Catalytic strategy for conversion of fructose to organic dyes, polymers, and liquid fuels

Article abstract of DOI:10.1039/d0gc01576h

We report a process to produce a versatile platform chemical from biomass-derived fructose for organic dye, polymer, and liquid fuel industries. An aldol-condensed chemical (HAH) is synthesized as a platform chemical from fructose by catalytic reactions in acetone/water solvent with non-noble metal catalysts (e.g., HCl, NaOH). Then, selective reactions (e.g., etherification, reduction, dimerization) of the functional groups, such as enone and hydroxyl groups, in the HAH molecule enable applications in organic dyes and polyether precursors. High yields of target products, such as 5-(hydroxymethyl) furfural (HMF) (85.9% from fructose) and HAH (86.3% from HMF) are achieved by sequential dehydration and aldol-condensation with a simple purification process (>99% HAH purity). The use of non-noble metal catalysts, the high yield of each reaction, and the simple purification of the target product allow for beneficial economics of the process. Techno-economic analysis indicates that the process produces HAH at minimum selling price (MSP) of $1958 per ton. The MSP of HAH product allows the economic viability of applications in organic dye and polyether markets by replacing its counterparts, such as anthraquinone ($3200-$3900 per ton) and bisphenol-A ($1360-$1720 per ton). This journal is

Full text of DOI:10.1039/d0gc01576h

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DOI: 10.1039/D0GC01576H
ARTICLE
Catalytic strategy for conversion of fructose to organic dyes,
polymers, and liquid fuels
Hochan Changa, Ishan Bajaja, George W. Hubera, Christos T. Maraveliasa,b, and James A.
Dumesic*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
We report a process to produce a versatile platform chemical from biomass-derived fructose for organic dye, polymer, and
liquid fuel industries. An aldol-condensed chemical (HAH) is synthesized as a platform chemical from fructose by catalytic
reactions in acetone/water solvent with non-noble metal catalysts (e.g., HCl, NaOH). Then, selective reactions (e.g.,
etherification, reduction, dimerization) of the functional groups, such as enone and hydroxyl groups, in the HAH molecule
enable applications in organic dyes and polyether precursors. High yields of target products, such as 5-(hydroxymethyl)
furfural (HMF) (85.9% from fructose) and HAH (86.3% from HMF) are achieved by sequential dehydration and aldol-
condensation with a simple purification process (>99% HAH purity). The use of non-noble metal catalysts, the high yield of
each reaction, and the simple purification of the target product allow for beneficial economics of the process. Techno-
economic analysis indicates that the process produces HAH at minimum selling price (MSP) of $1958/ton. The MSP of HAH
product allows the economic viability of applications in organic dye and polyether markets by replacing its counterparts,
such as anthraquinone ($3200-$3900/ton) and bisphenol-A ($1360-$1720/ton).
However, important challenges must be addressed to develop a
process to produce a versatile platform chemical from biomass that
Introduction
satisfy the markets of high-value chemicals (e.g., polymer, organic
dye). Firstly, high purity of the platform chemical needs to be
achieved from the process. This purity requirement can be
associated with severe separation and/or purification steps that
contribute high capital and operating costs. Secondly, the chemical
stability of the platform chemical is required to prevent uncontrolled
side-reactions, while promoting the desired reactions. An unstable
platform chemical can lead to expensive cost of transportation and
storage to minimize product degradation before selling. Lastly,
hazardous solvents and noble metal catalysts that are typically used
in biomass conversion need to be replaced by green solvents and
inexpensive catalysts. The above challenges have confined biomass
applications to be in liquid fuel industries since the fuels industries
allow for chemical mixtures as final products, and the chemical
stability of fuels is not of critical importance.
Biomass-derived platform chemicals have been considered to be
promising renewable sources for supplying energy (liquid fuels) and
chemicals. For example, 5-(hydroxymethyl) furfural (HMF) is one of
the platform chemicals which can produce 2,5-dimethyl furan (DMF)1
as a gasoline additive2 or 2,5-furandicarboxylic acid (FDCA)3 as a
polymer precursor4. Biomass resources, such as glucose and
fructose, have recently been shown to be converted to HMF in
organic solvents5. Levulinic acid is another promising platform
chemical which can be effectively synthesized from cellulose6. The
levulinic acid can be converted to GVL7 as a green solvent for diverse
biomass upgrading processes8–10 or for liquid fuel uses11–13
.
Recent decreases in liquid fuel prices and increases in demands of
polymers and organic dyes have attracted interest in the production
of high-value chemicals, which requires chemicals with high purity
controlled functional groups in their molecular structure. For
instance, organic dyes possess colorizing chemical features, called
chromophores, such as aromatic (quinone dye) or ketone (C=O)
functional groups to absorb the light in the visible and ultraviolet
(UV) range14. Similarly, functional polymers utilize specific chemical
functionalities, such as furan, α-ω diols or dicarboxyl acids, to
improve the control over various polymer properties, such as
In this paper, we develop a catalytic strategy that enables a process
for production of a new platform chemical (aldol-condensed
product, HAH) from fructose, and we demonstrate the applications
of the platform chemical for organic dyes and monomers. The
proposed reaction route is described in Scheme 1.
A high
concentration (9.1 wt%) of fructose was dehydrated in
acetone/water (75/25, v/v) solvent with HCl catalyst (60 mM) to
produce a high yield (85.9%) of HMF. Then, the acetone solvent was
evaporated under low temperature (~293 K) and pressure (~50
mbar) to minimize HMF degradation and prepare the appropriate
molar ratio of HMF and acetone for aldol-condensation. The distilled
solution, comprising HMF, acetone, HCl, and by-products, served as
a feed for aldol-condensation without purification of HMF. A
controlled amount of NaOH was used to neutralize HCl remaining
from the dehydration step, and to catalyze the aldol-condensation.
