvent and catalyst for furfural oxidation and the conversion of furfural can reach 100% while the yield of the MA and FA reached 95.7% under mild reaction temperature of 50 ℃ (Ni et al., 2019). During this study, we found that the presence of water in H2O2 impede the oxidation of furfural, so we want to know what will happen if the oxidant H2O2 aqueous solution is replaced by a solid oxidant with still using DES as the green solvent? In addition, during the conversion, the concentration of furfural is low, and efficient oxidant still need to be emplored.

    Recently, deep eutectic solvents (DESs) have attracted much attention for their simple, cheap and green feature, and DES is a series of transparent liquid eutectic mixtures that obtained through strong hydrogen-bonding interactions between hydrogen-bond acceptors (HBA) and hydrogen-bond donors (HBD) (Abbott et al., 2003; 2004), which owns properties of both organic solvents and ionic liquids (Ruß and König, 2012; Zhang et al., 2012). Among them, choline chloride (ChCl) is a typical HBA and can be mixed with various small organic components HBD to prepare DESs (Tang et al., 2017).

    It has been reported that the oxidation of furfural with NaClO3 as an oxidant and V2O5 as a catalyst and the yield of both MA and FA reached 58% (Tachibana et al., 2015). Here, the system was utilized to oxidate furfural to the MA and FA in various DESs, and try to develop a new route to the target (Fig. 1).

    Figure 1.  Conversion of furfural to fumaric acid (FA) and maleic acid (MA) in ChCl based deep eutectic solvents (DESs) using NaClO3 as oxidant and V2O5 as the catalyst.

2.   Materials and Methods
  • All reagents and solvents mentioned were purchased from Aladdin company. Furfural (98%), maleic acid (MA, 99.5%), NaClO3, ammonium metavanadate (chemically pure), coned, hydrochloric acid, oxalic acid (OA, 99.5%), fumaric acid (FA, 99%), acetic acid (AA, 99.5%), propionic acid (98%), butyric acid (99%), and malonic acid (99%) were supplied by Sinopharm. Choline chloride (ChCl, 98%), urea, and ZnCl2 were supplied by Macklin. Ultrapure water with a resistivity of 18 MΩ-cm was produced by a Milli-Q (Millipore, USA).

  • The 10 g of ammonium metavanadate was suspended in 100 mL of ultrapure water and then 15 mL of coned, hydrochloric acid was added under stirring to form a reddish-brown semi-colloidal precipitate, and it was washed several times with water and stood at room temperature for three days. Next, the precipitate was collected by filtration with repeat washing and dried for 12 h at 120°. For the solution of V2O5 in the DES, it was prepared by adding the powder of V2O5 into the DES solution under stirring at room temperature.

  • At first, furfural was purified by vacuum distillation. For the DES preparation, adding 0.4-1.0 g organic acids or other HBD and 1.0-1.8 g ChCl into a 25 mL flask, heating the container at 50 ℃ under a water bath for several minutes to form the liquid. Then, 0.2-1.0 g NaClO3 was added, and 3 min later adding 1-3 mmol furfural and the solution of V2O5 in the DES. The reaction was carried out for a various time at 70-95 ℃. At the end of the reaction, diluting the reaction solution 100 times by water to quench the reaction, and then it was through a 0.22 μm syringe filter for high performance liquid chromatography (HPLC) analysis.

  • High performance liquid chromatograph (Shimadzu), C-18 chromatographic column (5 µm, 4.6 mm × 250 mm, purchased from Agilent Technologies Inc.) with an ultraviolet detector. Mobile phase: 20% methanol + 80% phosphoric acid solution (1‰), column temperature of 40 ℃, and flow rate of 0.6 mL/min.

3.   Results and Discussion
  • The DESs are consistent with HBA and HBD, and the number of possible systems is huge. Here, we choose ChCl as the HBA and various compounds as the HBDs, such as urea, ZnCl2, OA, AA, propionic acid (PA), butyric acid (BA), and malonic acid (MaA) as the HBD, and then as the solvent for furfural oxidation with NaClO3 and V2O5 system, and the products were analyzed utilizing HPLC. Figure 2 shows the typical HPLC curves of the products when various DES were employed for the reaction. The products are relatively simple, and MA and FA are the main products, indicating the DESs system can be used as the solvent for furfural oxidation.

    Figure 2.  High performance liquid chromatography (HPLC) curves of products obtained from furfural oxidation with NaClO3 and V2O5 system in various deep eutectic solvent (DES): a) Urea/choline chloride (ChCl), b) Butyric acid/ChCl (BA/ChCl), c) Propionic acid/ChCl (PA/ChCl); d) AA/ChCl.

    Table 1 lists the results of the reactions with various DESs. It is found that for urea/ChCl DES, nearly no products formed while for ZnCl2/ChCl DES only little amount of the MA and FA appeared, indicating that weak alkalinity and Lewis acid-based DES are not suitable for the oxidation of furfural with NaClO3 and V2O5 system. Based on the mechanism of chlorate oxidation, acidity may promote the reaction. So a series of organic acids were used to prepare the DESs for the reaction. The oxidation of furfural took place in all the organic acids system to form MA and FA, and the yield of the MA and FA for diacid is lower than that of single acid, and the best is AA (50.1%) while butyric acid is also a potential choice (21.2%). In this study, AA/ChCl DES has been chosen as the green solvent for the oxidation of furfural.

