Accepted Manuscript

Short Communication

One-pot furfural production using choline chloride-dicarboxylic acid based deep

eutectic solvents under mild conditions

Cornelius Basil Tien Loong Lee, Ta Yeong Wu, Chow Hung Ting, Ju Kheng
Tan, Lee Fong Siow, Chin Kui Cheng, Jamaliah Md. Jahim, Abdul Wahab
Mohammad

PII: S0960-8524(18)31693-6
DOI: https://doi.org/10.1016/j.biortech.2018.12.034
Reference: BITE 20791

To appear in: Bioresource Technology

Received Date: 11 October 2018

Revised Date: 9 December 2018
Accepted Date: 10 December 2018

Please cite this article as: Lee, C.B.T., Wu, T.Y., Ting, C.H., Tan, J.K., Siow, L.F., Cheng, C.K., Jahim, J.M.,
Mohammad, A.W., One-pot furfural production using choline chloride-dicarboxylic acid based deep eutectic
solvents under mild conditions, Bioresource Technology (2018), doi: https://doi.org/10.1016/j.biortech.2018.12.034

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 1

One-pot furfural production using choline chloride-dicarboxylic acid based deep

eutectic solvents under mild conditions

Cornelius Basil Tien Loong Leea, Ta Yeong Wua,b,*, Chow Hung Tinga, Ju Kheng Tana,

Lee Fong Siowc, Chin Kui Chengd, Jamaliah Md. Jahime, Abdul Wahab Mohammade

a
Chemical Engineering Discipline, School of Engineering, Monash University, Jalan

Lagoon Selatan, 47500 Bandar Sunway, Selangor Darul Ehsan, Malaysia.

b
Monash-Industry Palm Oil Education and Research Platform (MIPO), School of

Engineering, Monash University, Jalan Lagoon Selatan, 47500 Bandar Sunway, Selangor

Darul Ehsan, Malaysia.

c
School of Science, Monash University, Jalan Lagoon Selatan, 47500 Bandar Sunway,

Selangor Darul Ehsan, Malaysia.

d
Faculty of Chemical and Natural Resources Engineering, Lebuhraya Tun Razak,

Universiti Malaysia Pahang, 26300 Gambang Kuantan, Pahang Darul Makmur, Malaysia.
e
Department of Chemical and Process Engineering, Faculty of Engineering and Built

Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan,

Malaysia.

Corresponding Author’s Information

*(T. Y. Wu) Tel: +60 3 55146258. Fax: +60 3 55146207.

Email: [email protected]; [email protected]

 2

Abstract

The performances of various anhydrous and aqueous choline chloride-dicarboxylic acid

based deep eutectic solvents (DESs) were evaluated for furfural production from oil palm

fronds without any additional catalyst. The effects of different carbon chain length

dicarboxylic acids and water content in each DES on furfural production were investigated.

Oil palm fronds, DES and water (0-5 ml) were mixed and reacted in an oil bath (60-300

min). Reacted oil palm fronds had the potential to be reused as cellulose-rich-valuable by-

products. At 100°C, aqueous choline chloride-oxalic acid (16.4 wt% H2O) produced the

highest furfural yield of 26.34% and cellulose composition up to 72.79% in the reacted oil

palm fronds. Despite operating at optimum reaction duration, aqueous choline chloride-

malonic acid and aqueous choline chloride-succinic acid performed poorly with furfural

yield of less than 1%.

Keywords: Biorefinery; Oil palm fronds; Oxalic acid; Malonic acid; Succinic acid
 3

1. Introduction

Increasing energy demand due to the increasing global population has led society to

venture towards sustainable development. A promising approach to produce energy,

platform chemicals, and materials is by utilizing biomass in biorefineries (Tan et al., 2016).

Typical compositional percentages of 30-40, 30-35, and 11-25% of cellulose,

hemicellulose, and lignin, respectively are observed in most lignocellulosic biomass. The

annual production of lignocellulosic biomass is estimated at 200 billion tonnes and is

generally in the form of energy crop, agricultural and forestry waste (Loow and Wu, 2018).