The initial molar ratio of the fructose-derived HMF and acetone
determined the yield of the HAH product, up to the maximum yield
of 83.6%. The difference in water solubility between the HAH
thermal resistance15, mechanical strength, and gas permeability16,17
.
Aldol-condensation is a chemical reaction that can append additional
functional groups to a target molecule. Therefore, aldol-condensed
chemicals can be used as new platform chemicals for applications in
high-value chemicals by providing versatile functional groups18,19
.
a. Department of Chemical and Biological Engineering, University of Wisconsin–
Madison, Madison, WI, USA. *Corresponding E-mail: jdumesic@wisc.edu
DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison,
1552 University Ave, Madison, WI 53726, USA.
b
Electronic Supplementary Information (ESI) available. See DOI: 10.1039/x0xx00000x
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product and impurities allowed for simple purification of the HAH economic viability of the process. The minimum selling price (MSP)
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product by washing with water. 1H NMR and 13C qNMR spectra were of HAH product was calculated to be $1958/ton and it suggests that
DOI: 10.1039/D0GC01576H
used to characterize the HAH molecule, and the purity of HAH anthraquinone ($3200-$3900/ton) and bisphenol-A ($1360-
product was measured to be >99% by HPLC analysis. The functional $1720/ton) would become potential markets for replacement by
groups, such as diols and enones, in HAH were selectively converted HAH. This production process of the new biomass-derived platform
by etherification, dimerization, and reduction reactions to chemical provides new directions for utilizing a sustainable resource
demonstrate applications in organic dye and polymer industries. in various high-value chemicals markets.
Furthermore, techno-economic analysis (TEA) assessed the
Scheme 1. Overall catalytic reaction route for HAH production from fructose by dehydration and aldol-condensation.
dehydration was performed at 393 K for 100 min in an acetone/water
(50/50, v/v) solvent containing 137mM HCl, fructose was almost
Results and Discussion
completely converted (94.0%), resulting in 49.7% HMF yield and
67.3% carbon balance (Fig.1.B). However, the fructose conversion,
HMF yield, and carbon balance increased to 98.6%, 88.8%, and
94.2%, respectively, when the reaction was conducted at 393 K for
30 min in an acetone/water (75/25, v/v) solvent containing 121 mM
HCl (Fig.1.C). The decrease in water content of the polar
aprotic/water co-solvent improved the catalytic turnover rates
towards the target products that were catalyzed by acid20. Therefore,
an appropriate amount (75 vol%) of acetone was used as the solvent
for fructose dehydration because addition of acetone leads to higher
HMF yield and carbon balance while it decreases the fructose
solubility.
Solvent effect on fructose dehydration to HMF
The acetone-rich solvent was shown to enhance the fructose
dehydration reactivity (Fig.1.A). 0.6 g of fructose was dehydrated in
8 mL of acetone/water solvent with different acetone composition
over Amberlyst-15 catalyst. Fructose conversion and HMF yield
increased from 38.5% to 71.3% and from 34.7% to 60.1%,
respectively, as the acetone/water volume ratio increased from 50%
to 70% after 150 min dehydration at 393 K. 91.3% fructose was
converted to HMF in 78.7% yield at 393 K and 90 min dehydration in
acetone/water (80/20, v/v) solvent. HMF selectivity was >76.8% and
remained stable in the acetone/water solvent. Therefore, the
fructose dehydration reaction demands the utilization of an acetone-
rich solvent (>70 vol% acetone) to maximize the HMF production
rate.
During fructose dehydration,
a minor acid-catalyzed aldol-
condensation was observed, leading to formation of HA. Thus, the
dehydrated solution mainly contained HMF, HA, and acidic by-
products (formic acid, levulinic acid) after the dehydration step
(Fig.1.D). Fructose was also converted to sugar isomers (mannose,
anhydro-sugar, cellobiose). 3.6% of the carbon of the fructose feed
was converted to humins that must be removed before further
processing to minimize the acid-catalyzed side-reactions21. In Fig.1.D,
activated carbon selectively adsorbed the humins without significant
changes in concentrations of other chemicals. A minor increase in
HMF concentration (Fig.1.D) after the humin removal resulted from
the measurement error of HPLC by acetone evaporation during the
activated carbon treatment.
Previous work reported that homogeneous acids are effective
catalysts for fructose dehydration in the acetone-rich solvent5. In this
respect, Amberlyst-15 catalyst was replaced with HCl to optimize the
HMF yield and carbon balance in the dehydration step. Moreover,
the solubility of fructose defined the upper limitation of the fructose
concentration as a feed. The fructose solubility decreased from 80.0
wt% to 8.3 wt% (Fig.S1) by adjusting the solvent from pure water to
acetone/water (80/20, v/v) mixture at 298 K. Operating a reaction at
the upper limitation of the feed concentration results in a higher
production rate of the target product (HMF). When fructose
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DOI: 10.1039/D0GC01576H
Fig.1. (A) Fructose conversion (Blue bar), HMF yield (Red bar), and HMF selectivity (Green dot) as a function of acetone ratio in the solvent (Reaction
conditions: 0.6 g fructose (~420 mM) in 8 mL acetone/water solvent at 393 K over 0.2 g Amberlyst-15 catalyst), (B) Fructose conversion (Blue),
HMF yield (Red), and Carbon balance (Black) as a function of reaction time (Reaction conditions: 19.6 wt% fructose in acetone/water (50/50, v/v)
solvent with 137 mM HCl), (C) Fructose conversion (Blue), HMF yield (Red), and Carbon balance (Black) as a function of reaction time (Reaction
conditions: 9.1 wt% fructose in acetone/water (75/25, v/v) solvent with 121 mM HCl), (D) Chemicals concentration in dehydrated solution before
(Green bar) and after (Yellow bar) the decolorization (Decolorization conditions: 1.7 wt% activated carbon and 23 wt% water were mixed with
dehydrated solution at 298 K for 30 min.
HMF degradation during vacuum distillation
slightly decreased (from ~85.9% to ≤83.2%) by acid-catalyzed
degradation in the distillation step.