    Solvent Yield of MA (%) Yield of FA (%) Yield of MA and FA (%)
    Urea/ChCl DES Trace Trace Trace
    ZnCl2/ChCl DES 0.4 0.6 1.0
    Oxalic acid/ChCl DES 9.5 10.0 19.5
    Acetic acid/ChCl DES 20.1 30 50.1
    Propionic acid/ChCl DES 7.8 11.2 19.0
    Butyric acid/ChCl DES 5.7 15.5 21.2
    Malonic acid/ChCl DES 12.2 6.9 19.1
    Water 8.2 32.5 40.7
    Notes: reaction conditions are 2 mmol furfural, 5 mL DES (HBD꞉HAD = 1꞉2), 2.6 mmol of NaClO3 with 0.07 mmol of V2O5, 50 ℃ and 24 h. MA, maleic acid; FA, fumaric acid.

    Table 1.  MA and FA yield from furfural by oxidation in various DES

    The mechanism of furfural oxidation with NaClO3 and V2O5 system had been suggested (Fig. 3) (Milas, 1928; Tachibana et al., 2015), and the amount of oxidant used is a key parameter. As shown in Fig. 4, the yield of MA and FA has a direct relationship to the amount of NaClO3. At the reaction temperature is 70 ℃, the yield of the MA decreased from 31% to 15% with the increase of the molar ratio of NaClO3 to furfural. However, the yield of the FA increased from 52.5% to 57.5% with more NaClO3 added, indicating a transmutation of the MA to FA under such condition. The total yield of MA and FA increased gradually.

    Figure 3.  Possible mechanism of furfural oxidation by NaClO3 and V2O5 system.

    Figure 4.  Effect of molar ratio of NaClO3 to furfural on yield of MA and FA in AA/ChCl DES solution. Reaction condition: furfural (2 mmol), 5 mL DES, 70 ℃, 12 h.

    When the reaction temperature was increased to 80 ℃, it may promote the reaction. As shown in Fig. 5, the yield of the FA increased quickly with the increase of the oxidant and catalyst, and the total yield of the MA and FA also increased up to 70% when 2.3 fold of NaClO3 was used. However, the yield of the MA decreased with the increase of the oxidant, which may be due to the temperature increase since more NaClO3 was added. Interestingly, with the increase of the formation of the FA, crystalline can be found in the system, which results from the low solubility of the FA in AA, even in the presence of the ChCl.

    Figure 5.  Effect of molar ratio of NaClO3 to furfural on yield of MA and FA in AA/ChCl DES solution. Reaction condition: furfural (2 mmol), 5 mL DES, 80 ℃, 12 h.

    Reaction time is another key point for the reaction, and the reaction was carried out at a temperature from 6 h to 24 h with other conditions kept the same. As shown in Fig. 6, at 6 h, the yield of the MA and FA are 20.1% and 30.0%, respectively. The yield of the FA increased at the beginning and then decreased with longed reaction time, and the maximum yield of the FA is 49.2% at 12 h while the total yield of the MA and FA is 66.1%. The reason may be the furthermore oxidation of the FA to carbon dioxide at a long reaction time with bubble generation. However, for the MA, the yield decreased with the prolonged reaction time, indicating much MA should take place transmutation or degraded to carbon dioxide.

    Figure 6.  Effect of reaction time on yield of MA and FA in AA/ChCl DES with NaClO3 and V2O5 system. Reaction condition: furfural (2 mmol), NaClO3 (3.4 mmol), 5 mL DES, 80 ℃.

    The effect of reaction temperature on the oxidation of furfural was also studied, and the results were shown in Fig. 7. Increasing reaction temperature promotes the formation of the FA while the yield of the MA decreases. At high temperature, the transmutation of the MA to FA occurs easily (Tachibana et al., 2015). Interestingly, at 100 ℃, the yield of the FA reaches 66.7% while the yield of MA is only 4.2%, indicating that the FA can be selectively synthesized in the system by controlling the reaction temperature. For the reaction, there are two distinct stages, a violent one followed by a mild one, while in the first one furfural is oxidated and the second one for the transmutation of the MA to FA. So, it is easy to increase the reaction temperature for the DES solvent compared with the aqueous system, and the reaction can be completed in a short time at high temperature.

    Figure 7.  Effect of reaction temperature on yield of MA and FA in AA/ChCl DES with NaClO3 and V2O5 system. Reaction condition: furfural (2 mmol), NaClO3 (3.4 mmol), 5 mL DES, 12 h.

4.   Conclusions
  • In this study, an efficient route was found to convert furfural to MA and FA using AA based DES and AA/ChCl as a solvent while sodium chlorate and vanadium pentoxide were used as oxidant and catalyst. The reaction can be carried out under temperature (70-100 ℃) at atmospheric pressure, and the total yield of the MA and FA reached 70% while the yield of FA reached 66.7%. It provides a new and green method to convert biomass to valuable chemicals.

Conflicts of interest
  • There are no conflicts to declare.

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