applied

sciences
Article
Production of Sorbitol via Catalytic Transfer
Hydrogenation of Glucose
Beatriz García , Jovita Moreno , Gabriel Morales , Juan A. Melero and Jose Iglesias *
Chemical & Environmental Engineering Group, Universidad Rey Juan Carlos, C/Tulipan s/n., E28933 Mostoles,
Madrid, Spain; [email protected] (B.G.); [email protected] (J.M.); [email protected] (G.M.);
[email protected] (J.A.M.)
* Correspondence: [email protected]; Tel.: +34-914-888-565




Received: 14 February 2020; Accepted: 4 March 2020; Published: 7 March 2020


Featured Application: Catalytic transfer hydrogenation from alcohols allow converting under
mild reaction conditions glucose into sorbitol.

Abstract: Sorbitol production from glucose was studied through catalytic transfer hydrogenation
(CTH) over Raney nickel catalysts in alcohol media, used as solvents and hydrogen donors. It was
found that alcohol sugars, sorbitol and mannitol, can be derived from two hydrogen transfer pathways,
one produced involving the sacrificing alcohol as a hydrogen donor, and a second one involving
glucose disproportionation. Comparison between short-chain alcohols evidenced that ethanol was
able to reduce glucose in the presence of Raney nickel under neutral conditions. Side reactions
include fructose and mannose production via glucose isomerization, which occur even in the absence
of the catalyst. Blank reaction tests allowed evaluating the extension of the isomerization pathway.
The influence of several operation parameters, like the temperature or the catalyst loading, as well as
the use of metal promoters (Mo and Fe-Cr) over Raney nickel, was examined. This strategy opens
new possibilities for the sustainable production of sugar alcohols.

Keywords: sorbitol; catalytic transfer hydrogenation; Raney nickel; glucose; biomass; catalysis

1. Introduction
Lignocellulose biomass is considered a promising alternative source to fossil fuels for the
sustainable production of useful chemicals and value-added products [1,2]. The abundance of this
feedstock makes biomass the only alternative to the traditional raw materials used in chemical
industries, with most of them based on the exploitation of crude oil derivatives. Lignocellulose biomass
is mainly composed of cellulose, hemicellulose, and lignin [3]—two polysaccharides (cellulose and
hemicellulose), and a random polymer mainly composed of phenyl derivatives (lignin). Lignocellulosic
biomass is the major component of agricultural waste and forest residue, which are inexpensive and
abundant raw materials, as well as a primary source of monosaccharides, including glucose and
fructose [4], which can be converted into a variety of different chemicals, including sugar polyols.
Sugar polyols are interesting monosaccharide-derived products, which find applications in several
fields, both as polyols and as starting materials for the preparation of different products. Sorbitol is
a sugar polyol extensively used in nutrition, cosmetics, and medical or industrial applications. It is
employed as a low-calorie sweetener, as a humectant in cosmetics and pharmaceutical products, and
as an intermediate platform for the production of value-added molecules (e.g., 1,4-sorbitan, isosorbide,
glycols, l-ascorbic acid, etc.) [5–7]. This versatility led to its inclusion in the top derived value-added
chemicals to be converted into high-value bio-based products from biomass [8].

Appl. Sci. 2020, 10, 1843; doi:10.3390/app10051843 www.mdpi.com/journal/applsci

Appl. Sci. 2020, 10, 1843 2 of 12

Sorbitol production was reported to be carried out using cellulose in the presence of noble metals [9]
and transition metal-based catalysts [10,11]. However, a most extended alternative is its production
starting from glucose. At an industrial scale, sorbitol is produced via glucose hydrogenation [2]
as it is the most affordable precursor [12], whose production is liable to be obtained via cellulose
hydrolysis [13,14]. The reaction mechanism consists of the reduction of carbonyl groups of saccharides
under hydrogen pressure in the presence of a solid metal catalyst based on Ni, Pd, Pt, or Ru [15,16].
All these catalysts are easily recoverable and display good catalytic activity in terms of sorbitol yield,
operating under aqueous-phase solution [6,17–20]. In recent years, Raney nickel and ruthenium
catalysts made a clean sweep on sorbitol production. Ru presents higher activity and selectivity to
sorbitol [16,21] than Raney nickel catalysts, but this metal is much more expensive than nickel-based
catalysts. In this way, Raney nickel was revealed as the most interesting active phase to be used in the
industrial-scale hydrogenation of glucose [21,22], mostly because of its low price [23]. Nevertheless, the
lower catalytic activity of nickel as compared to other precious-metal-based conventional hydrogenation
catalysts, such as ruthenium, results in the need for high hydrogen pressure and harsh operating
conditions. Consequently, a significant energy demand must be satisfied compared to that required
when using more active hydrogenation catalysts and, thus, higher environmental impacts are associated
with the use of Raney nickel catalysts [24].
This work focuses on gaining insights into a developing alternative reaction pathway to the
conventional hydrogenation procedure used to transform glucose into sorbitol by exploring the
feasibility of carrying out the transformation through catalytic transfer hydrogenation (CTH) using a
hydrogen donor. CTH is, a priori, a more sustainable alternative to conventional hydrogenation with
molecular hydrogen because of the lower requirements for high-pressure conditions. CTH is usually
performed in the presence of hydrogen donors, such as small alcohols and acids, which can be used
under liquid phase conditions and under moderate operation conditions, and which are potentially
easily prepared from renewable biomass feedstock [25–27].
Reduction of glucose to sorbitol via CTH is scarcely reported for catalysts based on Pt, Rh, or
Ru [28,29], and only a few contributions focused on using nickel catalysts [29,30]. Thus, Scholz et al. [30]
studied the CTH of glucose to sorbitol, in the presence of hydrotalcite-derived catalysts (Cu6−X NiX Al2 ),
suggesting that Ni-based catalysts, such as Raney-type metal sponges could display notable catalytic
activity in the CTH reduction of glucose. In previous work, we demonstrated that the use of the
already industrially implemented Raney nickel catalysts is a good option to be used in a different
operational procedure to that conventionally used for the ring-opening hydrogenation from glucose to
sorbitol [31]. Within this context, the present work deals with the understanding of the behavior of
several Raney nickel catalysts, as well as the influence of important operational parameters like the
temperature conditions or the catalyst loading, in the production of sorbitol from glucose through a
catalytic transfer hydrogenation mechanism, using short-chain alcohols as hydrogen donors.