The distillation of acetone solvent was used to control the molar ratio
of HMF and acetone for selective production of HAH by aldol-
condensation. Excess amounts of acetone produce HA as a major
product from aldol-condensation of fructose-derived HMF and
acetone19. Acid-catalyzed degradation of HMF and HA was observed
after vacuum distillation at 298 K, 50 mbar. 9.6% of HMF loss and
10% of HA loss were measured by analyzing the distilled solution
(Table S1). 14% formic acid was accumulated during the humin
formation by degradation of HMF and HA, which is consistent to
previous reports22. HMF degradation was suppressed (from 10±5%
to 6±3%) by reducing the amount of HCl catalyst (from 120 mM to
60mM) in the dehydration step, adding water to dilute HCl before
the distillation, and decreasing the distillation temperature (from
298 to 293 K). With reduced concentration of HCl catalyst (60 mM),
9.1 wt% fructose in acetone/water (75/25, v/v) solvent resulted in
the high HMF yield (85.9%) and carbon balance (96.4%). The major
Fig.2. Molar composition of HMF solution (feed for aldol-condensation)
three compounds of the distilled HMF solution were HMF, acetone, after the fructose dehydration, humin decolorization, and acetone
distillation.
and formic acid (Fig.2). As a result, the HMF yield from fructose
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Aldol-condensation of fructose-derived HMF and acetone
Crystallization and purification of HAH
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DOI: 10.1039/D0GC01576H
The fructose-derived HMF solution was acidic because it contained The fructose-derived HAH spontaneously crystallized during the
acidic by-products (e.g., formic acid, levulinic acid) and HCl catalyst aldol-condensation due to its low solubility in water19. The water
from the dehydration step. Therefore, addition of the controlled solubility of residual HMF, HA, salts (NaCl, sodium formate, sodium
amount of NaOH is necessary to neutralize the acids and catalyze the levulinate), and humins was higher than the HAH solubility. 6.2% of
aldol-condensation. Each concentration of acidic by-product was the produced HAH was dissolved in water with the water-soluble
measured by HPLC, and the concentration of HCl was assumed to be impurities and discarded with the purge stream after the
the same as the initial addition in the dehydration step because purification. >99% purity of the purified HAH was measured by HPLC
water solvation prevented the vaporization of HCl23 in the distillation analysis (Fig.S9.C). The spontaneous crystallization enables a simple
step. The yield of HAH and HA depended on the initial molar ratio of and inexpensive purification to produce high yield (80.9%) of purified
HMF
HAH from fructose-derived HMF.
HMF to acetone sources (Acetone + HA). The highest HAH yield from the
fructose-derived HMF was 86.3% with 93.0% carbon balance when
HMF
Acetone + HA (mol) ratio was 2.5 (Fig.3).
Previous work on the aldol-condensation of furfurals and ketones
reported that the presence of neutral salts does not affect the
reaction kinetics of aldol-condensation24. Thus, while sugar isomers
and humins are possible impurities that can cause side-reactions in
aldol-condensation step, the acidic by-products should not cause
side-reactions by forming the neutral salts (sodium formate, sodium
levulinate) before the aldol-condensation. Humin-free feed for aldol-
condensation was prepared by decolorization of the feed over
activated carbon to investigate the effect of humins on side-
reactions. There was no significant difference in HAH yield and
carbon balance between humin-free feed (Decolorized feed) and
humin-containing feed (Untreated feed) (Fig.S2.A). This result
indicates that the presence of sugar isomers affected the loss (7.0%)
in the carbon balance during aldol-condensation. Previous research
about the formation of carbohydrate complexes from alkaline
degradation of fructose and glucose25 supports the idea that the
sugar isomers induced humin formation. Moreover, acid-catalyzed
Fig.4. (A) 13C quantitative NMR (qNMR) spectrum of purified, fructose-
derived HAH (126 MHz, MeOD) δ: 190.49 (1C), 159.65 (2C), 152.51 (2C),
degradation of HMF and HA was observed during decolorization at
298 K (Fig.S2.B). Accordingly, decolorization of the feed has no
benefit for production of HAH.
131.01 (2C), 123.42 (2C), 118.84 (2C), 111.42 (2C), 57.61 (2C) ppm, (B)
1H standard NMR spectrum of purified, fructose-derived HAH (500 MHz,
MeOD) δ: 7.51 (s, 1H), 7.48 (s, 1H), 6.98 (s, 1H), 6.95 (s, 1H), 6.82 (d, 2H),
6.47 (d, 2H), 4.58 (s, 4H) ppm (MeOD: 4.87 (s) ppm).
Selective conversion of functional groups in HAH for organic dye
and polymer applications
The reactivity of diol functional group in HAH was investigated by the
etherification of HAH with methanol. 93.9% conversion of HAH and
the corresponding yield of the etherifed HAH were measured by 13
C
qNMR analysis after 9h reaction over a WOx-ZrO2 catalyst at 453 K in
methanol solvent. The Lewis and Brϕnsted acid sites of the catalyst
acted as catalytic active sites for etherification26,27. The etherification
of HAH was highly effective since minimal formation of by-products
(< 4.5 carbon%) was detected by 13C qNMR spectrum. The effective
etherification of diol groups in HAH suggests that HAH is a candidate
for polyether precursors in the presence of acid catalyst. In addition,
the carbonyl group of HAH was converted to a secondary alcohol by
selective reduction with the reduction agent, NaBH4. >95%
conversion of HAH and the corresponding yield of the selectively
Fig.3. Aldol-product yield (HAH: Light green bar, HA: Dark green bar) and
퐻푀퐹
fructose-derived HMF conversion (Red dot) as a function of 퐴푐푒푡표푛푒 + 퐻퐴
(mol) ratio (Reaction conditions: 0.12 M (70 min), 0.23 M (60 min), 0.21
퐻푀퐹
M (60 min) NaOH for 퐴푐푒푡표푛푒 + 퐻퐴 (mol) = 2.0, 2.2, 2.5 at 308 K).
