Accepted Manuscript

Direct conversion of furfural to levulinic acid/ester in dimethoxymethane:

Understanding the mechanism for polymerization

Yuewen Shao, Xun Hu, Zhanming Zhang, Kai Sun, Guanggang Gao, Tao Wei, Shu
Zhang, Song Hu, Jun Xiang, Yi Wang

PII: S2468-0257(18)30053-0
DOI: 10.1016/j.gee.2018.10.002
Reference: GEE 135

To appear in: Green Energy and Environment

Received Date: 25 May 2018

Revised Date: 29 September 2018
Accepted Date: 10 October 2018

Please cite this article as: Y. Shao, X. Hu, Z. Zhang, K. Sun, G. Gao, T. Wei, S. Zhang, S. Hu, J. Xiang,
Y. Wang, Direct conversion of furfural to levulinic acid/ester in dimethoxymethane: Understanding
the mechanism for polymerization, Green Energy & Environment (2018), doi: https://doi.org/10.1016/
j.gee.2018.10.002.

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 ACCEPTED MANUSCRIPT

1 Graphic Abstract
2

3 Direct conversion of furfural to levulinic acid/ester in dimethoxymethane:

4 Understanding the mechanism for polymerization
5

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6

7 Yuewen Shaoa, Xun Hu a,*, Zhanming Zhanga, Kai Suna, Guanggang Gaoa,

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8 Tao Weia, Shu Zhangb, Song Huc, Jun Xiangc, Yi Wangc,*
9

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10
11 Direct conversion of furfural to levulinic acid/ester
12 was achieved in dimethoxymethane/methanol via
13 only acid catalysis. The polymerization between

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14 levulinic acid/ester with dimethoxymethane was the
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15 key reason for diminishing the production of
16 levulinic acid/ester. Methanol as the
17 co-solvent/reactant alleviated the polymerization.
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 ACCEPTED MANUSCRIPT

1 Direct conversion of furfural to levulinic acid/ester in dimethoxymethane:

2 Understanding the mechanism for polymerization
3

4 Yuewen Shaoa, Xun Hua,*, Zhanming Zhanga, Kai Suna, Guanggang Gaoa,
5 Tao Weia, Shu Zhangb, Song Huc, Jun Xiangc, Yi Wangc,*

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6
a
7 School of Material Science and Engineering, University of Jinan, Jinan, 250022, P. R.

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8 China.
b
9 College of Materials Science and Engineering, Nanjing Forestry University, Nanjing

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10 210037, Jiangsu, P. R. China.
c

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11 School of Energy and Power Engineering, Huazhong University of Science and
12 Technology, Wuhan, 430074, P. R. China.
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*Corresponding author. Tel. /fax: +86–531–89736201; E-mail: [email protected]

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15 (X. Hu); [email protected] (Y. Wang).

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18 Submit to
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20 Green Energy & Environment

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21
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22 For consideration for publication

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1 Abstract
2 This study investigated the conversion of furfural to 5-hydroxymethylfurfural
3 (HMF) and further to levulinic acid/ester in dimethoxymethane under acidic
4 conditions, with the particular focus on understanding the mechanism for polymer
5 formation. The results showed that furfural could react with dimethoxymethane via

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6 electrophilic substitution reaction to form HMF or the ether/acetal of HMF, which
7 were further converted to levulinic acid and methyl levulinate. The polymerization of

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8 furfural and the cross-polymerization between dimethoxymethane and the levulinic
9 acid/ester produced were the main side reactions leading to the decreased yields of

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10 levulinic acid/ester. Comparing to the other solvent, methanol as the co-solvent helped
11 to alleviate but not totally inhibited the occurrences of the polymerization, as the

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12 polymerization reactions via aldol condensation did not eliminate the C=O
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13 functionalities. As a consequence, the polymerization reactions continued to proceed.
14 Other co-solvent used such as guaiacol, dimethyl sulfoxide and acetone interfered
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15 with the transformation of furfural to HMF or aided the polymerization reactions. The
16 polymer produced from the reactions between furfural and DMM was different from
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17 that produced from levulinic acid/ester. The former had a higher crystallinity, while
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18 the latter was more aliphatic. The DRIFTS and TG-MS studies showed that the
19 polymer had the carboxylic group, methyl group and the aliphatic structure in the
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20 skeleton. The removal of these functionalities was accompanied by the aromatization

21 of the polymer. The condensation of DMM with levulinic acid/ester was the key
reason for the diminished production of levulinic acid/ester.
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24 Keywords: Furfural; Dimethoxymethane; Levulinic acid/ester; Mechanism for

25 polymerization; Properties of the polymer
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1 1. Introduction
2 In recent years, much effort has been made in the research on the conversion of
3 biomass to the platform chemicals such as levulinic acid and furfural [1,2]. Levulinic
4 acid is a versatile building block chemical that can be used for manufacturing many
5 other value-added chemicals such as diphenolic acid [3,4], pyrrolidones [5−7],

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6 γ-valerolactone [8−11] and etc. Levulinate esters, the esters from esterification of
7 levulinic acid with alcohols, are also the important platform compounds that can be

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8 used as solvents and additives [12−17]. The productions of levulinic acid or
9 levulinates from cellulose in biomass or the C6 sugars (glucose, fructose,

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10 levoglucosan) have been the focus of many studies [18−29]. Levulinic acid can be
11 formed via the dehydration of C6 sugars to 5-hydroxymethylfurfural (HMF), and the

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12 subsequent decomposition of HMF to levulinic acid and formic acid [30−35].
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13 Both the dehydration of C6 sugars and decomposition of HMF are catalyzed by
14 acid catalysts [36]. In comparison, in the presence of a Brønsted acid catalyst, the
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15 conversion of the C5 sugars like xylose forms furfural as the main product, while
16 furfural mainly polymerize and could not be converted to levulinic acid with
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17 appreciable yields [37,38]. Xylose, in fact, can also be converted to levulinic acid via
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18 a dehydration step to form furfural, a hydrogenation step from furfural to furfuryl

19 alcohol and an acid-catalysis step from furfuryl alcohol to levulinic acid [39−43]. The
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20 above process for conversion of furfural to levulinic acid involves both hydrogenation
21 catalyst and acid catalyst, which results in the high cost and complicated reaction
process.
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23 If furfural could be transformed into HMF, the direct conversion of furfural to

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24 levulinic acid would be achieved via acid catalysis only. Formaldehyde is an

25 electrophile and it could potentially react with furfural to form HMF. Nevertheless,
26 the commercially available formaldehyde contains a large amount of water and our
27 pervious study has proved that the furans like HMF or furfural was prone to
28 polymerize in aqueous medium [44]. Further to this, both furfural and formaldehyde
29 are prone to polymerize, especially under acidic conditions. How to suppress the

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1 polymerization during the conversion of furfural to levulinic acid would be a key to

2 enhance the yield of levulinic acid from furfural.
3 In this study, instead of formaldehyde, we used dimethoxymethane (the acetal of
4 formaldehyde) to transform furfural to HMF and further to levulinic acid, which did
5 not involve the use of a hydrogenation catalyst or pressurized hydrogen. In addition,