2. Materials and Methods

2.1. Materials
d-Glucose (≥99.5%), fructose (≥99%), mannose (≥99%), sorbitol (99%), and mannitol (≥98%) were
purchased from Sigma-Aldrich (USA) and used without prior purification. A-4000, A-5000, and A-7063
sponge Nickel™ Catalyst were kindly provided by Johnson Matthey Process Technologies.

2.2. Catalytic Tests

The CTH catalytic tests were performed in a 100-mL stainless-steel batch reactor (Autoclave
Engineers) fitted with a temperature controller, a mechanical stirrer, and a pressure transducer to
monitor the reaction conditions. In a typical assay, 75 mL of a 90 mM d-glucose alcohol solution was
loaded in the reactor vessel together with an appropriate amount of Raney nickel catalyst. Before its use,
the catalyst was suspended in the same alcohol used for the catalytic test and outgassed by sonication.
Appl. Sci. 2020, 10, 1843 3 of 12

The autoclave was then closed and fluxed with nitrogen to ensure inert conditions, and the temperature
(130–190 ◦ C) and stirring condition (500 rpm) were set up. Autogenous pressure conditions were used
in all the experiments; thus, operation was performed in the pressure range 9–26 bar, depending on the
applied reaction temperature. Sample aliquots were periodically withdrawn from the reaction media
to monitor the conversion of the substrate and the yield toward the different products. The reaction
was cooled down with an ice water bath after 6 h. The catalysts were recovered by simple filtration
and washed with fresh solvent.

2.3. Analysis of Products

The analysis of the reaction products was performed using both HPLC and GC analyses.
High-performance liquid-phase chromatography was performed in an Agilent 1260 Infinity unit
coupled with evaporative light scattering and UV-diode array detectors. Product separations were
performed using a Hi-Plex Ca, 300 × 7.7 mm column, using water as the mobile phase at a flow rate of
0.6 mL·min−1 and operating at 80 ◦ C. GC analysis was used for the quantification of volatiles such
as the aldehydes coming from the dehydrogenation of the sacrificing alcohol. These assays were
performed on a GC (Agilent) system fitted with a CP-WAX 57 CB column (L = 50 m, D = 0.25 mm,
film = 0.20 µm) and an FID detector. The catalytic result is shown either in terms of conversion of
glucose/fructose (Xi ) or in terms of yields (Yi ), calculated as follows:

[mol of i loaded in the reactor − mol i in product]

Xi ( % ) = ·100,
[mol of i loaded in the reactor]

[mol i in product]
Yi (%) = ·100.
[mol of substrate loaded in the reactor]

3. Results and Discussion

3.1. Influence of Sacrificing Alcohol

The capability of Raney nickel to drive the catalytic transfer hydrogenation of glucose to sorbitol
was assessed using different short-chain alcohols as solvents and sacrificing alcohols. For this purpose,
methanol, ethanol, and 2-propanol were used as potential hydrogen donors in the presence of a
conventional nickel sponge catalyst. These alcohols were previously reported to be suitable hydrogen
donors in different CTH reactions in the presence of nickel-based catalysts. Figure 1 depicts the
results achieved (cumulative product yields and substrate conversion) in the transformation of glucose
and fructose solutions prepared from the tested reaction solvents, treated in the presence of Raney
nickel catalyst. The cumulative product yields and substrate conversion are depicted for all the tested
short-chain alcohols. Substrate conversion was almost complete after reacting for 6 h, regardless of
the used solvent. The results from the blank test, which was accomplished by treating an aqueous
solution of glucose in the absence of any hydrogen donor, but in water, revealed that this substrate can
be transformed in the presence of Raney nickel catalysts into hexitols (sorbitol and mannitol) in quite a
large extension. This behavior was previously described to occur because of the reducing capability of
glucose, coming from its ability to donate a hydrogen molecule through the oxidation of the hydroxyl
group located in the α position, thus leading to the formation of gluconolactone. The H2 molecule is
then transferred, mediated by the nickel catalyst, to a different molecule of glucose, thus leading to the
formation of sorbitol via ring-opening hydrogenation, in a sort of disproportionation transformation of
glucose (one molecule is oxidized whereas another one is reduced). This phenomenon was previously
described to occur in the presence of metal catalysts such as Pd [29] and, more recently, Ru [32].
Nevertheless, the auto reduction of glucose is not the only transformation taking place in the reaction
medium as, together with sorbitol, mannitol, and fructose are also produced through side reaction
pathways. Fructose is most probably produced by the isomerization of glucose, a transformation
which can be mediated by the aluminum traces remaining in the catalysts after the preparation of
Appl. Sci. 2020, 10, 1843 4 of 12

the sponge-like catalysts (which account for more than 5%) or simply because of a thermal effect.
Mannitol, on the contrary, is not produced via the isomerization of sorbitol, but through (catalytic
Appl. Sci. 2020, 10, x FOR PEER REVIEW 4 of 12
transfer) hydrogenation of fructose. All the detected chemical transformations are depicted in Scheme 1.
The ring-opening
produces, unlike in hydrogenation of this monosaccharide
the case of glucose, produces,
two different hexitol unlike
isomers, in theand
sorbitol casemannitol,
of glucose,
in
two different hexitol isomers, sorbitol and mannitol, in equimolecular amounts,
equimolecular amounts, depending on which side of the sugar ring is approached by the depending on which
nickel
side of the
catalyst sugar
to be ring is approached by the nickel catalyst to be reduced.
reduced.

(a) (b)

Figure
Figure 1. Cumulative product
1. Cumulative product yields
yields (left
(left axes)
axes) and
and substrate conversion (right
substrate conversion (right axes)
axes) in
in the
the catalytic
catalytic
transfer hydrogenation of (a) glucose and (b) fructose, with different solvents in the presence of
transfer hydrogenation of (a) glucose and (b) fructose, with different solvents in the presence of RaneyRaney
nickel catalysts. Reaction conditions: temperature = 150 ◦ C; substrate concentration = 90 mM; substrate
nickel catalysts. Reaction conditions: temperature = 150 °C; substrate concentration = 90 mM; substrate
to catalyst mass ratio = 1:1; reaction time = 6 h.
to catalyst mass ratio = 1:1; reaction time = 6 h.