4 | J. Name., 2012, 00, 1-3
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reduced HAH were measured by 13C qNMR analysis. The symmetric
structure and tri-hydroxy group (two primary and one secondary
alcohol groups) in the selectively reduced HAH enables a cross-linker
application, like glycerol.
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DOI: 10.1039/D0GC01576H
Scheme 2. Reaction mechanism of (A) HAH etherification with methanol
over WOx-ZrO2 catalyst, (B) HAH selective reduction in presence of
NaBH4, and (C) HAH dimerization with acetate anion.
An adjustable UV-vis absorption band and high molar excitation
coefficient of the molecule are of critical importance for organic dye
applications. The HAH molecule had a broad absorption spectrum
from two chromophores, 2-hydroxymethyl furan and 1,4-pentadien-
Fig.5. (A) UV-vis absorption spectrum of diluted HAH (Green), HAH
3-one, shown as (i) and (ii), respectively (Fig.5.A). Shifts in the dimer (Red), and etherified HAH (Blue) in methanol solvent. (i) (2-
hydroxymethyl furan) and (ii) (1,4-pentadien-3-one) represent the
absorption spectrum of HAH were achieved by dimerization and
chromophores of HAH. (B) Molar excitation coefficient (slope, M-1cm-1)
etherification (Fig.5.A). The dimerization ([2+2] cycloaddition) tuned
of diluted fructose-derived HAH in methanol solvent at 378 nm UV
the (ii) moiety (marked in Fig.5.A) in HAH and produced a HAH dimer
at room temperature for 8 days in the presence of acetate anion as
a hard base. 94.3% yield of HAH dimer from HAH was measured by
13C qNMR analysis after the dimerization. The HAH dimer yielded a
narrow UV-vis absorption spectrum by shifting the maximum
absorption wavelength from 378 nm (by HAH) to 334 nm. Similarly,
etherification eliminated the (i) moiety (marked in Fig.5.A) in HAH
and resulted in a sharp absorption band at 378 nm as the maximum
absorption wavelength. The molar excitation coefficient of HAH in
methanol solvent was measured to be 22,262 M-1∙cm-1 at 378 nm
incident UV light (Fig.5.B). This value of HAH is within the range of
typical molar excitation coefficients (from 2,900 to 43,000 M-1∙cm-1)
of organic dyes, monosubstituted anthraquinones, in methanol
solvent at UV incident light28. Note that HAH effectively absorbs UV
light (from 300 to 450 nm) and can thus serve as a functional organic
dye to protect materials from UV light.
incident light.
Techno-economic model analysis of HAH production process
We developed a process model for the conversion of fructose to HAH
(Fig.6) based on the aforementioned experimental data in Aspen
Plus. Then, we performed techno-economic analysis (TEA) for the
base design, based on fructose flow rate of 10,000 kg∙h-1. A detailed
description of the process is provided in the experimental methods
and supplementary information, with the process flow diagram
shown in Fig.S10. Other pertinent information required to estimate
the minimum selling price (MSP) of HAH are given in Tables S4-S6. If
the price of fructose is assumed to be $650/ton, the analysis suggests
that HAH can be produced using the proposed process at an MSP of
$1958/ton (Fig.7). The high yields of HMF and HAH, and the ease of
their separation from the solvent lead to favorable economics. The
costs of the feedstock (67%) and acetone (14%) are the biggest
contributors to the MSP of HAH. Reducing the price of the feedstock
and increasing the plant capacity reduces the MSP of HAH (Fig.S11).
For instance, if the price of fructose is reduced to $500/ton, then the
MSP of HAH is estimated to be $1675/ton. The results indicate that
HAH can be a sustainable and economically competitive alternative
to fossil fuels-derived polyether monomer, bisphenol-A ($1360-
$1720/ton)29 and organic dye, anthraquinone ($3200-$3900/ton)30.
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production rate less than the volume of the potenViteiwalArmticlaerOknelitnse,
DOI: 10.1039/D0GC01576H
suggests that the HAH product could replace current markets of
organic dyes (anthraquinone market price: $3200-$3900/ton) and
polyethers (bisphenol-A market price: $1360-$1720/ton). This
biomass-derived platform chemical from the optimized process
could thus supply organic dyes, polymers, and liquid fuels from
renewable sources in the future.
Fig.6. Overview of the process block-flow diagram to produce HAH from
fructose.
Experimental methods
Materials
Fructose (>99%, Sigma-Aldrich), acetone (HPLC grade, Fisher
Scientific), methanol (HPLC grade, Fisher Scientific), NaOH (FCC
specification, Fisher Scientific), HCl (6N, Fisher Scientific), activated
carbon (Norit SX-Ultra), HMF (98% AK Scientific), and Mill-Q water
(~18 MΩ cm) were used in all the experiments. Commercial
tungstated zirconium hydroxide (15 wt% WO3 loading, MEL
Chemicals, XZO1251/01), sodium borohydride (Sigma-Aldrich,
purum p.a. >96%), sodium acetate (Sigma-Aldrich), ethyl acetate
(HPLC grade, Fisher Chemical), hexane (HPLC grade, Sigma-Aldrich),
etherification reaction was performed in a 50 mL Parr reactor (Parr
Instrument Company).
Fig.7. Breakdown of the costs and revenue of the proposed approach.