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6 dimethoxymethane is the acetal of formaldehyde, which can be produced readily by
7 mixing formaldehyde and methanol. In practice, levulinic acid/ester can be produced

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8 via the abundantly available feedstock including furfural, formaldehyde,
9 methanol/ethanol and a catalyst, which will be more economically feasible. The study

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10 particularly focused on the reaction pathways for the formation of polymer and the
11 physicochemical properties of the polymer, aiming to provide useful information for

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12 understanding the mechanism for the polymerization and developing the methods to
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13 suppress the polymer formation.
14
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15 2. Experimental
16 2.1. Materials
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17 The solvents and reactants used in this study are analytical grade, such as
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18 methanol, ethanol, acetone, diethyl ether, N, N-dimethylformamide (DMF), dimethyl

19 sulfoxide (DMSO), tetrahydrofuran (THF) and furfural, which were purchased from
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20 Sinopharm Chemical Reagent Co., Ltd. Dimethoxymethane (DMM), levulinic acid

21 (LA), ethyl levulinate (EL), iso-eugenol and guaiacol were purchased from Shanghai
Macklin Biochemical Co., Ltd. 5-hydroxymethylfurfural (HMF) and methyl
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23 levulinate (ML) were purchased from Saan Chemical Technology (Shanghai) Co., Ltd.
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24 Ethyl formate and ethyl acetate were purchased from Tianjin Guangfu Fine Chemical
25 Co., Ltd. A solid catalyst (D008), a commercial solid acidic resin catalyst with the
26 maximum operating temperature of 190°C and an acid density of 1.55 mmol/g, was
27 purchased from Cary Environmental Technology. All the chemicals and the catalyst
28 were used directly without any pretreatment.
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1 2.2. Experimental procedure

2 Acid-catalyzed conversion of furfural was performed in a 100 ml autoclave made
3 of hastelloy (Oushite Instrument Technology Co., Ltd.). Firstly, reactants including
4 furfural and catalyst were mixed with solvents, and loaded into autoclave at room
5 temperature. After that, leakage of the reactor was checked, and the reactor was
purged with high-purity nitrogen for 3 times. Afterwards, the reaction temperature

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6

7 was raised to the setting value within ca. 30 min with a stirring rate of 300 rpm under

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8 auto-generated vapor pressure.
9 To probe progress of the reaction, sampling was conducted at 0, 20, 40, 60 and

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10 90 min, respectively. After finishing the experiments, the reactor was cooled down.
11 The catalyst and the liquid residual were collected and filtered, and ethanol was used

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12 to wash the catalyst until the filtrate was colorless. Afterwards, the used catalyst was
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13 dried at 105°C to a constant weight for measuring the yield of coke formed and for
14 further characterizations.
Definition of yield of levulinic acid/methyl levulinate is as follows:
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Mole of levulinic acid/methyl levulinate produced

Yield ሺ%ሻ= ×100%
Mole of furfural loaded
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18 Definition of yield of insoluble polymer is as follows:

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19
Weight of insoluble polymer formed
Yield ሺ%ሻ= ×100%
Weight of furfural loaded
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21 Definition of conversion of furfural is as follows:

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Mole of furfural converted
Conversion ሺ%ሻ= ×100%
Mole of furfural loaded
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24 2.3. Analytical methods

25 The products were analyzed by using a Shimadzu GC-MS-QP 2020 with a
26 capillary column (DB-Wax) (length: 30 m; internal diameter: 0.25 mm; film thickness:
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1 0.25 mm). Before the analysis, the samples were diluted with tetrahydrofuran (THF)
2 to ca. 2 wt. %, and then 0.5 µL of the sample was injected into the injection port with
3 a split ratio of 50 : 1. The column temperature was maintained at 35°C for 3 min and
4 then increased to 250°C with a heating rate of 10 °C/min, and maintained at 250°C for
5 3 min. Helium was used as the carrier gas with a flow rate of 4.0 mL/min. The

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6 identification of the compounds in the MS spectrum was achieved by comparing to
7 the standard spectra of the National Institute of Standards and Technology (NIST)

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8 library. As for some products without standard spectra in the library, they were
9 identified by studying the mass fragments in the spectrum. Standard chemicals were

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10 also injected to obtain the respond factors for quantitative analysis of the targeting
11 products. For the compounds without standards available, the peak areas were

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12 normalized for comparison of their relative abundance.
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13 UV-fluorescence spectra of the soluble polymers were measured with a
14 Shimadzu (RF-6000) fluorescence spectrometer. The scan rate was 600 nm/min, and
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15 the slit widths were 3 nm. All the samples were diluted to 400 ppm with ethanol, as
16 the concentration of 400 ppm was in the linear range of response. Different aromatic
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17 ring sizes correspond to different wavelength [45,46], which are related to the
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18 aromatic ring structure of samples. As shown in Fig. S1 in supporting information,

19 iso-eugenol, toluene, 2-methoxy-4-methylphenol and guaiacol have different aromatic
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20 ring structures, and their UV-fluorescence spectrums distributed at varied wavelength.

21 Generally, the bigger the size of the aromatic ring structure, the longer the wavelength.
In addition, the higher concentration corresponds to high intensity of the spectra. The
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23 fluorescence spectra intensity thus can reflect the abundance of the soluble polymers
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24 formed.
25 The soluble polymer was also characterized by ultraviolet spectrophotometer
26 (Metash Corp, UV-800S). Before the characterization, the liquid product was diluted
27 to 400 ppm with ethanol, and all measurements were operated at room temperature by
28 using corresponding solvent as blank. As for the UV-vis spectra, conjugated π-bonds
29 can be detected in the spectrum. The wavelength of some typical compounds was

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1 shown in Fig. S2. The peak of the compounds with conjugated π-bonds appears at
2 200–250 nm and 250–350 nm, respectively. Similarly, the bigger the conjugated
3 π-bonds, and the longer the wavelength.
4 The used catalyst together with the solid residual collected was characterized
5 with Fourier Transform Infrared Spectroscopy (FT-IR) by using Nicolet iS50

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6 instrument to probe the functionality groups of the catalyst. The spectrum represents
7 the average of 16 scans, and the spectral resolution is 4 cm-1. Before the analysis, the

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8 sample was mixed with KBr at a mass ratio of 1 : 100 and ground uniformly. The
9 mixture was then pretreated at 60°C in vacuum oven for 2 h. The dried sample was

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10 pressed into a tablet for the characterization. To further research the change of the
11 functionality groups in the insoluble polymer versus temperature, DRIFTS of the

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12 sample was obtained from the Nicolet iS50 equipped with a modified Harrick Praying
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13 Mantis DRIFT cell instrument. The powdered sample was pretreated at 60°C in a
14 vacuum oven for 2 h, and then the dried sample was pressed into the cell. After
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15 connecting the device, the cell was heated from 25 to 800°C at a heating rate of
16 10 °C/min in vacuum. The FT-IR spectrum was recorded during heating at an interval
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17 of 7 seconds.
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18 The crystal structure of the insoluble polymer in the catalyst was characterized
19 with Rigaku Ultima Ⅳ X-ray diffraction (XRD). The XRD was equipped with a
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20 graphite monochromatized Cu target (Kα-radiation source, λ = 1.5406 Å), and the

