Catalysis Today 394-396 (2022) 247–255

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Catalysis Today
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Glycerol as raw material to an Argentinian biorefinery

Lisandro Ferrari a, b, Fernando Tuler a, Ezequiel Promancio a, Leonardo Gusé a,
Diego García Touza b, Carlos Casas b, Raúl A. Comelli a, *
a
Instituto de Investigaciones en Catálisis y Petroquímica “Ing. José Miguel Parera” – INCAPE (UNL–CONICET), Centro Científico Tecnológico-CONICET-Santa Fe, 3000
Santa Fe, Argentina
b
VARTECO QUÍMICA PUNTANA S.A., 1672 Villa Lynch, Pcia. de Buenos Aires, Argentina

A R T I C L E I N F O A B S T R A C T

Keywords: Glycerol, the “co-product” in the biodiesel process, can be considered as a raw material to expand a biorefinery
Glycerol scheme. Selective reductions and oxidations and steam reforming of glycerol were studied to produce added-
Propylene glycol value chemicals and energetic compounds, and also to show a possible integration of processes into a bio­
Hydrogen
refinery framework. Selective reductions of glycerol in gas phase produced: i) propylene glycol on Cu-Ce/Al2O3,
Ethylene glycol
reaching 99.8% conversion and 83.2% selectivity to propylene glycol; and ii) ethylene glycol on Ni/SiO2,
Dihydroxyacetone
Biorefinery achieving 100% conversion and 91% selectivity to ethylene glycol in the liquid fraction. These reduction re­
actions demand hydrogen, which can also be obtained by steam reforming of glycerol using Ni/Al2O3 promoted
by adding compounds as Ce, Co, Mg, and Zr; the steam reforming also produced carbon oxides and methane,
being possible to use the syngas (hydrogen plus carbon monoxide) and methane as energetic compounds and
carbon dioxide to carbonylation. Selective oxidations of glycerol in liquid phase produced: i) dihydroxyacetone
on Pt/K-FER, being the first active and selective monometallic catalyst for this transformation, improving the
catalytic behavior by using Pt-Bi/K-FER, reaching 75.9% conversion and 93.9% selectivity to dihydroxyacetone;
and ii) lactic acid on Cu/Al2O3, obtaining 99.8% conversion and 86.5% selectivity to lactic acid. From the strong
link with the productive sector, one pilot plant to produce 100 t/y of propylene glycol from glycerol but versatile
to also obtain acetol and/or ethylene glycol is in the final building stage, and another one for reforming glycerol
to produce the hydrogen demanded for those reduction processes was finished. Consequently, glycerol was
converted to propylene glycol, ethylene glycol, hydrogen, dihydroxyacetone, lactic acid, syngas, carbon dioxide,
and methane; therefore, the possible integration of the corresponding processes allows consider the co-product of
biodiesel as a compound to expand a biorefinery scheme.

1. Introduction
Due to the future shortage of products derived from petroleum and
environmental restrictions, biomass has acquired an increasing impor­
tance because it is an unique, sustainable, and renewable resource that
can provide fuels for transport, chemical compounds, and materials
which could replace those ones obtained from fossil fuels. In this
context, Biorefinery is defined as the functional unit to transform biomass
into fuels and chemicals, being the oleaginous biomass a possible raw
material. Considering the soybean, the primary processes of grinding
and extraction allow obtaining flour and oil, the last one considered as a
platform compound in the framework of an oleaginous biorefinery; the
transesterification of this oil with methanol produces biodiesel, gener­
ating glycerol as by-product, approximately 10 wt% of total product.
The larger the biodiesel production, the larger the glycerol availability;
it decreases the glycerol price because its world demand is limited.
Hence, the glycerol transformation in order to adding value results
interesting because it enables both environmental and economical sus­
tainable developments.
Glycerol has a lot of industrial uses, such as solvent, plasticizer,
sweetener, softener, cosmetics, liquors, lubricants, inks, antifreezes, in
production of resins, humectants, soaps, emulsifier for cosmetic and
feeding, and in pharmaceutical formulations, being also an intermediary
for the production of other compounds [1]. Some added-value products
and the corresponding reactions are: acetol and acrolein by dehydration;
1,2-propanediol, also known as propylene glycol (PG), and 1,3-propane­
diol, by selective reductions; dihydroxyacetone (DHA) and glyceric,
glycolic, hydroxypyruvic, tartronic, and lactic acids by selective