Conclusion
Decolorization of the dehydrated solution on activated carbon
We designed a process for production of a biomass-derived platform
chemical (HAH) by optimizing the catalytic reactions, using green
solvents, non-noble metal catalysts, and a simple purification
strategy. The acetone/water (75/25, v/v) solvent with low
concentration of HCl (60 mM) catalyst allowed for production of HMF
in high yield (85.9%) from a high concentration fructose (9.1 wt%)
feed. Acetone distillation following HMF production was used to
provide a controlled molar ratio of HMF and acetone, with minimal
HMF degradation. High yield (86.3%) of HAH from the fructose-
derived HMF was achieved by aldol-condensation of the feed with
Activated carbon was received from Cabot Corporation and used as
received. The humins from fructose dehydration were selectively
adsorbed on activated carbon at 298 K. In a milligram scale
experiment, 0.35 g activated carbon was added to 7.4 g dehydrated
solution and stirred for 30 min. After the adsorption, activated
carbon was filtrated through 0.2 μm PTFE filter. In a gram-scale
experiment, 13.4 g water was added to 57 g dehydrated solution to
dilute HCl concentration before activated carbon adsorption. Then, 1
g activated carbon was added to 70.4 g diluted solution and stirred
for 30 min. After the adsorption, activated carbon was removed by
filtration of the solution through filter paper (Grade 50 filter,
Whatman). 0.1 mL of the filtered solution was diluted 10 times with
Milli-Q water and analyzed using HPLC (Aminex HPX-87H column,
Bio-Rad) to measure the concentrations of fructose, HMF, sugar
isomers, and acidic by-products (formic acid, levulinic acid). 0.1 mL
of the filtered solution was diluted 5 times with methanol and
analyzed using HPLC (Luna C18 column, Phenomenex) to measure
the concentration of HA.
HMF
the controlled molar ratio of the reactants (Acetone + HA=2.5). The
acidic by-products (e.g., formic acid, levulinic acid) and HCl were
converted to salts by neutralization before aldol-condensation to
minimize side-reactions in the aldol-condensation step. The HAH
product was purified simply (>99% purity) by washing with water due
to its low solubility in water. The applications of HAH were
demonstrated by selective conversion of the functional groups in
HAH molecules. The diol in HAH was etherified by methanol over a
WOx-ZrO2 catalyst, suggesting that HAH can be a candidate for the
polyether precursors. Selective reduction of the carbonyl group in
HAH produced a chemical with tri-hydroxy group, which can be used
as a cross-linker for polymer applications. Furthermore, two HAH
molecules were dimerized in the presence of acetate anion, leading
to a shift in the UV-vis absorption spectrum. The high molar
excitation coefficient (22,262 M-1∙cm-1) and the adjustable UV-vis
absorption band of HAH molecule enable uses for HAH as a suitable
candidate for an organic dye. Finally, techno-economic analysis of
the process was employed to evaluate the effectiveness of the
process by comparing the minimum selling price of HAH product with
market prices of current counterparts from petroleum. The
minimum selling price of HAH ($1958/ton), calculated at the
Vacuum distillation of dehydrated and decolorized product
The decolorized solution was distilled under ~100 mbar in the air
(~298 K). Acetone was evaporated before water under ~100 mbar
while the temperature of the solution decreased from 298 K to 290
K during acetone evaporation. After acetone evaporation, the
pressure was further decreased from ~100 to ~50 mbar to evaporate
water. During the water evaporation in the air, the temperature of
the solution was around 290-293 K. The density of decolorized
solution increased from 0.922 g/mL to 1.027 g/mL. The density of the
퐻푀퐹
solution was always more than 1.02 g/mL when 퐴푐푒푡표푛푒 + 퐻퐴 (mol) >
2.
HPLC analysis of dehydrated, decolorized, and distillated solution
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The chemical composition of the dehydrated, decolorized, and HMF conversion
View Article Online
distillated solution was quantified by High Performance Liquid
DOI: 10.1039/D0GC01576H
Moles of initial HMF ― Moles of final HMF
Chromatography (HPLC) analysis. 0.1 mL of dehydrated or
decolorized solution was diluted 10 times with Milli-Q water for
analyzing the concentration of fructose, HMF, sugar isomers, and
acidic by-products (formic acid, levulinic acid). Similarly, 0.1 mL of
dehydrated or decolorized solution was diluted 5 times with
methanol for analyzing the concentrations of HMF and HA. 0.04 mL
of distilled solution was diluted 20 times with Milli-Q water for
analyzing the concentrations of acetone, sugars, HMF, and acidic by-
products. Similarly, 0.04 mL of distilled solution was diluted 10 times
with methanol for analyzing the concentrations of HMF and HA. All
the diluted samples were filtrated through 0.2 μm PTFE filter before
the sample was injected into HPLC. The concentrations of fructose,
sugar isomers, and acidic by-products were measured by a Water
2695 separation module equipped with a Aminex HPX-87H (Bio-Rad)
column and RI detector, while HMF concentration was measured
with a Waters 2998 PDA detector at 320 nm. The temperature of the
HPLC column was maintained at 338 K, and the flow rate of the
mobile phase (pH 2 water, acidified by sulfuric acid) was 0.6 mL min-
1. The concentration of HA was measured by a Water 2695
separation module equipped with a Luna C18 (Phenomenex) column
and a Waters 2998 PDA detector set at 390 nm (for HA analysis). The
temperature of the HPLC column was held constant at 323 K. The
∙ 100 (%)
=
(5)
Moles of initial HMF
Fructose dehydration with HCl in acetone/water (75/25, v/v)
solvent
In a milligram-scale experiment, aqueous feed (25 wt% fructose) was
prepared by dissolving 5 g fructose and 1.26 mL of 3 M HCl solution
in 13.74 mL Milli-Q water. 2.69 g aqueous feed (0.67 g fructose, 2 mL
water, 0.02 g HCl) was mixed with 6 mL acetone in a 10 mL thick-
walled glass reactor (Chemglass). A triangular stir bar was added for
stirring at 700 rpm. The reactor was placed in an oil bath at 393 K for
75 min. In a gram scale experiment, 4 g fructose and 1.16 g of 3 M
HCl were dissolved in 11 g Milli-Q water to prepare the aqueous feed.
Then, 35.63 mL acetone was mixed with the aqueous feed in a 48 mL
thick-walled glass reactor (Ace glass). An egg-shaped stir bar was
added for stirring at 900 rpm. The reactor was placed in an oil bath
at 393 K for 95 min. The dehydration was terminated by cooling the
reactor in a water bath.