As for the influence of the type of short-chain alcohol used as a hydrogen donor, results evidenced
As for the influence of the type of short-chain alcohol used as a hydrogen donor, results
the formation of the same reaction products already described for the test performed in water. Large
evidenced the formation of the same reaction products already described for the test performed in
differences are evident between the product distributions achieved in the presence of each short-chain
water. Large differences are evident between the product distributions achieved in the presence of
alcohol, showing that the alcohol media do exert an influence on the product distribution. Thus,
each short-chain alcohol, showing that the alcohol media do exert an influence on the product
methanol provided a substantially lower amount of hexitols as compared to ethanol or 2-propanol.
distribution. Thus, methanol provided a substantially lower amount of hexitols as compared to
In this case, the presence of highly stable methyl glucopyranosides was detected in the reaction media,
ethanol or 2-propanol. In this case, the presence of highly stable methyl glucopyranosides was
coming from the etherification of the sugar monosaccharide in the α position with the alcohol solvent.
detected in the reaction media, coming from the etherification of the sugar monosaccharide in the α
This transformation avoids glucose undergoing dehydrogenative oxidation toward gluconolactone,
position with the alcohol solvent. This transformation avoids glucose undergoing dehydrogenative
depressing the extension of the sugar disproportionation and the consequent production of sorbitol.
oxidation toward gluconolactone, depressing the extension of the sugar disproportionation and the
On the other hand, alkyl glucopyranosides were detected in trace levels when using ethanol and
consequent production of sorbitol. On the other hand, alkyl glucopyranosides were detected in trace
2-propanol as hydrogen donors and reaction solvents. This is probably due to the better performance
levels when using ethanol and 2-propanol as hydrogen donors and reaction solvents. This is probably
of ethyl and 2-propyl moieties as leaving groups, and the consequent lower stability of the resultant
due to the better performance of ethyl and 2-propyl moieties as leaving groups, and the consequent
alkyl glucopyranosides under the tested reaction conditions. In this way, the achieved sorbitol yield in
lower stability of the resultant alkyl glucopyranosides under the tested reaction conditions. In this
tests performed in the presence of different alcohols varies according to the following trend: ethanol >
way, the achieved sorbitol yield in tests performed in the presence of different alcohols varies
2-propanol > methanol.
according to the following trend: ethanol > 2-propanol > methanol.
Unlike methanol, ethanol and 2-propanol provide sorbitol yield values higher than those obtained
Unlike methanol, ethanol and 2-propanol provide sorbitol yield values higher than those
in aqueous phase conditions, suggesting the existence of a net contribution to the formation of sorbitol
obtained in aqueous phase conditions, suggesting the existence of a net contribution to the formation
coming from the hydrogen transfer from these alcohol solvents to the sugar substrate. To assess this
of sorbitol coming from the hydrogen transfer from these alcohol solvents to the sugar substrate. To
possibility, several additional experiments were performed. Firstly, the analysis of the reaction media
assess this possibility, several additional experiments were performed. Firstly, the analysis of the
using gas chromatography analysis confirmed the presence of acetaldehyde and acetone evolved during
reaction media using gas chromatography analysis confirmed the presence of acetaldehyde and
the dehydrogenation of ethanol and 2-propanol, respectively. On the contrary, formaldehyde was
acetone evolved during the dehydrogenation of ethanol and 2-propanol, respectively. On the
not detected, evidencing that, unlike for ethanol and 2-propanol, the catalytic transfer hydrogenation
contrary, formaldehyde was not detected, evidencing that, unlike for ethanol and 2-propanol, the
from methanol does not occur under the tested conditions. Secondly, several catalytic tests were
catalytic transfer hydrogenation from methanol does not occur under the tested conditions. Secondly,
also performed, this time under the very same reaction conditions as those already described for
several catalytic tests were also performed, this time under the very same reaction conditions as those
glucose, instead using fructose as the reaction substrate. Fructose, unlike glucose, cannot undergo
already described for glucose, instead using fructose as the reaction substrate. Fructose, unlike
disproportionation because the quaternary carbon at the furanose sugar ring cannot donate an
glucose, cannot undergo disproportionation because the quaternary carbon at the furanose sugar ring
H2 molecule.
cannot donate an H2 molecule.
Appl. Sci. 2020, 10, 1843 5 of 12
Appl. Sci. 2020, 10, x FOR PEER REVIEW 5 of 12

Scheme
Scheme 1. 1.Chemical
Chemical transformations occurringwhen
transformations occurring whentreating
treatingglucose
glucosein in
thethe presence
presence of Raney
of Raney nickel
nickel in alcohol media: (a) catalytic transfer hydrogenation from glucose to sorbitol,
in alcohol media: (a) catalytic transfer hydrogenation from glucose to sorbitol, (b) glucose (b) glucose
dehydrogenation
dehydrogenation to to
gluconolactone,
gluconolactone, (c)(c)
glucose isomerization
glucose isomerizationto to
fructose, and
fructose, (d)(d)
and catalytic transfer
catalytic transfer
hydrogenation from fructose to sorbitol and mannitol.
hydrogenation from fructose to sorbitol and mannitol.