21 scanning rate was 10 º/min in the range of 5–80º.
Elemental analysis (EA) was used to analyze the elemental amounts of the
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23 insoluble polymers, by using a Euro EA3000-Single instrument. The contents of C, H,

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24 N and S elements were measured via combustion of the samples at 1150°C. Helium
25 was used as a carrier gas to blow the gaseous products into the different adsorption
26 tubes for separation and detection with TCD detectors to measure the element
27 contents.
28 Thermogravimetric analysis (TG) associated with an in-situ MS was conducted
29 with a HCT-1 microcomputer differential thermal balance (from Beijing hengyuan

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1 experimental equipment Co., Ltd.) to understand the pyrolysis characteristics of the

2 insoluble polymer. The catalyst together with the insoluble polymer was ground into
3 fine powder, and then 10 mg of the powder loaded into a ceramic crucible was firstly
4 heated from room temperature to 105°C, and was maintained at this temperature for
5 20 min to remove the physically absorbed water. After that, the temperature was

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6 increased to 900°C at a ramping rate of 20 °C/min in the atmosphere of nitrogen. The
7 release of the gaseous products including CO2, CO, H2, C2H4 and CH4 during the TG

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8 characterization was measured by an in-situ mass spectrometer (Pfeiffer, MS GSD
9 320).

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11 3. Results and discussion

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12 3.1 The effect of reaction medium
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13 Table 1 showed the remarkable effects of reaction medium on the formation of
14 levulinic acid/ester. When DMM was used as a single solvent in the reaction medium,
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15 the yield of levulinic ester (LE) was only 14.2% (entry 1, Table 1). The main reason
16 was due to the polymerization reactions, as evidenced in Fig. 1a, where the
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17 UV-florescence synchronous spectrums showed the formation of the soluble polymers

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18 [37]. The soluble polymers can be converted into the insoluble polymers with the
19 prolonged reaction time, leading to the decreased spectrum intensity. Interestingly, the
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20 yield of the insoluble polymer was higher than the amount of furfural loading (Entry 1,
21 Table 1). Clearly, DMM was also involved in the polymerization reactions, which will
be discussed later.
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23 Methanol as the sole solvent could not transform furfural into HMF and thus the
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24 yield of levulinic acid/ester was very low (Entry 2, Table 1), which was similar to our
25 previous study [37]. Nevertheless, the polymerization of furfural also formed
26 abundant soluble polymer (Fig. 1b). In fact, in methanol alone, majority of furfural
27 polymerized with the prolonged reaction time, as evidenced by the high yield of coke
28 in Entry 2 of Table 1. With DMM alone as the reaction medium, the significant
29 polymerization was probably responsible for the low yields of levulinic acid and

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1 levulinate. To suppress the polymerization reactions, several co-solvents were used in

2 the reaction medium.
3 In total the 13 solvents were used as a co-solvent of DMM for the conversion of
4 furfural to levulinic acid. The different solvent impacted the conversion of furfural in
5 distinct ways. Water as a solvent promoted the production of levulinic acid but not the

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6 total yields of levulinic acid/ester (Entry 3, Table 1). DMF is a base, which
7 deactivated the catalyst by neutralizing the acidic sites on surface of the catalysts [47].

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8 This was verified by titration of the acidic sites of the used catalyst. The conversion of
9 furfural to levulinic acid needed the aid of acid catalysts and in DMF the conversion

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10 of furfural was nil (Entry 4, Table 1). Acetone was very active towards polymerization
11 reactions, leading to a significant amount of coke while a decrease in the production

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12 of levulinic acid/ester (Entry 5, Table 1) [47]. DMSO could suppress the
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13 polymerization of furfural or 5-hydroxymethylfurfural, while it also could suppress
14 the electrophilic substitution reactions between furfural and dimethoxymethane, as
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15 evidenced by the low yields of levulinic acid/ester and the low conversion of furfural
16 (Entry 6, Table 1). It seemed ethyl formate also had some negative effects on the
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17 conversion of furfural, while ethyl acetate had fewer effects on the conversion of
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18 furfural to levulinic acid/ester. How did the two esters behave distinctly need further
19 investigation. In comparison, the ether like diethyl ether could remarkably promote
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20 the formation of levulinic acid/ester (Entry 9, Table 1). Under the acidic conditions,
21 diethyl ether could hydrolyze to ethanol, while ethanol could promote the formation
of levulinic acid/ester. THF is actually also an ether, which did not show remarkable
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23 promotional effects on levulinic acid formation, but promoted coke formation (Entry
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24 11, Table 1). The phenolics like guaiacol and iso-eugenol negatively affected the
25 reaction between furfural and dimethoxymethane. Both guaiacol and iso-eugenol were
26 phenolics and they have methoxyl group and hydroxyl group as electron-donating
27 functionalities, which promoted the electrophilic substitution reactions. These
28 phenolics probably reacted with dimethoxymethane, forming the insoluble polymer,
29 which competed with the reaction between furfural and dimethoxymethane. The

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1 GC-MS analysis showed the phenolics did react with dimethoxymethane, forming
2 some condensation products, as shown in Fig. S3 and Scheme S1. Toluene did not
3 have the oxygen-containing functionalities acting as strong electron-donating
4 functionalities, which has a much less effect on the conversion of furfural to levulinic
5 acid (Entry 13, Table 1) [25,38]. The conversion of furfural in the varied reaction

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6 mediums with longer reaction time were also conducted, similar conclusions were
7 obtained (Table S1 in Supporting Information). In general, the results presented here

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8 showed that the alcohols especially methanol showed the superior promotional effects
9 on the production of levulinic acid/ester and also some suppression on the formation

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10 of coke.
11 The soluble polymers formed in the varied reaction medium were also

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12 characterized with UV-fluorescence spectrometer (Fig. 1c). Basically, there were
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13 soluble polymers formed in almost all the reaction medium employed. The soluble
14 polymer could have three to five conjugated π-bonds system, as the excitation
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15 wavelength ranges from 375 to ca. 450 nm, which was an intermediate product from
16 furfural/dimethoxymethane to coke [47].
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18 3.2 Effects of DMM/methanol volumetric ratio on conversion of furfural

19 Since methanol as a co-solvent could help to promote the formation of levulinic
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20 acid/ester, the ratio of methanol in the DMM/methanol reaction medium was further
21 investigated. In general, at higher methanol content (Entry 1, Table 2), the yields of
levulinic acid/ester were relatively lower while the yield of coke was also lower.
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23 Methanol suppressed the polymerization reactions, which, however, also diluted the
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24 concentration of DMM in the reaction medium. This negatively impacted the

25 formation of levulinic acid/ester. The decrease of methanol content in DMM/methanol
26 promoted the production of levulinic acid/ester, which reached the maximum at the
27 DMM/methanol volumetric ratio of 33.3/26.7. The further decrease of methanol
28 content led to the decreased formation of levulinic acid/ester, while correspondingly
29 the production of coke was increased. The UV-fluorescence spectrum of the soluble