Fructose dehydration with HCl in acetone/water (50/50, v/v)
solvent
mobile phase was a gradient of methanol/water (with 0.1 wt% formic The aqueous feed (30 wt% fructose in water) was prepared by
acid) at a constant flow rate of 1.0 mL min-1 (0.1 wt% formic acid dissolving 6.5 g fructose and 0.75 mL 6 M HCl solution in 14.25 mL
water linearly changed to methanol in 20 min, held pure methanol Milli-Q water. 5.07 g aqueous feed (1.53 g fructose, 3.5 mL water,
for 7 min, and methanol linearly changed to 0.1 wt% formic acid 0.04 g HCl) was mixed with 3.5 mL acetone in a 10 mL thick-walled
water in 3 min).
glass reactor (Chemglass). A triangular stir bar was added for stirring
at 790 rpm. Each reactor was placed in an oil bath at 393 K for
different reaction times. The dehydration was terminated by cooling
the reactor in a water bath. 0.5 mL dehydrated sample was diluted
10 times with Milli-Q water and analyzed using HPLC (Aminex HPX-
87H column, Bio-Rad) to measure the concentration of fructose,
HMF, sugar isomers, and acidic by-products. The HPLC sample was
filtrated with 0.2 μm PTFE filter before the sample injection into
HPLC.
Moles of final HMF
∙ 100 (%)
HMF yield from fructose = Moles of initial fructose
(1)
Fructose conversion
Moles of initial fructose ― Moles of final fructose
∙ 100 (%)
=
(2)
Moles of initial fructose
HPLC analysis of aldol-condensed solution
Fructose dehydration in different ratios of acetone/water solvent
over Amberlyst-15
After aldol-condensation, residual HMF and aldol-condensed
products (HA, HAH) were quantified by HPLC analysis. The as-
synthesized solution was neutralized with HCl (pH of the solution was
measured by pH test strips) and diluted 4 times with methanol to
terminate aldol-condensation and dissolve precipitated HAH. 0.1 mL
of diluted solution was further diluted 10 times with methanol for
analyzing the concentrations of HMF and HA. Similarly, 0.01 mL
diluted solution was diluted 500 times with methanol for analyzing
the concentration of HAH to avoid the signal saturation of the PDA
detector. The diluted samples were filtrated through 0.2 μm PTFE
filter before the sample was injected into HPLC. The concentrations
of HMF, HA, and HAH were measured by a Water 2695 separation
module equipped with a Luna C18 (Phenomenex) column and a
Waters 2998 PDA detector, set at 320 nm (for HMF analysis) and 390
nm (for HA, HAH analysis). The temperature of the HPLC column and
mobile phase were same as described above. Purified chemical
standards of HA and HAH were used for the calibration of
concentration and integrated peak area.
For acetone/water (50/50, v/v) solvent experiments, 0.6 g fructose
was dissolved in the mixture of 4 mL Milli-Q water and 4 mL acetone.
For acetone/water (60/40, v/v) solvent experiments, 0.6 g fructose
was dissolved in the mixture of 3.2 mL Milli-Q water and 4.8 mL
acetone. For acetone/water (70/30, v/v) solvent experiments, 0.6 g
fructose was dissolved in the mixture of 2.4 mL Milli-Q water and 5.6
mL acetone. For acetone/water (80/20, v/v) solvent experiments,
0.54 g fructose was dissolved in the mixture of 1.6 mL Milli-Q water
and 6.4 mL acetone. 0.2 g Amberlyst-15 catalyst was added to the
fructose feed and the reactor was placed in an oil bath at 393 K. A
triangular stir bar was used for stirring at 650 rpm. 150 min reaction
time was used for the experiments of 50/50, 60/40, and 70/30
acetone/water solvents. 90 min reaction time was used for 80/20
acetone/water solvent experiment since the fructose conversion had
reached near the complete conversion. 10 mL thick-walled glass
reactors (Chemglass) were used for the experiments. The
dehydrated solution was decolorized on 0.06 g activated carbon for
30 min before HPLC analysis. 0.5 mL decolorized sample was diluted
10 times with Milli-Q water and filtrated with 0.2 μm PTFE filter
before the sample injection into HPLC.
Moles of final HA
∙ 100 (%)
HA yield from HMF = Moles of initial HMF
(3)
(4)
HAH yield from HMF = 2 ∙ Moles of final HAH
∙ 100 (%)
Moles of initial HMF
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Journal Name
Table.1 Fructose dehydration in different acetone/water solvents.
View Article Online
DOI: 10.1039/D0GC01576H
Solvent volume
composition
Fructose added (g)
Amberlyst-15 added Milli-Q water added Acetone added (mL) Reaction time (min)
(g)
(mL)
(acetone/water)
50/50
60/40
70/30
80/20
0.60
0.60
0.60
0.54
0.20
0.20
0.20
0.20
4.0
3.2
2.4
1.6
4.0
4.8
5.6
6.4
150
150
150
90
Aldol-condensation of fructose-derived HMF and acetone
acid) in the distilled solution. The required amount of NaOH solution
was added to the feed solution, containing a specific molar ratio of
퐻푀퐹
The concentrations of the distilled solution containing reactants
(HMF, acetone, HA) and acidic by-products (formic acid, levulinic
acid) were measured by HPLC analysis and this solution was used as
HMF and acetone sources (퐴푐푒푡표푛푒 + 퐻퐴), at room temperature and
then the solution was placed in an oil bath at 308 K. The cross-shaped
stir bar was used for stirring at 475 rpm. The reaction time was
a feed for aldol-condensation. The appropriate amount of acetone
19
determined by the kinetic model to maximize the HAH yield. The
퐻푀퐹
was added to the distillated solution for various initial
퐴푐푒푡표푛푒 + 퐻퐴 product solution was neutralized with 0.5 M HCl solution and diluted
experiments. Similarly, the appropriate amount of 3 M NaOH
solution was determined based on previous kinetic model 19 and the
amount required to neutralize the acids (HCl, formic acid, levulinic
with methanol for HPLC analysis.