Thus,
Thus, thethe
reduction
reduction of of
fructose under
fructose underthethe
tested
testedconditions
conditions should
should come
come from
from thethe
catalytic
catalytic
hydrogen transfer from the sacrificing alcohol. Under these conditions, methanol
hydrogen transfer from the sacrificing alcohol. Under these conditions, methanol only provided only provided traces
of traces
hexitols, confirming that methanol is not a good option as a hydrogen donor
of hexitols, confirming that methanol is not a good option as a hydrogen donor for glucose for glucose CTH.
OnCTH.
the contrary, both ethanol and 2-propanol led to quantifiable amounts of sorbitol
On the contrary, both ethanol and 2-propanol led to quantifiable amounts of sorbitol and and mannitol,
present in
mannitol, almost equimolar
present in almost amounts as that
equimolar corresponding
amounts as that to the non-stereotocontrolled
corresponding hydrogenation
the non-stereo controlled
of hydrogenation
fructose. Nevertheless, ethanol provided lower amounts of mannitol, probably
of fructose. Nevertheless, ethanol provided lower amounts of mannitol, as a consequence
probably as
of athe lower extentofofthe
consequence isomerization
lower extent reactions in the presence
of isomerization of thisin
reactions solvent. Furthermore,
the presence of thisethanol
solvent.
seems to be a better hydrogen donor than 2-propanol under the tested
Furthermore, ethanol seems to be a better hydrogen donor than 2-propanol under the conditions, bearing in mind
tested
theconditions,
higher hexitol yields
bearing in obtained
mind thewith the primary
higher alcohol.
hexitol yields This behavior
obtained with theis primary
probably alcohol.
due to theThis
neutral conditions used during the catalytic tests, which favor the dehydrogenation of
behavior is probably due to the neutral conditions used during the catalytic tests, which favor the primary alcohols
over secondary onesof[33].
dehydrogenation primaryThe alcohols
better performance
over secondaryof ethanol as The
ones [33]. a sacrificing alcohol as of
better performance compared
ethanol as
to amethanol
sacrificing alcohol as compared to methanol or 2-propanol introduces an additional advantagetofor
or 2-propanol introduces an additional advantage for the CTH reduction of glucose
sorbitol,
the CTH which is the possibility
reduction of glucose to toobtain ethanol
sorbitol, whichfrom renewable
is the possibilitybiomass via ethanol
to obtain fermentation through
from renewable
well-known industrially scaled processes.
biomass via fermentation through well-known industrially scaled processes.
3.2. Influence of the Reaction Temperature and Catalyst Loading
3.2. Influence of the Reaction Temperature and Catalyst Loading
Blank reactions were performed to assess the different side reactions taking place in the absence
Blank reactions were performed to assess the different side reactions taking place in the absence
of Raney nickel catalysts. These tests were performed in the temperature range 130–190 ◦ C. Results
of Raney nickel catalysts. These tests were performed in the temperature range 130–190 °C. Results
are depicted in Figure 2. Regardless of the temperature, fructose and mannose were obtained even
are depicted in Figure 2. Regardless of the temperature, fructose and mannose were obtained even in
in the milder conditions, most probably coming from the isomerization of the starting glucose.
the milder conditions, most probably coming from the isomerization of the starting glucose. The
The extension of these transformations increases as the temperature rises, although, at 190 ◦ C, lower
extension of these transformations increases as the temperature rises, although, at 190 °C, lower
yields toward both mannose and fructose were detected. This is probably related to the existence of
yields toward both mannose and fructose were detected. This is probably related to the existence of
sugar monosaccharide-consuming side reactions, such as the dehydration of glucose/fructose toward
sugar monosaccharide-consuming side reactions, such as the dehydration of glucose/fructose toward
5-hydroxymethyl furfural [34]. Finally, blank tests also served to confirm the true catalytic activity of
5-hydroxymethyl furfural [34]. Finally, blank tests also served to confirm the true catalytic activity of
nickel in the above-observed hydrogen transfer reduction from glucose to sorbitol, as, in the absence of
nickel in the above-observed hydrogen transfer reduction from glucose to sorbitol, as, in the absence
the metal catalyst, no sorbitol was detected.
of the metal catalyst, no sorbitol was detected.
Appl. Sci. 2020, 10, x FOR PEER REVIEW 6 of 12
Appl. Sci. 2020, 10, 1843 6 of 12

Figure 2. Cumulative product yields achieved in blank reactions performed at different temperatures.
Figure 2. Cumulative product
Reaction conditions: yields
substrate achieved=in
concentration 90blank time =performed
reactions
mM; reaction 6 h. at different temperatures.
Reaction conditions: substrate
The influence of severalconcentration = 90 mM;
operational parameters reaction
(reaction time = 6and
temperature h. catalyst loading) was
assessed in the catalytic transfer hydrogenation of glucose to sorbitol, using ethanol as a sacrificing
The influence of several
alcohol. Figure 3 depictsoperational parameters
the product yields (reaction
and substrate conversiontemperature
achieved in the and catalyst
catalytic testsloading) was
conducted at different temperatures, within the range 130–190 ◦ C, and in the presence of two catalyst
assessed in the catalytic transfer hydrogenation of glucose to sorbitol, using ethanol as a sacrificing
loadings (glucose to catalyst mass ratios = 8:1 and 1:1). The influence of both operation parameters
alcohol. Figure 3 depicts the product yields and substrate conversion achieved in the catalytic tests
on the glucose conversion rate was as expected, i.e., larger catalyst loading and temperature led to
conductedfaster
at different temperatures,
substrate conversion. withindistribution,
As for product the rangesorbitol
130–190 was°C, andasin
present thethe
mainpresence
product inofall two catalyst
tested conditions.
loadings (glucose to catalystHowever, mass theratios
influence of the
= 8:1 temperature
and 1:1). The and catalyst loading
influence of both on the selectivity parameters
operation
to the different products provided quite distinct results, as a consequence of a different effect of both
on the glucose conversion rate was as expected, i.e., larger catalyst loading and temperature led to
operation parameters on the extension of not only the main reaction but also of the different side
faster substrate
reactionsconversion.
taking place under As for theproduct distribution, sorbitol was present as the main product in
tested conditions.
all tested conditions.
The catalystHowever,
loading exerted thea dramatic
influence of the
influence temperature
on the and isomerization
extension of glucose catalyst loading to on the
fructose and mannose. Assays performed with a lower catalyst loading resulted
selectivity to the different products provided quite distinct results, as a consequence of a different in a poorer selectivity
toward the desired sorbitol, and a large amount of side products, such as mannose and fructose, were
effect of both operation parameters on the extension of not only the main reaction but also of the
observed (Figure 3a–d). This influence was even higher when increasing the applied temperature.
different side reactions
Increasing taking
the catalyst place
loading ledunder the tested
to substantial conditions.
suppression of the extension of sugar isomerization
reactions, and only a limited production
The catalyst loading exerted a dramatic influence on theof fructose and mannose, below 10% total of
extension yield, was observed,
glucose isomerization to
even in the highest-temperature conditions. These results, together with those achieved from the blank
fructose and mannose. Assays performed with a lower catalyst loading resulted in a poorer selectivity
tests, confirmed that the conversion of glucose into its different isomers is, under the tested reactions
toward theconditions,
desired sorbitol, and a large
a side transformation amount
not related of Raney
to the side products,
nickel catalystsuch asamannose
but to and fructose, were
thermal effect.
observed (Figure As for3a–d). This influence
the production was
of sorbitol, the even higher
extension whentransfer
of the catalytic increasing the applied
hydrogenation of glucosetemperature.
to this hexitol seems to be highly dependent on the catalyst
Increasing the catalyst loading led to substantial suppression of the extension of sugarloading. Thus, a substrate to catalyst
isomerization
mass ratio of 8:1 provided a limited production of sorbitol, even in the highest tested temperature
reactions, conditions,
and onlyleading a limited
to sorbitolproduction
yields alwaysof fructose
below and
25% of the mannose,
starting below 10%
glucose. Increasing total yield, was
the catalyst
observed, loading
even in to athe highest-temperature
substrate to catalyst mass ratio conditions. These
of 1:1 led to much moreresults, togetherofwith
efficient conversion those achieved
the sugar
monosaccharide
from the blank into sorbitol.
tests, confirmed Thisthe
that transformation
conversion wasofvery efficientinto
glucose in theits
lowest tested temperature
different isomers is, under the
conditions (130 ◦ C), and sorbitol yields around 60% were, thus, produced after reacting for 6 h. Total
tested reactions conditions, a side transformation not related to the Raney nickel catalyst but to a
carbon balance was, under these conditions, very high, and about 80% of the starting substrate could
thermal effect.
be quantified as different products after reacting for 6 h. This result is strong evidence of the catalytic
As fortransfer
the production
hydrogenation ofmainly
sorbitol,
takingthe extension
place of the catalytic
from the sacrificing ethanol totransfer hydrogenation
sorbitol, not from the sugar of glucose
disproportionation, and a confirmation of the high potential of CTH for the transformation of glucose
to this hexitol seems to be highly dependent on the catalyst loading. Thus, a substrate to catalyst mass
into sorbitol using sacrificing alcohols.
ratio of 8:1 provided a limited production of sorbitol, even in the highest tested temperature
conditions, leading to sorbitol yields always below 25% of the starting glucose. Increasing the catalyst
loading to a substrate to catalyst mass ratio of 1:1 led to much more efficient conversion of the sugar
monosaccharide into sorbitol. This transformation was very efficient in the lowest tested temperature
conditions (130 °C), and sorbitol yields around 60% were, thus, produced after reacting for 6 h. Total
carbon balance was, under these conditions, very high, and about 80% of the starting substrate could
be quantified as different products after reacting for 6 h. This result is strong evidence of the catalytic
Appl. Sci. 2020, 10, 1843 7 of 12
Appl. Sci. 2020, 10, x FOR PEER REVIEW 7 of 12