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1 polymer was shown in Fig. 2a. According to the fluorescence spectra of the standards
2 chemicals as shown in Fig. S1, the soluble polymer formed in the DMM/methanol
3 have three to five conjugate π-bonds structures [47]. The characterization of the
4 soluble polymer by FT-IR (Fig. 2b) showed that the C=C bonds and the ketone group
5 [48] became more obvious with the decrease of the ratio of methanol. Further to this,

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6 the absorption of the carboxyl group [48] also became more obvious with the decrease
7 of methanol content in the reaction medium. The yield of levulinic acid decreased

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8 with the decrease of methanol content, which might be induced by the conversion of
9 levulinic acid into soluble polymer. UV-vis spectra can also illustrate the similar

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10 results (Fig. 2c). The results showed that methanol is thus crucial for suppression of
11 the polymerization reactions [37]. In addition to reaction medium, the effects of other

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12 reaction parameters such as reaction temperature and reaction time were further
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13 investigated, aiming to understand how methanol impacted the conversion of furfural
14 to levulinic acid/ester.
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16 3.3 The effect of reaction temperature

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17 The conversion of furfural and distribution of the main products were shown in
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18 Fig. 3a and 3b. At the temperature below 110°C, although furfural was converted to
19 some extent, the yield of methyl levulinate was very small. From furfural to methyl
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20 levulinate, there were several reaction intermediates including HDMF, DOF, DMMF,
21 MMF and HMF formed, as shown in Fig. 3d. DOF was formed from the acetalization
of furfural with methanol. The etherification product of HMF (MMF) was formed
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23 from the electrophilic substitution reaction between furfural and DMM. MMF could
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24 hydrolyze to HMF or be converted to DMMF via acetalization reaction. DMMF was

25 also formed by the electrophilic substitution between DOF and DMM. HMF including
26 its ethers or acetals was further converted to levulinic acid/ester via acid catalysis. The
27 reaction equilibrium of levulinic acid and methyl levulinate was regulated by the
28 water content in the reaction medium. The reaction scheme was shown in Scheme 1.
29 Higher reaction temperature promoted the conversion of the reaction

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1 intermediates into levulinic acid/ester, as shown in Fig. 3b and 3c. Nevertheless,

2 higher reaction temperature promoted the etherification between the methanol
3 molecules, forming more water in the reaction medium, which favored the formation
4 of levulinic acid from methyl levulinate (Fig. 3c). More importantly, higher reaction
5 temperature promoted the polymerization reactions, as shown in Fig. S4a. With the

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6 reaction temperature above 130°C, the conversion of the soluble polymer to insoluble
7 polymers proceeded quicker. With the prolonged reaction time and the increase of

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8 temperature, the soluble polymer was further converted into insoluble polymer. The
9 UV-vis spectra (Fig. S4b) showed that the absorbance of the soluble polymer

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10 experienced a maximum and then decreased at a prolonged reaction time, indicating
11 their transformation into the coke. The yields of coke increased monotonously with

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12 the increasing temperature (Fig. 3e). In addition, even at 190°C, the maximum
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13 temperature investigated, the conversion of furfural did not reach 70%, and the
14 reaction intermediates were not completely converted. More acid catalyst might be
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15 needed to be loaded to accelerate the conversion of furfural. Thus, further experiments

16 with a higher loading of the acid catalysts were subsequently conducted.
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18 3.4 Effects of catalyst loading

19 The availability of acidic sites significantly affected the conversion of furfural.
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20 Higher loading of the acid catalyst accelerated the conversion of furfural (Fig. 4a),
21 which, however, also led to the decreased formation of methyl levulinate (Fig. 4b) via
the consumption of methyl levulinate through other reactions. The higher loading of
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23 the acids enhanced the etherification of methanol to form more water (Fig. S5), which
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24 would shift the reaction equilibrium between methyl levulinate and levulinic acid to
25 the acid side. This is because the levulinic acid could be formed from the hydrolysis
26 of methyl levulinate. Nevertheless, the formation of levulinic acid at the high acid
27 loading also decreased versus the prolonged reaction time, especially in the
28 experiments with higher acid loadings (Fig. 4c). Meanwhile, the yields of coke
29 increased monotonously with the increase of catalyst loading (Fig. 4d), indicating that

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1 the further polymerization of levulinic acid or methyl levulinate contributed to the

2 production of the insoluble polymer.
3 The formation of the soluble polymer was also confirmed with the
4 UV-fluorescence spectra (Fig. S6a) and the UV-vis spectra (Fig. S6b). Even with the
5 low loading of the acid catalyst, the soluble polymer with the conjugated π-bonds

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6 structures was formed [47]. The further increase of catalyst loading led to the decrease
7 of the abundance of the soluble polymer but an increase for the formation of insoluble

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8 polymer (Fig. 4d), indicating the transformation of the soluble polymer into the
9 insoluble polymer (coke). The characterizations with FT-IR showed that abundant

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10 methyl, ether bond, ketone group and carbon-carbon double bonds were present in the
11 soluble polymer (Fig. S7) [48]. The further conversion of levulinic acid/ester versus

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12 the prolonged reaction time with the high loading of acid catalyst clearly indicated
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13 that levulinic acid or methyl levulinate was also the intermediate products. In water,
14 levulinic acid was generally stable as water did not react with levulinic acid [47, 49].
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15 The reaction between dimethoxymethane and levulinic acid and methyl levulinate
16 were further investigated.
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18 3.5 Polymerization of levulinic acid/ester

19 The results in Fig. 5a showed that levulinic acid and methyl levulinate were not
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20 stable in dimethoxymethane. Both were further converted. The higher conversion of

21 levulinic acid at the initial stage of the experiment was due to the esterification
reaction of levulinic acid with methanol. The UV-florescence spectra (Fig. 5b and 5c)
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23 of the liquid products showed that the intermediate products contain three to five
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24 conjugated π-bonds, which was also confirmed with the UV-vis spectra (Fig. 5d and
25 5e). In either levulinic acid or methyl levulinate molecule, there were no conjugated
26 π-bonds. The aldol condensation reaction between DMM and methyl levulinate or
27 levulinic acid were verified via identification of the typical products like methyl
28 3-methylene-4-oxopentanoate (MMO) and methyl 4-ketohex-5-enoate (MKE), which,
29 shown in Scheme 2, led to the formation of the conjugated π-bonds. The abundance of

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1 MMO and MKE versus reaction time was shown in Fig. S8. The production of the
2 soluble polymer further led to the formation of the coke, as shown in Fig. 5f. It has
3 been reported that under the acidic conditions furfural was prone to polymerize
4 [47,50], while during the conversion of furfural to levulinic acid/ester, the
5 polymerization of levulinic acid/ester also need to be taken into consideration. From

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6 the characterization of the liquid products, it was known that aldol condensation
7 reaction played a role in the polymerization reactions. To further understand the

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8 mechanism for the polymerization during the conversion of furfural to levulinic
9 acid/ester, the coke formed was further characterized.