Table 2. Feed conditions and reaction time for various initial molar ratio of HMF and acetone source
HMF
Acetone added
(g)
3 M NaOH
solution added
(mL)
HMF in
distillated
solution (g)
HA in distillated
solution (g)
Acetone in
distillated
solution (g)
Reaction time
(min)
Acetone + HA (mol)
2.0
2.2
2.5
0.0100
0.0000
0.0075
0.400
0.175
0.173
0.310
0.094
0.096
0.010
0.004
0.004
0.030
0.018
0.016
70
60
60
Purification of HAH by water washing filtration
Purified HA solution (light yellow liquid) was collected. Ethyl acetate
and hexane were evaporated at 313 K under 200 mbar. The purity of
1
HA was determined by H and 13C NMR spectrum (Figure S3). The
As-synthesized HAH from aldol-condensation of fructose-derived
HMF and acetone was purified by spontaneous crystallization in
water. The aldol-condensed solution was neutralized by HCl before
purified HA was used as the calibration standard for HPLC analysis.
the purification. The neutralized solution was washed by passing Preparation of etherified HAH
water slowly during the paper filtration, leading to HAH precipitation
6 g commercial tungstated zirconium hydroxide was calcined at 923
and removal of water-soluble impurities (HMF, HA, salt, sugars).
After collecting the washed HAH, the solid state of purified HAH was
dried at 323-333 K overnight (>18 h) to remove residual water. The
purity of the dried HAH was analyzed by HPLC and the molecular
K for 3 h in a muffle furnace. The temperature was raised from room
temperature to 923 K with 5 K∙min-1 ramping rate. 31 mg calcined
WOx-ZrO2 catalyst was placed in a 50 mL Parr reactor. 153 mg of HAH
was completely dissolved in 10 mL methanol to prepare the feed. The
HAH solution in methanol (56 mM) was added in the Parr reactor.
The reactor was purged twice with 20 bar Ar to displace the air in the
reactor. Then, 20 bar Ar was filled into the reactor for the
etherification at room temperature. The Parr reactor was heated to
453 K in 1 h (final pressure increased to 55 bar at 453 K). The reactor
was kept at 453 K for 9 h with 450 rpm stirring speed, and then cooled
to room temperature by natural convection. The solid catalyst was
separated from the etherified HAH by filtration. The methanol
solvent was evaporated under 100 mbar at 313 K and the product
was characterized by 1H NMR, 13C quantitative NMR, and high-
resolution mass spectrometry (HRMS) (Fig.S.4). The conversion and
yield were measured by 13C quantitative NMR spectrum.
1
structures of HAH was characterized by H and 13C NMR spectrum
(Fig.4).
Preparation of HA chemical standard by column chromatography
89 mg of commercial HMF was dissolved in a solution containing 0.5
ml acetone and 0.48 ml Milli-Q water in a 10 mL glass vial. A cross-
shaped stir bar was added to the glass vial for mixing and the solution
was heated to 308 K in an oil bath. The solution was kept at 308 K for
15 min before the addition of NaOH to reach thermal equilibrium.
0.135 ml of 1 M NaOH solution was injected to the HMF solution and
the solution was stirred (800 rpm) at 308 K for 10 min. After the
required time had elapsed, 1.11 ml of 0.1 M HCl solution was added
to the product solution to terminate aldol-condensation. Column
chromatography isolated HA and produced a standard chemical for Preparation of selectively reduced HAH
HPLC quantification. Prior to chromatography, water solvent was
137 mg HAH was dissolved in 10mL methanol solvent to prepare the
evaporated at 313 K, under 50 mbar from the product mixture
obtained after aldol-condensation. The concentrated product
solution was separated by passing it through a silica gel column. Ethyl
acetate/hexane mixture (50/50 (v/v)) was used as the eluent.
feed solution. 38 mg NaBH4 was added in the HAH solution with
vigorous stirring for 2 h at arbitrary room temperature. 30 mL ethyl
acetate and 10 mL saturated NaCl solution in water were added into
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퐻푀퐹
the reduced HAH solution for the extraction. The organic phase was
separated and evaporated under 150 mbar at 313 K and the product
was characterized by 1H NMR, 13C quantitative NMR, and high-
resolution mass spectrometry (HRMS) (Fig.S.5). The conversion and
yield were measured by 13C quantitative NMR spectrum.
= 2.5 onViemwoAlreticbleaOsnilsine
for aldol-condensation reaction
(
)
.
퐴푐푒푡표푛푒 + 퐻퐴
DOI: 10.1039/D0GC01576H
Following the solvent recovery section, HMF is converted to HA and
HAH in the aldol-condensation reactor (R-2) in the presence of
sodium hydroxide in 3.3% and 86.3% molar yields, respectively.
While NaOH is a catalyst for aldol-condensation, acetone acts as both
a reactant and solvent. Water, acetone, and NaOH are added such
that the concentrations of HMF, acetone, and NaOH at the reactor
throat are 655 mM, 325 mM, and 210 mM, respectively. In the HAH
purification section, first HCl is added to neutralize NaOH. Thereafter,
HAH is purified in a filtration tank (S-4), where it is precipitated and
the remaining components including unreacted fructose and HMF,
acetone, and HA dissolve in water and are sent to the wastewater
treatment facility. Finally, the HAH cake contains some water and it
is dried by circulating filtered hot air in a dryer (S-5). Then, we
simulate a base design case with a fructose feedstock flow rate of
10,000 kg∙h-1. The mass and energy balances, temperature and
pressure conditions of key process streams are given in Table S2.