Furfural is a bio-based chemical from the furan family and has garnered interest as a

sustainable chemical due to its versatility. Furfural can be utilized in the production of

solvents, agrochemicals, polymers, pharmaceuticals, and flavouring agents (Peleteiro et al.,

2016). The annual global production of furfural is estimated to be around 700 thousand

tonnes (Cai et al., 2014). Currently, industrial furfural production process is based on a

H2SO4-catalyzed reaction at temperatures of up to 240°C, producing around 50-55% of the

theoretical yield (Cai et al., 2014). However, the current process suffers from equipment

corrosion issues, low furfural yield, and is highly energy intensive (Zhang et al., 2014).

The emergence of ionic liquids paved a promising path for catalytic reactions of

biomass due to its good dissolving capacity, chemical and thermal stability, and ability to

enhance catalytic activities (Peleteiro et al., 2016). Recently, deep eutectic solvents (DESs)

attract interest as another viable solvent due to their similar physiochemical properties to

ionic liquids (Loow et al., 2017a). DESs are clear homogenous solution commonly

prepared by heating a solid mixture of hydrogen bond acceptor (HBA) and hydrogen bond

donor (HBD) at moderate temperatures (<100°C) under agitation (Loow et al., 2017a). DES
 4

holds several advantages over ionic liquids such as lower cost and toxicity, ease of

synthesis and more biodegradable. DES can be classified into various types. Until now,

Type III DESs receive the greatest attention among the other type of DESs. Type III DES

typically has a HBD and an organic salt as the HBA (Loow et al., 2017a).

In Malaysia, the palm oil industry produces a huge amount of oil palm biomass. Oil

palm fronds accounts for 70% of the residue produced and is estimated to have a global

production of 250 million tonnes (Tan et al., 2016). The current oil palm fronds disposal

method, on-site degradation after pruning to improve soil quality and water retention,

returns little value to the industry (Loow and Wu, 2018). The objective of this study was to

determine the most suitable Type III dicarboxylic acid based DESs (i.e. ChCl-oxalic acid,

ChCl-malonic acid, ChCl-succinic acid) and optimum reaction conditions (reaction

duration and water content in the DES) to produce furfural from oil palm fronds without

any additional catalyst via one-pot method. Oil palm fronds, DES and water were

transferred into a Schott bottle and reacted in an oil bath. Analysis of reacted oil palm

fronds were performed to identify further processing potential.

2. Material and methods

2.1. Chemicals and preparation of lignocellulosic biomass

Choline chloride (ChCl), sulfuric acid, oxalic acid, malonic acid, succinic acid, D-

(+)-glucose, D-(+)-xylose, and L-(+)-arabinose, furfural and acetonitrile were purchased

from Sigma-Aldrich and were of analytical grade. Fresh oil palm fronds were acquired

from an oil palm plantation owned by the National University of Malaysia (UKM). The
 5

leaves were separated from the petioles. The petioles were pressed using a sugarcane press

machine to remove liquid and left to dry for two days. The dried petioles were cut,

grounded and subjected to mechanical sieving with sieve tray size of 0.5 mm. The sieved

petioles were dried at 55°C in an oven for 48 h. Dried oil palm fronds petioles with

dimensions of less than 0.5 mm were termed as OPF and used in this study.

2.2. Raw and reacted OPF compositional analysis

Acid hydrolysis method was employed to determine cellulose, hemicellulose and

lignin compositions in the OPF. The remaining solid OPF and hydrolyzate were separated

by vacuum filtration. The filtrate was centrifuged at 13500 rpm and 10 min (Labogene

Scanspeed Mini). The supernatant was filtered through a 0.22 µm syringe filter prior to

further analysis. Lignin content was determined via dry weight difference (Loow et al.,

2017b). Water extractives were determined by performing a Soxhlet extraction under reflux

with 200 ml of distilled water for 8 h. Ethanol extractives were determined using the same

reflux system with 200 ml of 95% ethanol for 24 h (Loow et al., 2018). Ash content

analysis was done by subjecting OPF, in porcelain crucibles, to a temperature of 575°C for

24 h in a furnace (Carbolite CWF 11/13). The crucibles were left to cool down in a

desiccator for an hour prior to weighing the ash content. The compositions of raw OPF (dry

weight basis) used in this study were: glucan (45.00±0.45%), xylan (19.79±0.63%),

arabinan (0.77±0.44%), lignin (19.53±0.08%), ash (0.40±0.21%), water extractives

(11.33±0.71%) and ethanol extractives (3.77±0.49%).