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10

11 3.6 Characterizations of the insoluble polymer (coke)

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12 3.6.1 Elemental analysis
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13 Table 3 showed the elemental composition of the coke produced in the typical
14 experiments. Comparing with that in the blank catalyst, after the experiments for the
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15 conversion of furfural, the carbon content for all the spent catalysts increased. The
16 molar ratio of C/H also increased remarkably, indicating that the coke formed was
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17 more aromatic. The ratio of DMM/methanol did not significantly affect the elemental
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18 composition of coke, but the coke formed with methanol as the sole solvent did have a
19 lower content of carbon, hydrogen while a correspondingly higher content of oxygen,
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20 indicating that DMM was involved in the polymerization reactions and changed the
21 coke structures.
Reaction medium affected the composition of coke. The coke formed in
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22

23 DMM/co-solvent had distinct carbon or hydrogen content as well as the different C/H
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24 ratio, which was related to the different involvement of the solvent in the
25 polymerization reactions. Water promoted the polymerization reactions, while acetone
26 and toluene reacted with DMM, and the reaction intermediates probably further
27 condensed into the coke. Acetone had a higher hydrogen content and the
28 corresponding coke, and it also had a higher hydrogen content. The opposite case was
29 that of toluene. The elemental composition of the coke also related to the reactants.

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1 Levulinic acid and methyl levulinate have a higher hydrogen content, oxygen content
2 and lower carbon content than furfural. Correspondingly, the coke from levulinic acid
3 or methyl levulinate had a higher hydrogen and oxygen content (Entry 10 and 11,
4 Table 3). The elemental features of the reactants were clearly transferred into the coke.
5 The coke species have different elemental composition, which also might have

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6 different structures and functionalities. This was further investigated.
7

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8 3.6.2 TG-MS characterization of the coke
9 The TG-MS characterizations of the spent catalysts were shown in Fig. 6. The

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10 D008 catalyst was made from polystyrene, which was not thermally stable and the
11 degradation of the catalyst initiated at ca. 365°C. The weight loss was more

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12 significant for the fresh catalyst than the spent catalyst. The polymer deposited into
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13 the catalyst clearly had a different structure with a relatively higher stability. The
14 gaseous products released during the TG characterization were also measured with an
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15 in-situ MS, as shown in Fig. 6b. Comparing to the fresh catalyst and spent catalyst,
16 the MS signal intensity for CO and CO2 fragment was the most significant. CO was
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17 the main gaseous product of fresh catalyst, and CO2 was the main gaseous product of
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18 polymer, which was probably come from the decarboxylation reactions at the elevated
19 temperature. The results suggested that the polymer probably contains the carboxylic
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20 groups. In addition, at the elevated temperature, there were CH4 released, indicating
21 the presence of methyl group in the polymer formed. Further to this, there was also a
small amount of H2 released (Fig. 6b), indicating the occurrence of the
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22

23 dehydrogenation reactions. The formation of CH4 and H2 during the thermal treatment
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24 showed that there existed aliphatic structures in the polymer formed [51].
25

26 3.6.3 FT-IR analysis of the coke

27 The spent catalyst was further characterized by FT-IR and the results were shown
28 in Fig. 7. The fresh catalyst mainly showed the absorption of the C-H bond and the
29 C=C bond in the aromatic ring structure of the polystyrene (Fig. 7a) [52–54]. The

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1 spent catalyst after catalyzing the conversion of furfural at 130°C showed the
2 absorption of the C=O and the aliphatic C-H functionalities [55]. For spent catalyst
3 used at 190°C, the ratio of the intensity for C=O/C=C increased significantly,
4 indicating the formation of more C=O on surface of the catalyst. During the TG-MS
5 characterization, the release of significant amount of CO2 was observed, which can be

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6 contributed to the presence of the carboxylic group in the polymer. In addition, the
7 C-O stretching functionalities became very significant, indicating the polymer formed

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8 was more aliphatic than the catalyst.
9 Fig. 7b showed the IR spectra of the polymer formed in methanol alone and in

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10 DMM alone and in the DMM/methanol. The ratio of the intensity of C=O to C=C was
11 1.2 for the polymer formed in methanol alone, which was much lower than that

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12 formed in DMM alone (1.8). Methanol does not have a C=O functional group. DMM
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13 is the acetal of formaldehyde, which clearly cross-polymerized with the reaction
14 intermediates and the C=O was maintained in the polymer. In the conversion of
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15 furfural in DMM/co-solvent, the co-solvent like that of acetone also involve in the
16 polymerization reactions, as evidenced by the strong absorption of the C=O
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17 functionality (Fig. 7c). The polymer formed from the conversion of levulinic
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18 acid/ester was generally similar to that in conversion of furfural. However, -C-O-

19 stretch and the absorption of aliphatic ketone was more significant (Fig. 7d),
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20 indicating that the polymer formed from the cross-polymerization of levulinic

21 acid/ester and DMM was more aliphatic than that of furfural. Levulinic acid/ester has
a more aliphatic structure than furfural, which subsequently affected the structure of
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22

23 the polymer formed.

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24

25 3.6.4 XRD characterization

26 Internal crystal structure of the fresh and spent catalysts was characterized by
27 XRD (Fig. 8), and the catalyst shown two diffraction peaks, which was the (002) peak
28 (2θ = 10−30º) and the (100) peak (2θ = 35−45º). The (002) peak and the (100) peak
29 indicates the formation of aromatic carbon sheets [56]. The fresh catalyst had no

16
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1 directional graphite structure. The XRD patterns indicated that the coke was
2 composed of aromatic carbon sheets, and the graphite structure was formed.
3 With the increase of the reaction temperature from 130 to 190°C, the (002) peak
4 for the spent catalyst moved slightly towards low degree, and its intensity increased
5 remarkably (Fig. 8a). This result indicated that the structure of aromatic carbon sheets

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6 tended to be denser and the graphitization was more remarkable. Fig. 8b showed that
7 the peak position for the polymer formed in methanol alone and in DMM alone were

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8 different, indicating the distinct structure of the polymer, which originated the
9 involvement of DMM in the polymerization reactions. DMM was possibly

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10 contributed to the formation of more oxygen-containing functional group, which
11 might increase the orderliness of the polymer and advance the graphitization. The

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12 co-solvent in the reaction medium also significantly affected the orderliness of the
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13 polymer, as evidenced by the increased intensity of the (002) peak and the (100) peak
14 (Fig. 8c). In addition to DMM, both acetone and toluene were involved in the
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15 polymerization reactions in the conversion of furfural. Fig. 8d showed the comparison

16 of the diffraction of the polymer formed in the conversion of furfural and in the
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17 conversion of levulinic acid/ester. The location of the (002) peak was slightly different
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18 and the orderliness of the polymer formed from the conversion of furfural was higher
19 than that of levulinic acid or methyl levulinate. The structure of the coke formed from
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20 the conversion of furfural or levulinic acid/ester were clearly different.