* Corresponding author.
E-mail address: rcomelli@fiq.unl.edu.ar (R.A. Comelli).

https://doi.org/10.1016/j.cattod.2021.09.005
Received 21 February 2021; Received in revised form 20 August 2021; Accepted 10 September 2021
Available online 16 September 2021
0920-5861/© 2021 Elsevier B.V. All rights reserved.
L. Ferrari et al.
oxidations; glycidol by epoxidation; glycerol carbonate by carbonyla­
tion; glycerides by selective etherification; and polyglycerols by poly­
merization. Some energetic compounds from glycerol and the
corresponding reactions are: hydrogen (proposed as the next-generation
renewable fuel) and syngas (a mixture of hydrogen and carbon mon­
oxide) by reforming processes; methanol by hydrogenolysis, making the
synthesis of biodiesel completely sustainable because in fact, methanol
is raw material for this current process as well; and ethers of glycerol, by
etherification with light alkenes.
Selective reduction of glycerol to PG is an interesting process to
obtain this added-value compound. PG is an important chemical com­
modity produced mainly from propylene oxide, having applications in
pharmaceuticals, cosmetics, food, liquid detergents, tobacco humec­
tants, flavors and fragrances, personal care products, paints, and animal
feedstuffs, being also used as functional fluid. That selective reduction,
in liquid phase and operating at high pressures, has been reported using
catalysts such as Raney Ni, Ru/C, Pt/C, Ni/C, and copper chromite,
reaching the last one the best performance [2,3]. Liquid-phase tech­
nologies to produce PG from glycerol are employed by both ADM and
Oleon, while Orlen is finishing a new plant. Copper-containing catalysts
having a high efficiency for the hydrogenation/dehydrogenation of
C–O bonds and a poor activity to cut C–C bonds were considered as
alternative materials [4]. Selective reduction of glycerol to PG in gas
phase has few reported results. In 2007, Ashland Inc and Cargill agreed
in principle to create a new joint venture dedicated exclusively to the
development and production of chemicals from renewable resources,
announcing the production of PG from glycerol using the gas-phase
technology of Johnson Matthey’s DAVY process; nevertheless, this
project was dismissed.
Selective reduction of glycerol also needs hydrogen as raw material,
being glycerol a bio-renewable substrate to produce it. Glycerol
reforming technologies include aqueous-phase and steam reforming,
partial oxidation, autothermal reforming, and supercritical water
reforming [5]. In recent years, the glycerol steam reforming has been
extensively investigated using supported catalysts with metals such as
Pt, Pd, Ru, Rh, Co, and Ni. By comparing the catalytic behavior of mono-
and bimetallic catalysts having Pt and Ni impregnated on alumina
(Al2O3), Ni reached the best performance with high hydrogen selectivity
[6]; the hydrogen selectivity reached with Ni/Al2O3 was strongly
affected by reaction temperature, taking place deactivation by carbo­
naceous deposit formation [7]. Co-Ni/Al2O3 was used for methane dry
reforming, glycerol aqueous-phase reforming, and glycerol and acetol
steam reforming [8]. The steam reforming of glycerol also produces
carbon oxides and methane as by-products; then, adequate catalysts and
operating conditions can mainly produce syngas (carbon monoxide and
hydrogen), which is raw material for either Fischer-Tropsch or methanol
synthesis [9]. Ce, Mg, and Zr were evaluated as promoters, taking into
account that Ce can favor the water gas shift reaction promoting the
syngas production while Zr and Mg can modify the acidity of alumina
affecting deactivation processes and decreasing the carbonaceous de­
posits formed during the reaction [10,11].
Selective oxidations of glycerol to glyceraldehyde and glyceric and
tartronic acids were evaluated using mono- and bimetallic catalysts such
as Pt/C, Pd/C, Au/C, Au-Pd/C, and Au-Pt/C [12]. Another interesting
product obtained by selective oxidation of glycerol is DHA, which is
widely used in the cosmetic industry to make artificial tans and it is also
employed for the treatment of vitiligo, a disease which produces white
spots of irregular form in the skin, due its tanning capability. Consid­
ering the high reactivity of DHA, it finds an important application as a of