 6

2.3. Production of furfural from OPF via DES systems

The DESs used in this study were ChCl-oxalic acid, ChCl-malonic acid and ChCl-

succinic acid, each prepared in 1:1 molar ratios (Abbott et al., 2004). The respective solid

mixtures were heated under mechanical agitation on a magnetic stirrer (Heidolph MR Hei-

Tec) at 90°C and 120 rpm for an hour until a homogeneous colourless solution was formed.

Firstly, 0.80 g of raw OPF and 88.00 mmol DES were transferred into a 50 ml

Schott bottle. The reaction mixture was heated under agitation in an oil bath at 100°C and

120 rpm for the assigned duration of 60-300 min. Once the optimum reaction duration was

determined, optimum water content for furfural production was investigated. Similarly,

0.80 g of raw OPF and 88.00 mmol DES were transferred into a 50 ml Schott bottle. Water

was then added into each DES systems in the range of 1-5 ml. Each DES system would be

reacted in an oil bath at 100°C and 120 rpm, using the pre-determined optimum reaction

duration. After each reaction, the Schott bottle was quenched in an ice bath. The resulting

solution was centrifuged, and the supernatant was filtered through a 0.22 µm syringe filter

and diluted by a factor of 150 prior to analysis. The reacted OPF were washed using

distilled water, filtered and transferred to a petri dish to be dried in an oven at 60°C

overnight. Dried samples were then kept for further analysis. Triplicate sets of data were

obtained for each condition studied. A constant temperature of 100°C was employed in this

study due to the thermal instability of ChCl-malonic acid at higher temperature (Skulcova

et al., 2017).
 7

2.4. High Performance Liquid Chromatography (HPLC) Analysis

The concentrations of monomeric sugars and furfural were analyzed using an

Agilent series 1200 infinity HPLC system. Analysis of monomeric sugars was done using a

Refractive Index Detector and a Bio-Rad Aminex HPX-87H column. Analysis of furfural

was done with a MWD Detector at 280 nm and a ZORBAX Eclipse XDB-C18 column.

2.5. Statistical Analysis

Statistical analysis to determine significant difference between data sets was done

using IBM SPSS Statistics 24. One-way analysis of variance (ANOVA) using Tukey’s test

and a significance level of P < 0.05 were used to identify homogenous subsets of furfural

yields based on varying parameters.

3. Results and discussion

3.1. Effect of reaction duration on furfural yield

Furfural yield for all three anhydrous DES systems increased initially as reaction

duration increased (Table 1). The increase was due to the dissolution of hemicellulose to

xylan of OPF by the DES. The presence of protons, supplied by dicarboxylic acid, in the

DES broke down β-1,4 glycosidic linkages in xylan to form xylobiose and xylose (Enslow

and Bell, 2012). The dissolved xylose would then undergo dehydration to produce furfural

via a closed chain mechanism (Cai et al., 2014). Further increasing the reaction duration

beyond 135 and 120 min for ChCl-oxalic acid and ChCl-malonic acid, respectively caused

reduction in furfural yield (Table 1). As reaction duration increased, furfural concentration
 8

in the DES increased which led to parallel furfural loss reactions (Wang et al., 2017). It was

postulated that beyond the threshold furfural concentration, furfural loss occurred at a faster

rate than furfural production and led to reduced yield. The threshold concentrations for the

ChCl-oxalic acid and ChCl-malonic acid DES systems in this study were 1.234 and 0.043

g/L, respectively. Furfural yield for the ChCl-succinic acid DES system showed no

reduction and remained relatively constant between reaction durations of 240 and 300 min

(Table 1). Due to the ineffectiveness of ChCl-succinic acid for this reaction, the furfural

concentration in this DES system remained relatively low. The low furfural concentration

in ChCl-succinic acid meant that the threshold concentration was not achieved.