21
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22 3.6.5 DRIFTS study

23 The spent catalyst after the acid-catalyzed conversion of furfural was
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24 characterized by the DRIFTS, aiming to understand the change of the surface

25 functionalities versus temperature. The result was shown in Fig. 9a and 9b. The peak
26 between 2300 and 2360 cm-1 was due to the formation of CO2. As shown in TG-MS
27 (Fig. 6b), the CO2 began to be produced at 300−400°C, which was consistent with the
28 results of the DRIFTS, and the carbon-carbon triple bond was formed by the further
29 dehydrogenation. The spectra contained the characteristic absorption of carbonyl

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1 group (1817and 1756 cm-1) [57], carbon-carton double bonds (1648and 1573 cm-1)
2 [58], -C-O- bonds (1275 to 1142 cm-1), carboxyl group (955 to 915 cm-1) and Ar-H
3 bonds (878 to 742 cm-1) [59], which were the main functional groups of the polymer.
4 With the increase of the temperature above 500°C, the C=O functionalities,
5 carbon-carbon double bonds and the Ar-H bonds became more remarkable. Clearly,

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6 aromatization of the polymer took place at this stage. In addition, the absorption of
7 CO2 peak was also become significant, which originated from the CO2 released from

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8 the decarboxylation of the carboxylic group, as also evidenced in the TG-MS
9 characterization (Fig. 6b). Furthermore, the absorption of the -C-O- bonds and -CH3

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10 was still remarkable even at 800°C, indicating that the aliphatic structure in the spent
11 catalyst or in the coke were very stable.

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12
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13

14 4. Conclusions
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15 In summary, with DMM as an electrophile, furfural could be converted to

16 levulinic acid/ester with the formation of HMF or the ether/acetal of HMF as the
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17 reaction intermediates. This is a new reaction route for the direct conversion of
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18 furfural to levulinic acid and levulinic esters via only catalysis

19 dimethoxymethane/methanol without the separation of the reaction intermediates or
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20 catalysts, so that this process was more economically viable. The polymerization of
21 furfural and the cross-polymerization of DMM with levulinic acid and methyl
levulinate were the main reason for the decreased production of levulinic acid/ester.
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22

23 Using methanol as the co-solvent could suppress the polymerization reactions, but
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24 only to a limited extent. This is because that the polymerization reactions did not
25 eliminate the C=O functionalities. The polymerization via aldol condensation
26 reactions could continue to proceed to form the soluble polymer as the intermediates
27 and the insoluble polymer as the final products.
28 The use of other co-solvents also could not effectively suppress the
29 polymerization while could interfere with the transformation of furfural to HMF via

18
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1 the electrophilic substitution reactions. The characterizations showed that the polymer
2 produced from the conversion of furfural in DMM/methanol had different structure
3 with that produced from levulinic acid or methyl levulinate. The polymer from
4 levulinic acid/ester was more aliphatic than that from furfural, while the polymer from
5 the conversion of furfural has a higher crystallinity, and it has carboxylic group,

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6 methyl group and the aliphatic structure in skeleton. The removal of these
7 functionalities accompanied with the aromatization of the polymer during the heating

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8 process.
9 Levulinic acid or methyl levulinate was the intermediate product in the

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10 conversion of furfural in DMM/co-solvent reaction medium, as they could continue
11 react or polymerize with DMM. The involvement of DMM in the polymerization

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12 reactions especially with levulinic acid/ester was the key reason for the diminished
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13 production of levulinic acid/ester. How to inhibit the reaction between DMM and
14 levulinic acid/ester is a key issue to be solved.
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15

16 Acknowledgements
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17 This work was supported by the National Natural Science Foundation of China
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18 (No. 51876080), the Strategic International Scientific and Technological Innovation

19 Cooperation Special Funds of National Key R&D Program of China (No.
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20 2016YFE0204000), the Program for Taishan Scholars of Shandong Province

21 Government, the Recruitment Program of Global Young Experts (Thousand Youth
Talents Plan), the Natural Science Fund of Shandong Province (ZR2017BB002) and
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22

23 the Key R&D Program of Shandong Province (2018GSF116014).

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24

25

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1 Table 1 Conversion of furfural to levulinic acid (LA) and levulinic ester (LE)a
Key parameters Yield (%)
Entry Conversion (%)
Reaction medium LE LA LE+LA Coke
1 DMM 91.4 14.2 1.4 15.6 103.2
2 Methanol 85.7 1.3 0.47 1.8 68.3
3 DMM/H2O 98.3 6.8 5.3 12.1 61.1
4 DMM/DMF 0.0 0.0 0.0 0.0 4.2

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5 DMM/acetone 28.4 2.5 0.5 3.0 116.4
6 DMM/DMSO 25.1 1.6 0.4 2.0 14.0
7 DMM/ethyl formate 46.7 7.3b 0.4 7.7 60.1
14.1b

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8 DMM/ethyl acetate 78.2 1.2 15.3 103.2
9 DMM/diethyl ether 82.5 25.7b 2.6 28.3 107.4
10 DMM/iso-eugenol 6.7 0.6 0.0 0.6 34.3

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11 DMM/THF 75.2 15.3 2.1 17.4 112.2
12 DMM/guaiacol 5.0 0.5 0.2 0.7 35.0
13 DMM/toluene 86.2 17.5 1.4 18.9 100.3

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14 DMM/ethanol 80.9 16.7 2.9 19.6 95.0
15 DMM/methanol 71.6 35.3 3.8 39.1 78.4
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a
2 Other reaction conditions: furfural loading = 6.9 wt. %; catalyst loaded = 4 g; T =
3 190°C; t = 60 min; solvent: 60 mL; P = autogenous vapour pressure. Volumetric ratio
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4 = DMM/co-solvent: 33.3/26.7. Stirring rate = 300 rpm.

b
5 The total yield of methyl levulinate and ethyl levulinate.
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1 Table 2 Conversion of furfural under different volumetric ratio of methanol and

2 DMMa

Key parameters Yield (%)

Entry Conversion (%)
Reaction medium LE LA LE+LA Coke
b
1 DMM/methanol (20/40) 68.6 26.6 2.6 29.2 70.2
2 DMM/methanol (30/30) 69.7 31.8 2.3 34.1 77.3

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3 DMM/methanol (33.3/26.7) 71.6 35.3 3.8 39.1 78.4
4 DMM/methanol (37.5/22.5) 80.8 33.2 4.2 37.4 82.0
5 DMM/methanol (42.9/17.1) 85.8 30.7 4.1 34.8 90.2

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6 DMM/methanol (50/10) 86.2 25.5 2.5 28.0 92.1
7 DMM/methanol (54.5/5.5) 89.0 20.4 1.8 22.2 94.3
a
3 Reaction conditions: furfural loading = 6.9 wt. %; catalyst loaded = 4 g; T = 190°C; t

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4 = 60 min; solvent: 60 mL; P = autogenous vapour pressure; stirring rate: 300 rpm.
b
5 The volumetric ratio of DMM/methanol.