(e)
(a)

(b) (f)

(c) (g)

(d) (h)

Figure3.3.Cumulative
Figure Cumulative product
productyields (bars,
yields left axes)
(bars, and substrate
left axes) conversion
and substrate (dots, right
conversion axes)
(dots, achieved
right axes)
in the catalytic
achieved in thetransfer
catalytichydrogenation of glucoseofinglucose
transfer hydrogenation ethanolininethanol
the presence of Raneyof
in the presence nickel
Raneycatalyst
nickel
with different
catalyst substrate-to-catalyst
with different weight ratios
substrate-to-catalyst weight(1:8—left column, column,
ratios (1:8—left graphs a–d); (1:1—right
graphs column,
a–d); (1:1—right
graphs e–h). Reaction conditions: substrate concentration = 90 mM; reaction time
column, graphs e–h). Reaction conditions: substrate concentration = 90 mM; reaction time = 6 h; = 6 h; reaction
temperature = 130 ◦ C =(a,e),
reaction temperature 130 150
◦ C (b,f), 170 ◦ C (c,g), and 190 ◦ C (d,h).
°C (a,e), 150 °C (b,f), 170 °C (c,g), and 190 °C (d,h).
Appl. Sci. 2020, 10, 1843 8 of 12

Increasing the reaction temperature led to, as stated above, acceleration of the substrate conversion,
as well as diminishing sorbitol yields at long reaction times. The reasons for this phenomenon can
be found in the enhancement of side reactions, such as sugar isomerization, as well as some other
transformations related to the consumption of sorbitol, such as its hydrogenolysis. These side reactions
usually take place in high-temperature conditions, such that these are highly influenced by a thermal
effect. The transformations occur through the cleavage of sorbitol into different smaller polyols.
The analysis of the liquid phase of the reaction media using GC allowed detecting some of the heavier
products coming from these transformations, such as ethylene glycol, 1,2-propanediol, and glycerol.

3.3. Influence of Catalyst Doping Agents

Unlike for glucose hydrogenation, where extensive literature can be found, studies devoted to
ascertaining the influence in CTH of different dopants in the catalytic activity of Raney-type nickel
catalysts are not yet reported. Thus, this section is focused on evaluating the influence of typical metal
promoters for Raney nickel catalysts, like Fe–Cr and Mo (Table 1), on their ability to promote glucose
conversion to sorbitol via CTH from ethanol. Nickel, like other metals from the VIII group, can interact
with glucose through the carbonyl group, which is the basis of the catalytic activity of nickel in the
hydrogenation of glucose. Fe–Cr and Mo species in Raney nickel catalysts act as Lewis acid sites,
providing oxophilicity to the catalyst [15,22,35–37], and they modify the affinity of nickel for the C=O
group, necessarily conditioning its activity in hydrogenation or hydrogen transfer reactions. Figure 4
depicts the kinetic profiles obtained in the conversion of glucose to sorbitol, as well as the evolution of
side products, performed at 150 ◦ C, and in the presence of different Raney nickel catalysts (Table 1).

Table 1. Chemical composition of Raney nickel catalyst used in this work.