The effectiveness of DESs were in the order of ChCl-oxalic acid (9.74%) > ChCl-

malonic acid (0.36%) > ChCl-succinic acid (0.17%) (Table 1). These results suggested that

furfural yield was strongly affected by the acid strength of the system. As the pKa of

carboxylic acids in DES is approximately similar to their pKa in water (Abbott et al., 2018),

oxalic acid (pKa=1.23) produced the highest furfural yield, followed by malonic acid

(pKa=2.83) and succinic acid (pKa=4.16). The differences in effectiveness were attributed

to the different carbon chain lengths of oxalic acid (C2), malonic acid (C3) and succinic acid

(C4). Increased carbon chain length enhanced the electron donating effect of the alkyl

group. It was postulated that the enhanced electron donating effect reduced the strength of

the hydrogen bonds formed between the HBA and HBD, and the hydrogen donating ability

of the DES. The reduced hydrogen donating ability decreased the H+ ions concentration in

the system for hydrolysis and dehydration reactions. As the concentration of H+ ion is first

order in the rate-limiting step of xylan hydrolysis (Enslow and Bell, 2012), xylose recovery

by ChCl-oxalic acid was better than the other ChCl-dicarboxylic acids. The huge difference
 9

in furfural yield between ChCl-oxalic acid and ChCl-malonic acid was suspected to be due

to the thermal instability of ChCl-malonic acid. Skulcova et al. (2017) reported that ChCl-

malonic acid showed steady weight loss at temperatures below 120°C. Weight loss of

ChCl-malonic acid can be translated to reduced H+ ion concentration. Interactions between

DES and biomass depended on the strength and stability of the hydrogen bonding

interactions between the HBA and HBD (Zahrina et al., 2017). It was postulated that

succinic acid could not form strong and stable hydrogen bonds with ChCl. Hence, the

interaction between ChCl-succinic acid and OPF was adversely affected.

3.2. Effect of water content on furfural yield

An addition of 2 ml of water into ChCl-oxalic acid (16.4 wt% H2O) produced

improvement in furfural yields, from 9.74 to 26.34%, followed by the addition of 1 ml of

water into ChCl-malonic acid (8.5 wt% H2O), from 0.36 to 0.65% (Table 1). These

improvements were postulated to be due to the ability of water to aid in the saccharification

of hemicellulose and xylose recovery. The improvements could also be due to better mass

transfer, leading to a better penetration of DES into the lignocellulosic matrix (New et al.,

2018). Xylan contents of aqueous ChCl-oxalic acid (16.4 wt% H2O) and anhydrous ChCl-

oxalic acid reacted OPF were 5.23 and 15.49%, respectively. The lower xylan content in

the aqueous ChCl-oxalic acid reacted OPF translated to more effective xylose recovery.

Another possible explanation to the more effective xylose recovery is the delignification

ability of OPF by aqueous DES. By performing compositional analysis, lignin content in

raw OPF, anhydrous ChCl-oxalic acid reacted OPF, and aqueous ChCl-oxalic acid reacted

OPF were 19.53, 18.99, and 18.27%, respectively. The compositional analysis results
 10

indicated that aqueous DES had better delignification and hemicellulose extraction abilities.

Compositional analysis also showed that raw OPF, anhydrous ChCl-oxalic acid reacted

OPF, and aqueous ChCl-oxalic acid reacted OPF had glucan contents of 45.00%, 51.34%,

and 72.79%, respectively. The higher glucan content in aqueous ChCl-oxalic acid reacted

OPF was due to the more effective removal of hemicellulose and lignin which exposed

cellulose (Loow et al., 2017b).

However, it was observed that further water addition into each DES system caused a

decline in furfural yield (Table 1). The decline could be due to the nanostructure of DES

being disrupted at higher hydration levels (Hammond et al., 2017). The disruption

hampered DES catalytic effect and DES interaction with OPF. Wang et al. (2017) stated

that water, a polar protic solvent, enhanced side reactions which resulted in lower furfural

yield. Hence, based on the results obtained, an optimum amount of water enhanced furfural

yield by improving xylose recovery. In comparison to anhydrous DES, furfural yields were

enhanced by 170.4 and 80.6% for aqueous ChCl-oxalic acid (16.4 wt% H2O) and aqueous

ChCl-malonic acid (8.5 wt% H2O), respectively. However, excessive amount of water

(>19.7 wt% H2O for ChCl-oxalic acid, > 15.6 wt% H2O for ChCl-malonic acid) adversely

affected DES catalytic effect and enhanced side reactions. Jiang et al. (2018) reported

furfural yield of 16.9% using aqueous oxalic acid which was lower compared to the furfural

yield of 26.3% in this study. ChCl in the DES had the ability to increase proton reactivity

and availability by affecting the stability of protons (Chen et al., 2018), which enhanced

OPF hydrolysis and furfural production.