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1 Table 3 The elemental analysis characterization of the catalyst after reaction
Element (%) Molar
Entry Reaction condition ratio of
C H S O C/Ha
Furfural: 6.4 wt. %; catalyst loading: 3.2 wt. %; 58.1 4.1 5.5 32.3 1.18
1
T = 130Ⅳ; DMM/methanol = (37.5/22.5)
Furfural: 6.4 wt. %; catalyst loading: 3.2 wt. %; 62.7 4.5 4.6 28.1 1.15
2

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T = 190Ⅳ; DMM/methanol = (37.5/22.5)
Furfural: 7.0 wt. %; catalyst loading: 7.0 wt. %; 62.1 4.4 3.9 29.6 1.18
3
T = 190Ⅳ; DMM/methanol = (20/40)

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Furfural: 6.9 wt. %; catalyst loading: 6.9 wt. %; 63.1 4.7 3.8 28.4 1.13
4
T = 190Ⅳ; DMM/methanol = (33.3/26.7)
Furfural: 6.7 wt. %; catalyst loading: 6.7 wt. %; 63.2 4.9 3.3 28.7 1.08

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5
T = 190Ⅳ; DMM
Furfural: 7.2 wt. %; catalyst loading: 7.2 wt. %; 60.1 3.8 4.5 31.6 1.32
6
T = 190Ⅳ; Methanol

U
Furfural: 6.3 wt. %; catalyst loading: 6.3 wt. %; 59.5 4.9 4.7 30.9 1.01
7
AN
T = 190Ⅳ; DMM/H2Ob
Furfural: 6.9 wt. %; catalyst loading: 6.9 wt. %; 66.6 5.4 4.0 24.0 1.02
8
T = 190Ⅳ; DMM/acetone
M

Furfural: 6.7 wt. %; catalyst loading: 6.7 wt. %; 65.8 3.4 4.3 26.4 1.59
9
T = 190Ⅳ; DMM/toluene
MLc: 6.9 wt. %; catalyst loading: 6.9 wt. %; T = 52.8 4.5 7.1 35.6 0.98
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10
190Ⅳ; DMM/methanol
LA: 6.9 wt. %; catalyst loading: 6.9 wt. %; T = 52.8 4.7 7.9 34.6 0.93
TE

11
190Ⅳ; DMM/methanol
12 Fresh D008 catalyst 40.3 4.6 10.4 44.7 0.73
EP

a
2 The molar ratio of C/H was keep at two decimal places.
b
3 As for the DMM/co-solvent without parameter, its volumetric ratio was 33.3/26.7.
C

c
4 Methyl levulinate (ML); Levulinic acid ( LA).
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PT
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1
2 Scheme 1. Conversion of furfural to methyl levulinate and levulinic acid in
3 DMM/methanol. HDMF: 5-(hydroxymethyl)-2-(dimethoxymethyl) furan; DMMF: 2-
4

U
(dimethoxymethyl)-5-(methoxy methyl) furan; DOF: 2-(dimethoxymethyl) furan (the
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5 acetal of furfural); MMF: 5-(methoxymethyl)-2-furancarboxadhyde.
M
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PT
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U SC
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1
M

2 Scheme 2. Conversion of methyl levulinate or levulinic acid in DMM/methanol. All

D

3 the products were detected by GC-MS. Methyl 3-methylene-4-oxopentanoate (MMO);

4 Methyl 4-ketohex-5-enoate (MKE); 3-methylene-4-oxopentanoic acid (MOA).
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(a)
60
Furfural in DMM
326 nm 0 min
311 nm 20 min
40 406 nm 40 min

Intensity (a. u.)

60 min
90 min

20

PT
0
250 300 350 400 450 500 550 600

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(b) Wavelength (nm)
120
Furfural in
305 nm DMM
Methanol

SC
90
Intensity (a. u.)

60 326 nm

U
406 nm
30
AN
0
250 300 350 400 450 500 550 600
Wavelength (nm)
(c)
M

100
311 nm
Furfural in
326 nm
DMM/H2O
80
DMM/ethanol
D

DMM/acetone
Intensity (a. u.)

60 DMM/ethyl formate
DMM/ethyl acetate
TE

40 DMM/methanol
406 nm
20
EP

0
250 300 350 400 450 500 550 600
Wavelength (nm)
1
C

2 Fig. 1. Fluorescence synchronous spectra for the soluble polymers formed from the
AC

3 acid-catalyzed conversion of furfural (a) in DMM versus the reaction time; (b) in
4 DMM and in methanol; (c) in DMM/co-solvents.

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(a)
60
Volumetric ratio of DMM/methanol
309 nm 20.0/40.0
30.0/30.0
33.3/26.7
40 406 nm 37.5/22.5

Intensity (a. u.)

42.9/17.1
50.0/10.0
54.5/5.5
20

PT
0

250 300 350 400 450 500 550 600

(b) Wavelength (nm)

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3 C-O
-COOH
Absorbance (a. u.)

SC
2 C=O C=C

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AN
2000 1750 1500 1250 1000 750 500
Wavenumber (cm-1)
(c)
M
Absorbance (a. u.)

0.92
0.69
0.46
D

0.23
0.00
200 250 300 350
TE

1 Wavelength (nm)

2 Fig. 2. Characterizations of for the soluble polymers from the acid-catalyzed

3 conversion of furfural at the different volumetric ratio of DMM/methanol. (a)
EP

4 Fluorescence synchronous spectrum; (b) FT-IR spectrum; (c) Ultraviolet spectrum.

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(a) (d)
70
90°C 110°C DMMF
60 130°C 150°C

Conversion of furfural (%)

A bundance (a.u.)
170°C 190°C O
O
50 O
O

40
HDMF
30
O
O
20 O
HO
10

PT
MMF

A bundance (a.u.)
0
0 20 40 60 80 O
(b) Reaction time (min) O
25
O
Yield of methyl levulinate (%)

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20 DOF
O
O
15
O
10

SC
HMF

Yield (% )
0.51
5 O
0.34 O
0.17
0 HO
0.00
90 120 150 180

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0 20 40 60 80
(c) Reaction time (min) (e) Temperature (°C)
2.0
50 Coke formed in DMM/methanol
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Yield of levulinic acid (%)

1.5
40 37.9%
Yield of coke (%)

32.0%
1.0 30 27.3%
21.9%
M

20
0.5
12.7%
10 7.2%
0.0
0
D

0 20 40 60 80 90 110 130 150 170 190

Reaction time (min) Reaction temperature (°C)
1
TE

2 Fig. 3. Distribution of the products in conversion of furfural in DMM/methanol at the

3 different temperatures. (a) Furfural conversion; (b) Methyl levulinate yield; (c)
EP

4 Levulinic acid yield; (d) Abundance of the reaction intermediates and HMF yield; (e)
5 Coke yield. Reaction conditions: furfural loading: 6.4 wt. %; catalyst loading: 3.3
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6 wt. %; volumetric ratio: DMM/methanol = 40/24.