great versatile raw material to obtain compounds like lactic and
hydroxypyruvic acids and 1,2-propanediol [1,13,14]. DHA is produced
by a microbiological process using Gluconobacter oxydans, through the
incomplete oxidation of glycerol by means of the
glycerol-dehydrogenase enzyme [15]. Pt-Bi/C was reported as an active
and selective catalyst to obtain DHA by glycerol oxidation, meanwhile
Pt/C did not produce DHA [16]. Glycerol can be also selectively oxidized
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Catalysis Today 394-396 (2022) 247–255
to lactic acid by heterogeneous catalysis [17]; it was also reported under
inert conditions in the presence of platinum-based catalysts [18].
Finally, the high reactivity of glycerol allowing obtain a lot of
products and the possible integration of the corresponding processes in a
same facility allowed us to consider glycerol as a key compound in a
Biorefinery framework [19]. Recently, ORLEN Południe communicated
the production of 30 kt/y of eco-friendly propylene glycol from glycerol
beginning at the end of 2021, and adding a hydrogen plant as one part of
the complex; it was showed as the important stage in the transformation
of the company, which is gradually transforming into a modern bio­
refinery [20]. Argentine is a world referent as soybean and biodiesel
producer, having the province of Santa Fe an installed capacity of 4.4
Mt/y of biodiesel production; hence, 0.44 Mt/y of glycerol would be
available with only 0.2 Mt/y of USP grade glycerol, representing it a
great opportunity to produce added-value compounds in origin. It is
necessary to define the best strategy according to the development
model of the country, either adopting a strategy of mono product, which
would become the new problem or a diversification approach, trans­
forming glycerol into chemicals and/or fuels, considering the potential
specific demand of sustainable or green products.
Catalytic results of glycerol conversion to: i) PG and EG by selective
reductions, ii) hydrogen and/or syngas by steam reforming, and iii) DHA
and lactic acid by selective oxidations, are presented. Preparing and
characterization of materials and their catalytic performances in the
corresponding reactions are discussed. The scaling up phase to pilot
plant of both selective reduction and steam reforming processes to
produce 100 t/y of glycols, currently in the final building stage, is cited
as an example of the positive interaction with the productive sector.
2. Experimental
2.1. Catalyst preparation
2.1.1. Selective reductions
1) To PG: A commercial sample of copper chromite (HARSHAW,
43% CuO and 39% Cr2O3, 49 m2 g− 1 specific surface area and 0.21 cm3
g− 1 pore volume, identified as Cu-Cr) was used, while commercial
samples of γ-alumina (CK-300 Cyanamid Ketjen, 199 m2 g− 1 specific
surface area and 0.51 cm3 g− 1 pore volume, and AFC, 259 m2 g− 1 spe­
cific surface area and 0.35 cm3 g− 1 pore volume, identified as Al2O3),
and both acid and potassium ferrierites (TOSOH, 17.8 SiO2/Al2O3 molar
ratio, identified as H-FER and K-FER, respectively) were impregnated by
incipient wetness impregnation (IWI) using copper(II)nitrate trihydrate
and cerium(III)nitrate hexahydrate as Cu and Ce precursors, respec­
tively, reaching loadings of 2–40 wt% Cu and 2–29 wt% Ce. Impreg­
nated samples were maintained in desiccator at room temperature by 4
h, and dried in oven at 110 ◦ C by 12 h; then, they were calcined at 350 ◦ C
in 50 ml min− 1 air flow during 3 h, and finally reduced at 300 ◦ C in 100
ml min− 1 hydrogen stream. Bimetallic catalysts were prepared
impregnating the second precursor on the calcined monometallic ma­
terial, and then submitted to the same former treatments. Materials were
identified as Cu/K-FER, Cu/H-FER, Cu/Al2O3, Cu-Ce/Al2O3, and Ce-Cu/
Al2O3. 2) To EG: Commercial samples of silica (AEROSIL@, with
different specific surface areas (200, 300, and 380 m2 g− 1) identified as
SiO2) as supports and nickel(II)nitrate hexahydrate as Ni precursor,
were used; materials were impregnated by IWI obtaining 2–10 wt% Ni
loadings. Details of preparations and pretreatments were previously
reported [21]. Materials were identified as Ni(y)/SiO2(Sg), being "y" the
Ni loading expressed in wt% and "Sg" the specific surface area of silica