An addition of water showed no significant improvements in furfural yield for

ChCl-succinic acid (Table 1). To investigate the contradicting result obtained from ChCl-
 11

succinic acid, the effect of water content in each DES were studied. It was observed that

upon addition of excess water (> 63.7 wt% H2O), solid white precipitates were formed only

in ChCl-succinic acid. It was postulated that water molecules competed to form hydrogen

bonds with ChCl and could displace succinic acid, indicating low stability and strength of

hydrogen bonding interactions between ChCl and succinic acid. The instability of ChCl-

succinic acid led to possible disruption of its structure at low water content.

4. Conclusion

Aqueous ChCl-oxalic acid (16.4 wt% H2O) produced furfural yield of 26.34% at

100°C and 1 atm. DES with short carbon chain dicarboxylic acid produced higher furfural

yield due to the higher stability and hydrogen donating ability. Aqueous DES produced

higher furfural yield due to improved delignification and hemicellulose extraction.

Additionally, aqueous ChCl-oxalic acid reacted OPF had 72.79% cellulose composition,

indicating its potential to be reused to derive other high value products. Pre-treatment on

raw OPF prior to the reaction could enhance hemicellulose extraction and improve furfural

yield. The utilization of aqueous DES enabled furfural production at mild conditions.

Acknowledgements

The funding of this study is supported by Ministry of Higher Education under

Fundamental-Malaysia’s Research Star Award (FRGS-

MRSA/1/2018/WAB01/MUSM/02/1). Additionally, the authors would like to thank

Monash University Malaysia for providing C.B.T.L. Lee with a postgraduate scholarship.
 12

Appendix A. Supplementary data

Supplementary data associated with this article can be found in the online version.

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Table 1 Furfural yield from anhydrous and aqueous DES studied. All reactions were

performed at 100°C and 1 atm. Values annotated with different alphabets represents

different significance levels (one-way ANOVA, Tukey’s test; P < 0.05)

DES Water Content (ml) Duration (min) Furfural Yield (mol%)

Anhydrous
ChCl-oxalic acid 0.0 60 3.51 ± 1.36a
0.0 90 5.52 ± 1.21a,b
0.0 120 7.07 ± 0.54b
0.0 135 9.74 ± 0.35c
0.0 150 7.78 ± 0.49b,c
ChCl-malonic acid 0.0 60 0.22 ± 0.03A
0.0 120 0.36 ± 0.03B
0.0 180 0.30 ± 0.03A,B
0.0 240 0.27 ± 0.03A
0.0 300 0.22 ± 0.04A
ChCl-succinic acid 0.0 60 0.03 ± 0.01w*
0.0 120 0.08 ± 0.00x*
0.0 180 0.13 ± 0.01y*
0.0 240 0.17 ± 0.01z*
0.0 300 0.19 ± 0.01z*
Aqueous
ChCl-oxalic acid 0.0 135 9.74 ± 0.35a
1.0 135 22.30 ± 0.95b
1.5 135 23.25 ± 1.73b
2.0 135 26.34 ± 1.27c
2.5 135 18.06 ± 0.32d
3.0 135 13.33 ± 0.77e
ChCl-malonic acid 0.0 120 0.36 ± 0.03A,B
1.0 120 0.65 ± 0.11C
2.0 120 0.45 ± 0.03B
3.0 120 0.26 ± 0.04A,D
4.0 120 0.21 ± 0.02D
5.0 120 0.19 ± 0.03D
ChCl-succinic acid 0.0 240 0.17 ± 0.01w*,x*
1.0 240 0.18 ± 0.01w*
2.0 240 0.16 ± 0.02x*
3.0 240 0.12 ± 0.01y*
4.0 240 0.10 ± 0.01y*,z*
5.0 240 0.09 ± 0.01z*
 16

Highlights:

 Furfural production under mild conditions via ChCl-dicarboxylic acid based DES

 Components of the DES showed synergistic effects in improving furfural yield

 DES reaction produced cellulose-rich-valuable by-product

 Insights into the mechanism were gained based on FE-SEM, FTIR and XRD

analysis