Catalogue # Ni (wt.%) Al (wt.%) Fe (wt.%) Mo (wt.%) Cr (wt.%)

A-5000 93.9 5.5 — — —
A-7063 93.3 5.8 — 1.1 —
A-4000 85.6 8.6 2.3 — 2.5

The conversion of glucose in the presence of unpromoted Raney nickel catalyst (Figure 4a) reached
64.9% after reacting for 6 h. Sorbitol evolved as the main product, together with small quantities of
fructose. Fe–Cr-doped Raney nickel led to an almost identical profile for glucose conversion, maybe
slightly faster during the early stages of the reaction (Figure 4b). However, this catalyst provided lower
substrate conversion (~60%) than the unpromoted catalyst, probably as a consequence of a deactivation
phenomenon, conventionally occurring on Fe–Cr-doped Raney nickel through the leaching of the
dopant agents [22]. The achieved sorbitol yield was much lower in the presence of Fe–Cr-doped catalyst
than in the unpromoted one and, thus, only 11.5% of the starting glucose was obtained as sorbitol.
Interestingly, a major fraction of the evolving sorbitol was obtained during the early stages of the
reaction (up to 1 h), resulting in the concentration of this product becoming almost constant during the
rest of the reaction. This low amount of sorbitol was accompanied by the evolution of fructose, which
was produced after the first hour, reaching yield values around 10%–15%. This poor performance of
the Ni–Cr-doped catalyst seems to be related to the leaching of the iron and chromium species and
their dissolution in the solvent of the reaction [22]. Iron and chromium act as hydrogenation promoters
for nickel, but their lixiviation eliminates their capacity to bind glucose molecules to the surface of
the catalyst, although their Lewis acid features remain intact. In this way, the leached, Lewis acid Cr
and Fe species do not promote catalytic transfer hydrogenation, but the isomerization of glucose to
fructose [38,39], which seems to become the dominant reaction after the first hour. Fructose is, unlike
glucose, a substrate more resistant to undergoing CTH and, thus, only scarce evolution of sorbitol was
detected after its production. The different kinetic profiles achieved for the products obtained in the
presence of the Fe–Cr-promoted catalyst suggest that the deactivation of this material occurred during
the first hour of the catalytic test.
 Appl. Sci. 2020, 10, x FOR PEER REVIEW 9 of 12

Appl. Sci. 2020,

catalyst 10, 1843that
suggest 9 of 12
the deactivation of this material occurred during the first hour of the catalytic
test.
The molybdenum-promoted Raney nickel displayed a completely different catalytic
The molybdenum-promoted Raney nickel displayed a completely different catalytic performance
performance to that shown by the Fe–Cr-doped material. In this case, a faster and more selective
to that shown by the Fe–Cr-doped material. In this case, a faster and more selective transformation
transformation of glucose into sorbitol was observed (glucose conversion of ~78.5% and sorbitol yield
of glucose into sorbitol was observed (glucose conversion of ~78.5% and sorbitol yield of 38.4%).
of 38.4%). Interestingly, low amounts of fructose were observed during the overall reaction test (<6%),
Interestingly, low amounts of fructose were observed during the overall reaction test (<6%), suggesting
suggesting that, despite the Lewis acid features shown by molybdenum sites, its catalytic activity in
that, despite the Lewis acid features shown by molybdenum sites, its catalytic activity in glucose
glucose isomerization seems quite limited, and the beneficial influence of this metal on the capability
isomerization seems quite limited, and the beneficial influence of this metal on the capability of nickel
of nickel to promote CTH becomes dominant.
to promote CTH becomes dominant.

(a)

(b)

(c)

Figure
Figure Kinetic
4. 4. profiles
Kinetic obtained
profiles obtainedforfor
glucose conversion
glucose conversion toto
sorbitol inin
sorbitol the presence
the ofof
presence Raney
Raneynickel
nickel
type
type catalysts in ethanol: (a) unpromoted Raney nickel, (b) Fe–Cr-promoted Raney nickel, and (c) (c)
catalysts in ethanol: (a) unpromoted Raney nickel, (b) Fe–Cr-promoted Raney nickel, and Mo-
Mo-promoted
promoted Raney Raney nickel.
nickel. Reaction
Reaction conditions:
conditions: [glucose] = 90=mM,
[glucose] 90 mM, catalyst
catalyst to substrate
to substrate weight
weight ratio =
1:4;=reaction
ratio 1:4; reaction = 150=°C.
temperature
temperature 150 ◦ C.
Appl. Sci. 2020, 10, 1843 10 of 12

This better performance of Mo as compared to Fe–Cr dopants seems to be related to its stability in
the catalyst, something that can be ascertained from the negligible amount of leached Mo detected in
the reaction media after the catalytic tests. In this way, the influence of Mo dopant is interpreted based
on its capacity to bind glucose to the metal surface. Its oxophilicity leads to the interaction with the
aldehyde group of glucose and, thus, an upward configuration is assumed for the carbonyl group,
in which the η1 (O) adsorbed species is formed by the donation of a lone electron pair from the oxygen
atom at the C=O group to the molybdenum atom. As a result, the C=O bond gets polarized and the
carbon atom can undergo a nucleophilic attack from a hydride group located at adjacent nickel atoms,
thus leading to its reduction [22,40]. Hydride groups can be formed via the dehydrogenation of the
sacrificing alcohol anywhere over the surface of the Raney nickel catalysts, before migrating through
a spillover effect to the CHT sites. These results prompt Mo-promoted Raney-nickel catalysts as a
promising selective catalyst for the catalytic transfer hydrogenation of glucose to sorbitol.

4. Conclusions
The production of sorbitol via catalytic transfer hydrogenation with Raney nickel catalysts was
evaluated using short-chain alcohols as hydrogen donors. The comparative study of the performance
shown using different sacrificing alcohols demonstrated ethanol as the best hydrogen donor under the
tested conditions. This implies advantages from an environmental point of view, as the production of
ethanol from biomass is an economic and technical feasible possibility. Moreover, glucose was proven
to be able to undergo a disproportionation reaction, thus confirming that the production of sorbitol can
be accomplished using self-reduction and catalytic transfer hydrogenation from the sacrificing alcohol.
Catalyst loading was revealed as a key parameter conditioning the product distribution obtained when
treating ethanolic solutions of glucose. High catalytic loadings enhanced the production of sorbitol,
which, in combination with low-temperature conditions, led to the efficient transformation of glucose
into sorbitol through the catalytic transfer hydrogenation pathway. Finally, the use of Raney nickel
catalysts doped with different promoters is another factor liable to be used to enhance the yield to
sorbitol. The use of molybdenum-doped Raney nickel catalyst exerts a beneficial effect, favoring the
stability of nickel and enhancing the reduction of glucose to sorbitol.