expressed in m2 g− 1.
2.1.2. Steam reforming
To Hydrogen and/or Syngas: A commercial sample of γ-alumina
(CK-300 Cyanamid Ketjen, 199 m2 g− 1 specific surface area and 0.51
cm3 g− 1 pore volume, identified as Al2O3) as support and nickel(II)ni­
trate hexahydrate as Ni precursor, were used to prepare catalysts by IWI,
L. Ferrari et al.
obtaining 4–9 wt% Ni loadings. Ce, Co, Mg, or Zr precursors were also
impregnated to modify the monometallic material. Details of prepara­
tion and pretreatments were previously reported [22,23]. Materials
were identified as Ni(y)-M(z)/Al2O3, being “M” the second metal and "y"
and “z” the Ni and M loadings, respectively, expressed in wt%.
2.1.3. Selective oxidations
1) To DHA: Commercial sample of coal (CARBONAC GA-160,
identified as C) and K-FER were starting materials to prepare sup­
ported catalysts, while tetraammineplatinum(II)chloride hydrate and
bismuth hydroxide were Pt and Bi precursors, respectively. Materials
were prepared by IWI using solutions that assured loadings of 2.5–7.5 wt
% Pt and 5–10 wt% Bi on the supports. Impregnated samples were
maintained in desiccator at room temperature, dried in oven, and
calcined under similar conditions to previous samples, being finally
reduced at 250 ◦ C in 100 ml min− 1 hydrogen stream. Bimetallic catalysts
were prepared impregnating the second precursor on the reduced
monometallic material, and then submitted to the same former treat­
ments. Materials were identified as Pt/C, Pt/K-FER, Bi/K-FER, Pt-Bi/C,
and Pt-Bi/K-FER. 2) To lactic acid: A commercial sample of
γ-alumina (AFC, 259 m2 g− 1 specific surface area and 0.35 cm3 g− 1 pore
volume, identified as Al2O3) as support and copper(II)nitrate trihydrate
as Cu precursor, were used; catalysts were prepared by IWI, obtaining
loadings of 6–40 wt% Cu. Impregnated materials were kept in desiccator
at room temperature by 5 h and dried in oven at 110 ◦ C overnight; then,
they were calcined at 350 ◦ C in 50 ml min− 1 air flow during 3 h. Samples
were identified as Cu(x)/Al2O3, being "x" the Cu loading expressed in wt
%.
2.2. Catalyst characterization
Textural properties were determined by N2 adsorption and surface
species reducibility by temperature-programmed reduction (TPR).
Ammonia temperature-programmed desorption was carried out to
characterize both total acidity and acid strength distribution. Crystalline
structure was analyzed by X-ray diffraction (XRD), being surface species
characterized by FTIR. Details of characterization techniques and
equipments were previously published [19]. TEM measurements were
made using a PHILIPS EM 201 equipment, with a 3.4 Å resolution; im­
ages were registered using a 60 × 90 mm photographic negatives sys­
tem, working with 1500 × to 200,000 × magnifications and a digital
image, and finally processing with the IMAGE-J software.
2.3. Measurements of catalytic performance
Selective reductions and steam reforming of glycerol were studied in
gas phase, using a continuous down-flow fixed-bed quartz tubular
reactor operated at atmospheric pressure; system details were previ­
ously reported [22,23]. Operating conditions were: i) for selective re­
ductions, 180–240 ◦ C, 0.1 MPa, 50–100 ml min− 1 hydrogen, 0.5–10.0 ml
h− 1 of 20–50 wt% glycerol aqueous solution, and 4 h; and ii) for steam
reforming, 500–700 ◦ C, 0.1 MPa, WHSV 10 h− 1, 16:1:9 water:glycerol:
helium ratio, 0.17 ml min− 1 of 50 wt% glycerol aqueous solution, and 8
h.
Both selective oxidations of glycerol were studied in liquid phase.
Oxidation to DHA took place in a glass reactor under semi-continuous
operation, bubbling a continuous airflow into the liquid and exiting a
gas flow containing the unreacted gas and volatile products; reaction
conditions were 50–70 ◦ C, 0.1 MPa, 30 ml of 10–20 wt% glycerol
aqueous solution, pH 2–4, 300–900 ml min− 1 airflow, 200–400 mg of
catalyst, and 6 h-on-stream. Oxidation to lactic acid was measured in a
high-pressure reaction system having a stainless steel reactor of 250 ml
with an electromagnetic stirrer; operation was batch and reaction con­
ditions were 180–240 ◦ C, 1.4 MPa of N2, 50 ml of 5–15 wt% glycerol
aqueous solution, 1.5 NaOH:glycerol molar ratio, 500–900 mg of cata­
lyst, and 4.5 h-on-stream.
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Catalysis Today 394-396 (2022) 247–255