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(a) (b)
100 Furfural in DMM/methanol

Yield of methyl levulinate (%)

Conversion of furfural (%)
30
80

20
60

Catalyst loading
40 10
1.7 wt. %
3.3 wt. %

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6.4 wt. %
20 9.5 wt. %
0
0 20 40 60 80 0 20 40 60 80
(c) Reaction time (min) (d) Reaction time (min)
150

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4
Coke formed in DMM/methanol
Yield of levulinic acid (%)

120
3 99.3%

Yield of coke (%)

SC
90
71.1%
2
60
38.2%
1
30

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18.1%

0 0
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0 20 40 60 80 1.7 3.3 6.4 9.5
Reaction time (min) Catalyst loading (wt. %)
1
2 Fig. 4. Conversion of furfural to levulinic acid/ester versus catalyst loadings. Reaction
M

3 conditions: furfural loaded = 4 g; T = 190°C; volumetric ratio: DMM/methanol =

4 40/24. Catalyst loading = 1.7 wt. %, 3.3 wt. %, 6.4 wt. % and 9.5 wt. %.
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(a) (b)
100
Methyl levulinate in DMM/methanol
200
302 nm
80
Methyl levulinate 20 min
311 nm 40 min
Levulinic acid 150
Conversion (%)

Intensity (a.u.)
60 60 min
90 min
100
40
404 nm
357 nm
50
20

PT
0 0
0 20 40 60 80 250 300 350 400 450 500 550 600
(c) Reaction time (min) (d) Wavelength (nm)
Levulinic acid in DMM/methanol Methyl levulinate in DMM/methanol

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80 1.6
404 nm
302 nm

Absorbance (a. u.)

60 1.2 214 nm
Intensity (a. u.)

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40 0.8
357 nm

20 0.4

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250 300 350 400 450 500 550 600 200 250 300 350 400
(e) Wavelength (nm) (f) Wavelength (nm)
Levulinic acid in DMM/methanol 25 Coke formed in DMM/methanol
1.5

214 nm 19.3%
M

20
Absorbance (a. u.)

Yield of coke (%)

1.0 14.1%
15
D

10
0.5
5
TE

0.0 0
200 250 300 350 400 Methyl levuliante Levulinic acid
Wavelength (nm) Reactant
1
EP

2 Fig. 5. Conversion of methyl levulinate/levulinic acid and characterizations of the

3 soluble polymers versus the reaction time. (a) the conversion in DMM/methanol; (b)
C

4 and (c) fluorescence synchronous spectrums; (d) and (e) ultraviolet spectrums; (f) the
AC

5 yield of coke. Reaction conditions: methyl levulinate or levulinic acid loading = 6.9
6 wt. %; catalyst loading = 6.9 wt. %; volumetric ratio: DMM/methanol = 33.3/26.7.

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(a) (b) 40
0.5
Fresh catalyst in nitrogen Catalyst after reaction in nitrogen
100 100
0.4 30

MS signal (a. u.)

TG
Weight loss (%)

Weight loss / %
MS signal (a. u.)
80 CH4
0.3 80
CO 20
CO2
60 0.2
H2 Weight loss: 35 %
60 10
Weight loss:54 %
0.1

PT
40

40 0
0.0
200 400 600 800 200 400 600 800
Temperature (°C) Temperature (°C)
1

RI
2 Fig. 6. TG-MS curves for (a) the fresh catalyst and (b) the spent catalyst after the
3 conversion of furfural in DMM/methanol (Reaction conditions: furfural = 6.9 wt. %;

SC
4 catalyst loading = 6.9 wt. %; T = 190°C; volumetric ratio: DMM/methanol =
5 33.3/26.7).
6

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(a) (b)
Fresh catalyst -CH3 Methanol
C=O C-O -CH3
130°C DMM C-O
0.3 190°C DMM : methanol (20.0 : 40.0)
C=C 0.4 DMM : methanol (33.3 : 26.7)
Absorbance (a. u.)

Absorbance (a. u.)

C-H
-CH -COOH
-COOH
0.2 O-H stretch C=C Ar-H
O-H stretch Ar-H
C=O
0.2

0.1

PT
0.0 0.0
4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)
(c) (d)

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DMM/co-solvents Conversion of
DMM: H2O Furfural
C-O
DMM: acetone =O
C= -CH3 0.4 Methyl levulinate
0.6 DMM: toluene Levulinic acid -C-O
Absorbance (a. u.)

Absorbance (a. u.)

DMM: methanol

SC
C-H C=O
0.3
-COOH -CH3
0.4
O-H stretch =C
C=
-COOH
Ar-H 0.2 C=C Ar-H

0.2

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0.1

0.0 0.0
AN
4000 3500 3000 2500 2000 1500 1000 500 1750 1500 1250 1000 750 500
-1 -1
Wavenumber (cm ) Wavenumber (cm )
1
2 Fig. 7. FT-IR curves of the insoluble polymer formed in the acid-catalyzed conversion
M

3 of furfural (a) in DMM/methanol at different reaction temperature; (b) in

4 DMM/methanol with different volumetric ratio; (c) in DMM/co-solvents. (d) FT-IR
D

5 characterization of the insoluble polymer formed from the acid-catalyzed conversion

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6 of furfural/methyl levulinate/levulinic acid.

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(a) (b)
(002) Fresh catalyst 1.6x10
5 (002) Fresh catalyst
1.6x105 130°°C In DMM
190°°C In Methanol
5
1.2x10
1.2x105
Intensity (a. u.)

Intensity (a.u.)
(100)
8.0x104 (100) 8.0x104

4.0x104 4.0x104

PT
0.0
20 40 60 80 20 40 60 80

(c) 2 Theta/degree (d) 2 Theta/degree

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(002) Fresh catalyst 1.6x105 Fresh catalyst
1.6x105 DMM/co-solvents: (002)
Reactant:
DMM/H2O Furfural
DMM/acetone 1.2x105 Levulinic acid
1.2x105

Intensity (a. u.)

Intensity (a. u.)

SC
DMM/toluene Methyl levulinate
DMM/methanol
8.0x104
(100) 8.0x104 (100)

4.0x104 4.0x104

0.0

U 0.0
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20 40 60 80 20 40 60 80
2 Theta/degree 2 Theta/degree
1
2 Fig. 8. The XRD patterns of the spent catalyst after different reaction conditions: (a)
M

3 different reaction temperatures; (b) different reaction solvent; (c) different

4 DMM/co-solvents; (d) different reactants.
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(a) CO2 C ≡ C C=O

C-O stretch
-COOH
Ar-H (b)
-CH
C-H stretch C=C 3
2.0
100°C
200°C
1.5 300°C
400°C
Absorbance (a. u.)

500°C
1.0 600°C
700°C
800°C
0.5

0.0

PT
-0.5
4000 3500 3000 2500 2000 1500 1000

Wavenumber (cm-1)

RI
2 Fig. 9. The DRIFTS curves of the spent catalyst. The catalyst was obtained after the
3 conversion of furfural in DMM/methanol. Reaction conditions: furfural: 6.9 wt. %;

SC
4 catalyst loading: 6.9 wt. %, T = 190°C; volumetric ratio: DMM/methanol = 33.3/26.7.

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M
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