Author Contributions: Conceptualization, J.I. and J.M.; methodology, B.G.; validation, G.M. and J.A.M.; formal
analysis, J.I.; investigation, B.G.; writing—original draft preparation, B.G. and J.I.; writing—review and editing,
J.M., G.M., J.A.M., and J.I.; supervision, J.M. and J.I.; project administration, G.M., J.A.M., and J.I.; funding
acquisition, G.M., J.A.M., and J.I. All authors read and agreed to the published version of the manuscript.
Funding: This research was funded by the Spanish Ministry of Science, Innovation and Universities (project
RTI2018-094918-B-C42) and by the Regional Government of Madrid (project BIOTRES-CM P2018/EMT-4344).
Acknowledgments: B. García kindly acknowledges the Regional Government of Madrid for a research contract
(PEJD-2016/AMB-2321) funded through the European Social Fund. Johnson Matthey Process Technologies Co. is
kindly acknowledged for providing the Raney nickel catalysts used in this investigation.
Conflicts of Interest: The authors declare no conflicts of interest.

References
1. Murillo Leo, I.; López Granados, M.; Fierro, J.L.G.; Mariscal, R. Selective conversion of sorbitol to glycols
and stability of nickel–ruthenium supported on calcium hydroxide catalysts. Appl. Catal. B Environ. 2016,
185, 141–149. [CrossRef]
2. Romero, A.; Alonso, E.; Sastre, Á.; Nieto-Márquez, A. Conversion of biomass into sorbitol: Cellulose
hydrolysis on MCM-48 and d-Glucose hydrogenation on Ru/MCM-48. Microporous Mesoporous Mater. 2016,
224, 1–8. [CrossRef]
3. Kumar, P.; Barrett, D.M.; Delwiche, M.J.; Stroeve, P. Methods for Pretreatment of Lignocellulosic Biomass for
Efficient Hydrolysis and Biofuel Production. Ind. Eng. Chem. Res. 2009, 48, 3713–3729. [CrossRef]
4. Patil, C.R.; Rode, C.V. Synthesis of diesel additives from fructose over PWA/SBA-15 catalyst. Fuel 2018, 217,
38–44. [CrossRef]
Appl. Sci. 2020, 10, 1843 11 of 12

5. Robinson, J.M.; Wadle, A.M.; Reno, M.D.; Kidd, R.; Barrett Hinsz, S.R.; Urquieta, J. Solvent- and
Microwave-Assisted Dehydrations of Polyols to Anhydro and Dianhydro Polyols. Energy Fuels 2015,
29, 6529–6535. [CrossRef]
6. Zada, B.; Chen, M.; Chen, C.; Yan, L.; Xu, Q.; Li, W.; Guo, Q.; Fu, Y. Recent advances in catalytic production
of sugar alcohols and their applications. Sci. China Chem. 2017, 60, 853–869. [CrossRef]
7. Zhang, J.; Li, J.B.; Wu, S.B.; Liu, Y. Advances in the Catalytic Production and Utilization of Sorbitol. Ind. Eng.
Chem. Res. 2013, 52, 11799–11815. [CrossRef]
8. Bozell, J.J.; Petersen, G.R. Technology development for the production of biobased products from biorefinery
carbohydrates—The US Department of Energy’s “Top 10” revisited. Green Chem. 2010, 12, 539–554. [CrossRef]
9. Fukuoka, A.; Dhepe, P.L. Catalytic Conversion of Cellulose into Sugar Alcohols. Angew. Chem. Int. Ed. 2006,
45, 5161–5163. [CrossRef]
10. Ji, N.; Zhang, T.; Zheng, M.; Wang, A.; Wang, H.; Wang, X.; Chen, J.G. Direct Catalytic Conversion of Cellulose
into Ethylene Glycol Using Nickel-Promoted Tungsten Carbide Catalysts. Angew. Chem. Int. Ed. 2008, 47,
8510–8513. [CrossRef]
11. Van de Vyver, S.; Geboers, J.; Dusselier, M.; Schepers, H.; Vosch, T.; Zhang, L.; Van Tendeloo, G.; Jacobs, P.A.;
Sels, B.F. Selective Bifunctional Catalytic Conversion of Cellulose over Reshaped Ni Particles at the Tip of
Carbon Nanofibers. ChemSusChem 2010, 3, 698–701. [CrossRef] [PubMed]
12. Singh, H.; Rai, A.; Yadav, R.; Sinha, A.K. Glucose hydrogenation to sorbitol over unsupported mesoporous
Ni/NiO catalyst. Mol. Catal. 2018, 451, 186–191. [CrossRef]
13. Hausoul, P.J.C.; Beine, A.K.; Neghadar, L.; Palkovits, R. Kinetics study of the Ru/C-catalysed hydrogenolysis
of polyols—Insight into the interactions with the metal surface. Catal. Sci. Technol. 2017, 7, 56–63. [CrossRef]
14. Li, J.; Soares, H.S.; Moulijn, J.A.; Makkee, M. Simultaneous hydrolysis and hydrogenation of cellobiose to
sorbitol in molten salt hydrate media. Catal. Sci. Technol. 2013, 3, 1565–1572. [CrossRef]
15. Hoffer, B.W.; Crezee, E.; Mooijman, P.R.M.; van Langeveld, A.D.; Kapteijn, F.; Moulijn, J.A. Carbon supported
Ru catalysts as promising alternative for Raney-type Ni in the selective hydrogenation of d-glucose. Catal.
Today 2003, 79–80, 35–41. [CrossRef]
16. van Gorp, K.; Boerman, E.; Cavenaghi, C.V.; Berben, P.H. Catalytic hydrogenation of fine chemicals: Sorbitol
production. Catal. Today 1999, 52, 349–361. [CrossRef]
17. Li, Z.; Liu, Y.; Wu, S. Efficient Conversion of D-Glucose into D-Sorbitol over Carbonized Cassava
Dregs-Supported Ruthenium Nanoparticles Catalyst. BioResources 2018, 13, 1278–1288. [CrossRef]
18. Ribeiro, L.S.; Órfão, J.J.; Pereira, M.F.R. Comparative study of different catalysts for the direct conversion of
cellulose to sorbitol. Green Process. Synth. 2015, 4, 71–78. [CrossRef]
19. Yamaguchi, A.; Sato, O.; Mimura, N.; Shirai, M. Catalytic production of sugar alcohols from lignocellulosic
biomass. Catal. Today 2016, 265, 199–202. [CrossRef]
20. Zhang, X.; Durndell, L.J.; Isaacs, M.A.; Parlett, C.M.A.; Lee, A.F.; Wilson, K. Platinum-Catalyzed
Aqueous-Phase Hydrogenation of d-Glucose to d-Sorbitol. ACS Catal. 2016, 6, 7409–7417. [CrossRef]
21. Aho, A.; Roggan, S.; Eränen, K.; Salmi, T.; Murzin, D.Y. Continuous hydrogenation of glucose with ruthenium
on carbon nanotube catalysts. Catal. Sci. Technol. 2015, 5, 953–959. [CrossRef]
22. Gallezot, P.; Nicolaus, N.; Flèche, G.; Fuertes, P.; Perrard, A. Glucose Hydrogenation on Ruthenium Catalysts
in a Trickle-Bed Reactor. J. Catal. 1998, 180, 51–55. [CrossRef]
23. Zhang, J.; Wu, S.; Liu, Y.; Li, B. Hydrogenation of glucose over reduced Ni/Cu/Al hydrotalcite precursors.
Catal. Commun. 2013, 35, 23–26. [CrossRef]
24. Gericke, D.; Ott, D.; Matveeva, V.G.; Sulman, E.; Aho, A.; Murzin, D.Y.; Roggan, S.; Danilova, L.; Hessel, V.;
Loeb, P.; et al. Green catalysis by nanoparticulate catalysts developed for flow processing? Case study of
glucose hydrogenation. RSC Adv. 2015, 5, 15898–15908. [CrossRef]
25. Bulushev, D.A.; Ross, J.R. Towards Sustainable Production of Formic Acid. ChemSusChem 2018, 11, 821–836.
[CrossRef]
26. Sarkar, N.; Ghosh, S.K.; Bannerjee, S.; Aikat, K. Bioethanol production from agricultural wastes: An overview.
Renew. Energy 2012, 37, 19–27. [CrossRef]
27. Gilkey, M.J.; Xu, B. Heterogeneous Catalytic Transfer Hydrogenation as an Effective Pathway in Biomass
Upgrading. ACS Catal. 2016, 6, 1420–1436. [CrossRef]
Appl. Sci. 2020, 10, 1843 12 of 12