Selective reductions, steam reforming, and oxidation to DHA were
followed by both on- and off-line gas chromatography, quantifying
glycerol, acetol, PG, EG, and DHA using 1-butanol as internal standard,
and hydrogen, carbon oxides, and methane using a certified standard
containing these gases; more details were previously reported [19,
21–23]. Selective oxidation to lactic acid was followed by HPLC, in an
YL-Instrument, YL-9100 model, having both UV-Vis and RID detectors,
using an Aminex HPX-87H column, 300 × 7.8 mm, hydrogen form,
BioRad. Liquid reaction products were identified by gas
chromatography-mass spectrometry in GC-MS SHIMADZU QP-2010
equipment, using the same column employed for chromatographic
analysis. Finally, catalytic performance is expressed as: glycerol con­
version (molar ratio between consumed and fed glycerol), selectivity to
interesting products (fraction of each one referred to the glycerol con­
verted), yield of interesting product (conversion by selectivity), and/or
molar ratio between products.
3. Results and discussion
Selective reduction of glycerol to PG in gas phase was evaluated on
different catalysts, displaying Fig. 1 their behaviors. Cu-Cr reached high
glycerol conversion, producing both PG and acetol, while Cu impreg­
nated on H-FER and K-FER showed low activity and selectivity to PG
with differences between them, indicating that both metallic and acid
sites affect catalytic performance. Cu/Al2O3 reached lower glycerol
conversion and selectivity to PG than Cu-Cr but a higher selectivity to PG
plus acetol (95.7% vs 73.0%); catalysts containing Cu and Ce impreg­
nated on Al2O3 reached the best performance (47.5% selectivity to PG),
under the same reaction conditions. After optimizing operational con­
ditions, Cu-Ce/Al2O3 obtained 99.8% glycerol conversion and 83.2%
and 14.3% selectivities to PG and acetol, respectively [24–27]. Reaction
scheme proposed for the selective reduction of glycerol to PG considers
two steps: the dehydration of glycerol to acetol, and then, its hydroge­
nation to PG [28]; dehydration needs acid sites while hydrogenation
metallic ones. Fig. 2 shows XRD patterns of alumina and Cu and Ce
impregnated on alumina, corresponding peaks at 28◦ and 56◦ to Ce
while the one at 43◦ is related to Cu; from these patterns and applying
the Scherrer equation, the crystallite sizes resulted: 25.1 nm CuO on
Cu/Al2O3; 7.0 nm CeO2 on Ce/Al2O3; 4.7 nm CeO2 and 24.2 nm CuO on
Cu-Ce/Al2O3; 6.8 nm CeO2 and 30.3 nm CuO on Ce-Cu/Al2O3. The
impregnation order of Cu and Ce produced differences in the XRD pat­
terns; it could be associated to the improvement in catalytic
performance.
These results corresponding to catalytic process for the production of
PG from glycerol in the presence of a Ce and Cu catalyst were protected
[24–27], and also transferred to the productive sector. Nowadays, a pilot
plant to produce 100 t/y of PG by selective reduction of glycerol in gas
phase is in the final building stage; it will allow validate the developed
technology. This technology in gas phase has several advantages respect
to the liquid phase one: i) reaction system in gas phase demands only
low operating pressure (0.1 MPa) meanwhile the liquid phase operation
requires high pressures (7.5–20 MPa); ii) feeding hydrogen at low
pressure significantly improves plant safety; iii) operating at low pres­
sure also reduces equipment cost by reducing the vessel wall thickness;
iv) the Cu-Ce impregnated on alumina catalyst used in the gas phase
process does not include noble metals that having catalysts employed in
the liquid phase one; v) the large excess of hydrogen assurances an
uniform temperature profile in the catalyst fixed bed and a short resi­
dence time of glycerol and products through it, resulting a very selective
process mainly to PG and acetol with a minimum fraction of EG; vi)
reaction taking place in gas phase does not need the separation of solid
catalyst to the reaction products; and vii) catalyst regeneration can be
rapidly made after shut down the reaction and the system, quickly
restarted after it.
Selective reduction of glycerol needs feeding hydrogen, which can
also be obtained by reforming of glycerol; the steam reforming of
L. Ferrari et al. Catalysis Today 394-396 (2022) 247–255