Preparation of HAH dimer
50 mg of HAH was mixed with 5 mL water and sonicated to produce
colloidal dispersion. 60 mg of sodium acetate was added to the HAH
colloidal solution. The colloidal HAH solution was vigorously stirred
for 8 days at arbitrary room temperature. The dimerized product was
precipitated by centrifugation (3000 rpm, 10 min) and the aqueous
phase was gently separated by using pipette. The precipitated
product was evaporated under 50 mbar at 313 K and the product was
characterized by 1H NMR, 13C quantitative NMR, and high-resolution
mass spectrometry (HRMS) (Fig.S.6). The conversion and yield were
measured by 13C quantitative NMR spectrum.
Second, we optimize energy usage by performing heat integration
using Aspen Energy Analyzer (V10 Aspen Technology). Without heat
integration, the total heat required is 30 MW, and the total cooling
required is 30.5 MW. Vacuum evaporator consumes almost half of
the total required energy for heating and the condenser that liquifies
acetone/water vapor stream from vacuum evaporator expends 60%
of the total cooling requirements. Finally, the electricity requirement
of the process is estimated to be 48.1 kW. Energy recovery of 6.2 MW
is obtained (Table S3) by heat integration of the stream exiting S-1
and the stream entering S-3. It is assumed that the required
electricity, heating and cooling are satisfied by external sources.
UV-vis absorption spectrum of HAH, HAH dimer, and etherified
HAH
HAH, HAH dimer, and etherified HAH were diluted in methanol
solvent until the absorbance signals of the detector were not
saturated. 12 mg of fructose-derived HAH was dissolved in 40 mL of
methanol solvent to prepare the parent HAH solution (~0.001M) for
molar excitation coefficient measurement. The parent HAH solution
(~0.001M) was further diluted in methanol solvent to prepare
0.000054, 0.000027, 0.000014, and 0.000005M HAH solution. All
diluted samples were placed to absorption glass cell (Fisherbrand,
Absorption Macro Special Optical Glass) and measured by UV-vis
spectrophotometer (Beckman Coulter, DU-520). Pure methanol
solvent was scanned for background signal from 250 to 700 nm.
Third, equipment sizes and the corresponding costs are estimated.
The costs of the reactors, filtration tank, adsorption columns and
dryer are estimated using the cost data in the NREL report31. The
costs of the remaining equipment are estimated using Aspen Process
Economic Analyzer (V10 Aspen Technology). All the equipment and
Techno-economic analysis
To demonstrate the economic feasibility of the approach, the material costs are adjusted to a common year (2018) using
minimum selling price (MSP) of HAH was computed. The techno- appropriate cost indices. The capital and operating costs are
economic analysis follows four steps. First, we design a process to summarized in Table S4 and S5, respectively. Total capital investment
convert fructose to HAH. The process consists of four sections as is computed to be $30.3 million and the operating cost is estimated
illustrated in Fig. 6. A more detailed process flow diagram, with the to be $86.06 million/year.
main equipment, is given in Fig. S10. The models for each of the
Fourth, we calculate the minimum selling price (MSP) of HAH using
discounted cash flow analysis (economic parameters given in Table
S6). The MSP is computed to be $1958 per ton of HAH for a plant
with production capacity of 46 kton/year of HAH.
sections were developed using Aspen Plus (V10 Aspen Technology).
While the models for HMF production, HAH production and HAH
purification sections are based on experimental results, flash
columns in solvent recovery section are simulated using Aspen. In the
HMF production section, the yields of HMF, HA, and byproducts from
fructose are 85.9%, 2.7%, and 9.3%, respectively. Although the
byproducts consist of several components, for simplicity, all the
byproducts are labeled as humins. The HMF production reactor (R-1)
is operated at 393 K and 10 bar so that all the components are in
liquid phase. The stream exiting the reactor then enters the solvent
recovery section, where it is passed through a throttling valve into a
flash drum (S-1). Due to the reduction in pressure, a fraction of
acetone/water is recovered as vapor and recycled to the HMF
production section. The liquid outlet of the flash drum is then sent to
an adsorption column (S-2), where activated carbon selectively
adsorbs humins. Following the separation of humins, the stream
enters a vacuum flash column (S-3), where more solvent is recovered
in the vapor phase. Before recycling the vapor stream to the HMF
production section, the vapor stream is liquified using a refrigerant
available at 248 K. The evaporator operates at 293 K. This allows us
to meet the required ratio of HMF to HA and acetone that is desirable
Conflicts of interest
Authors declare that there is no conflict of interest.
Acknowledgements
This material is based upon work supported in part by the Great
Lakes Bioenergy Research Center, U.S. Department of Energy, Office
of Science, Office of Biological and Environmental Research under
Award Number DE-SC0018409 and in part by U.S. Department of
Energy under Award Number DE-EE0008353. We thank the Mass
Spectrometry and NMR facilities that are funded by: Thermo Q
ExactiveTM Plus by NIH 1S10 OD020022-1; Bruker Quazar APEX2 and
Bruker Avance-500 by a generous gift from Paul J. and Margaret M.
This journal is © The Royal Society of Chemistry 20xx
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Bender; Bruker Avance-600 by NIH S10 OK012245; Bruker Avance-
400 by NSF CHE-414 1048642 and the University of Wisconsin-
Madison. We thank Minsoo Ju for help in NMR analysis of HAH dimer.
Mubarak, R. M. Kriegel and W. J. Koros, Polymer, 2014, 55,
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6861–6869.
DOI: 10.1039/D0GC01576H
17
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DOI: 10.1039/D0GC01576H
Table of contents
Catalytic strategy for conversion of fructose to organic dyes, polymers, and
liquid fuels
Hochan Changa, Ishan Bajaja, George W. Hubera, Christos T. Maraveliasa, and James A. Dumesic*a,b
a Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, WI 53706, USA.
b DOE Great Lakes Bioenergy Research Center, University of Wisconsin-Madison, 1552 University Ave, Madison, WI
53726, USA.
* Corresponding author: James A. Dumesic (jdumesic@wisc.edu)
One sentence summary:
Catalytic pathway for supplying sustainable organic dyes, polymers, and liquid fuels from
fructose by production of a versatile platform chemical