28. Komanoya, T.; Kobayashi, H.; Hara, K.; Chun, W.-J.; Fukuoka, A. Simultaneous formation of sorbitol and
gluconic acid from cellobiose using carbon-supported ruthenium catalysts. J. Energy Chem. 2013, 22, 290–295.
[CrossRef]
29. van Hengstum, A.J.; Kieboom, A.P.G.; van Bekkum, H. Catalytic Transfer Hydrogenation of Glucose-Fructose
Syrups in Alkaline Solution. Starch Stärke 1984, 36, 317–320. [CrossRef]
30. Scholz, D.; Aellig, C.; Mondelli, C.; Pérez-Ramírez, J. Continuous Transfer Hydrogenation of Sugars to
Alditols with Bioderived Donors over Cu–Ni–Al Catalysts. ChemCatChem 2015, 7, 1551–1558. [CrossRef]
31. García, B.; Moreno, J.; Iglesias, J.; Melero, J.A.; Morales, G. Transformation of Glucose into Sorbitol on Raney
Nickel Catalysts in the Absence of Molecular Hydrogen: Sugar Disproportionation vs. Catalytic Hydrogen
Transfer. Top. Catal. 2019, 62, 570–578. [CrossRef]
32. Kobayashi, H.; Matsuhashi, H.; Komanoya, T.; Hara, K.; Fukuoka, A. Transfer hydrogenation of cellulose to
sugar alcohols over supported ruthenium catalysts. Chem. Commun. 2011, 47, 2366–2368. [CrossRef]
33. Chaloner, P.A.; Esteruelas, M.A.; Joo, F.; Oro, L. Homogeneous Hydrogenation; Kluwer Academic Publishers:
Dordrecht, The Netherlands, 1994; Volume 15.
34. Jing, Q.; LÜ, X. Kinetics of Non-catalyzed Decomposition of Glucose in High-temperature Liquid Water.
Chin. J. Chem. Eng. 2008, 16, 890–894. [CrossRef]
35. Hoffer, B.W.; Crezee, E.; Devred, F.; Mooijman, P.R.M.; Sloof, W.G.; Kooyman, P.J.; van Langeveld, A.D.;
Kapteijn, F.; Moulijn, J.A. The role of the active phase of Raney-type Ni catalysts in the selective hydrogenation
of d-glucose to d-sorbitol. Appl. Catal. A Gen. 2003, 253, 437–452. [CrossRef]
36. Cerino, P.J.; Fleche, G.; Gallezot, P.; Salome, J.P. Activity and Stability of Promoted Raney-Nickel Catalysts in
Glucose Hydrogenation. In Studies in Surface Science and Catalysis; Guisnet, M., Barrault, J., Bouchoule, C.,
Duprez, D., Pérot, G., Maurel, R., Montassier, C., Eds.; Elsevier: Amsterdam, The Netherlands, 1991; Volume
59, pp. 231–236.
37. Court, J.; Damon, J.P.; Masson, J.; Wierzchowski, P. Hydrogenation of Glucose with Bimetallic Catalysts (NiM)
of Raney Type. In Studies in Surface Science and Catalysis; Guisnet, M., Barrault, J., Bouchoule, C., Duprez, D.,
Montassier, C., Pérot, G., Eds.; Elsevier: Amsterdam, The Netherlands, 1988; Volume 41, pp. 189–196.
38. Delidovich, I.; Palkovits, R. Catalytic Isomerization of Biomass-Derived Aldoses: A Review. ChemSusChem
2016, 9, 547–561. [CrossRef]
39. Caratzoulas, S.; Davis, M.E.; Gorte, R.J.; Gounder, R.; Lobo, R.F.; Nikolakis, V.; Sandler, S.I.; Snyder, M.A.;
Tsapatsis, M.; Vlachos, D.G. Challenges of and Insights into Acid-Catalyzed Transformations of Sugars.
J. Phys. Chem. C 2014, 118, 22815–22833. [CrossRef]
40. Noller, H.; Lin, W.M. Effect of additives upon Raney-Nickel alloy catalysts. React. Kinet. Catal. Lett. 1982, 21,
479–483. [CrossRef]

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