1 1
Fig. 1. Glycerol conversion (X) and selectivities (S) to PG and acetol for different catalysts. Reaction conditions: 200 ◦ C, 0.1 MPa, 70 ml min− H2, 1 ml h− 20%
aqueous glycerol solution, and 4 h-on-stream.

Ce
Cu
Ce

Ce-Cu/Al2O3
Intensity (a.u.)

Cu-Ce/Al2O3

Ce/Al2O3

Cu/Al2O3

Al2O3

10 20 30 40 50 60 70
2θ (º)
Fig. 2. XRD patterns of alumina and Cu and Ce impregnated on alumina.

glycerol produce mainly hydrogen (H2, the highest fraction), CO2, CO,
and CH4 (the lowest fraction), changing their proportions according to
catalysts and operational conditions. Fig. 3 displays catalytic behavior of
Ni(5)-Ce(2)/Al2O3, increasing hydrogen up to 79% during the first
90 min and maintaining it up to 4 h, decreasing then slightly by fouling
and/or partial blockage of the active metal sites by reactions that
generate carbonaceous deposits [29]. During reaction at 700 ◦ C, the
H2/CO molar ratio varied between 2.5 and 3.6, being adequate to use
directly as syngas, which is raw material to both methanol and
Fisher-Tropsch synthesis [9]. Table 1 presents textural properties of
calcined alumina and reduced Ni-containing catalysts. The impregna­
tion of Ni did not change significantly neither SBET nor VP referred to the
support ones, while the addition of Co generated the largest lost of SBET
with the corresponding VP decrease, probably related to the high
metallic loading. Adsorption isotherms showed mainly mesoporous with
diameter between 60 Å and 120 Å, which were mildly blocked by Ni
species meanwhile Co and Ce blocked porous of 120–225 Å.
A glycerol steam reforming pilot plant was recently finished to pro­
duce 8–10 m3 h− 1 of hydrogen, being designed to obtain the hydrogen
required to operate the PG pilot plant. This integration could be shown

250
L. Ferrari et al. Catalysis Today 394-396 (2022) 247–255

Fig. 3. H2, CO2, CO, and CH4 (%) for the steam reforming of glycerol on Ni(5)-Ce(2)/Al2O3. Reaction conditions: 700 ◦ C, 0.1 MPa, WHSV 10 h− 1, 16:1:9 water:glycerol:
helium ratio, 0.17 ml min− 1 of 50 wt% glycerol aqueous solution, and 8 h-on-stream.

Table 1 Table 2
Specific surface area (SBET), pore volume (VP), and pore medium diameter (DP) Glycerol conversion (XG), ratio of CO to converted glycerol (CO/Gconverted), and
of calcined γ-Al2O3 support and reduced Ni-containing catalysts. selectivity to EG, acetol, and PG in the liquid phase, during the selective
reduction of glycerol in gas phase, using Ni impregnated catalysts. Reaction
Catalyst SBET (m2 g− 1) VP (ml g− 1) DP (Å)
conditions: 230 ◦ C, 0.1 MPa, 70 ml min− 1 H2, 1 ml h− 1 20% aqueous glycerol so­
Al2O3 195.1 0.477 97.8 lution, and 4 h-on-stream.
Ni(4)/Al2O3 194.2 0.514 105.9
Co(4)-Ni(4)/Al2O3 85.7 0.253 108.0 Catalyst XG (mol%) CO/Gconverted (mol%) Liquid phase selectivity
Ni(5)-Ce(4)/Al2O3 169.7 0.414 94.5 (mol%)
Mg(10)-Ni(5)/Al2O3 191.9 0.484 101.0 EG Acetol PG

SiO2(380) 3 0.0 0.0 0.0 0.0

as an example of a biorefinery, as reported by Orlen [20], but the main Ni(2.5)/SiO2(200) 100 51.0 91.0 2.1 5.1
Ni(2.5)/SiO2(380) 100 46.4 68.1 2.2 8.9
consideration for producing hydrogen on site was that the hydrogen
Ni(5.0)/SiO2(380) 100 44.1 90.5 2.6 5.0
availability becomes an important issue to resolve before locating the Ni(7.5)/SiO2(380) 100 27.2 59.0 6.0 23.0
facility. Moreover, the out-stream of the glycerol steam reforming pro­
cess could be fed either to specially designed internal combustion en­
gines to produce electrical energy or to solid oxide fuel cell (SOFC) proportion of both acetol and PG. The effect of preparation techniques
combined systems to produce power and heat. Nowadays, 95% of and operational conditions over catalytic performance gave original
hydrogen is produced by methane reforming, being identified as “grey” results, allowing their protection by patent [32]. Fig. 4 presents TEM
hydrogen; appearing also “blue” and “green” hydrogen according to the images corresponding to SiO2(380) and Ni(5.0)/SiO2(380); the support
used non-renewable or renewable resources and the net reduction of had a structure formed by small particles without micro porosity, while
greenhouse gases emissions. Taking into account the sight for a transi­ Ni(5.0)/SiO2(380) showed NiO particles with 7.9 nm average size. It
tion to a future climate neutral economy and its decarbonisation, agrees with previous results of SiO2 impregnated with 5.0% Ni, which
hydrogen appears as the future clean energy but its cost remains under reported particle sizes with an average value of 9.1 ± 0.5 nm, charac­
analysis, including the renewable resources, their regional availability, terizing by TEM [33]. The pilot plant to produce PG was designed ver­
and the Life Cycle Assessment (LCA) [30]. Glycerol steam reforming satile to also convert glycerol into EG, only changing the designed
produces “green” hydrogen because the raw material is a renewable catalyst.
resource and the CO2 obtained is neutralized in the LCA. Finally, the Fig. 5 compares catalytic behavior during the selective oxidation of
selective reduction of glycerol using hydrogen obtained by steam glycerol to DHA. Pt/C was active but not selective to DHA, meanwhile
reforming of glycerol allows obtain a “green” PG which is completely adding Bi on Pt/C produced DHA, agreeing with previous results [16].
renewable; it was shown that the price of hydrogen produced by steam Pt/K-FER improved activity and also produced DHA, reaching 19.6%
reforming of glycerol is not competitive with its price from other sour­ DHA yield; it was the first monometallic catalyst capable to oxidize the
ces, but the “green” PG is still economically viable compared to PG secondary hydroxyl group of glycerol, producing similar DHA yield to
produced from fossil sources [31]. Pt-Bi/C. Bi/K-FER was practically inactive, while Pt-Bi/K-FER reached
Table 2 shows catalytic behavior of Ni/SiO2 during the selective similar conversion to Pt/K-FER but improving significantly the selec­
reduction of glycerol to EG, in gas phase. Silica support did not practi­ tivity to DHA up to 90.1%, under the same reaction conditions. After
cally present activity, while Ni impregnated on SiO2 reached 100% optimizing operational conditions, Pt-Bi/K-FER reached 71.3% DHA
glycerol conversion, decreasing the ratio of CO to converted glycerol by yield, with 75.9% glycerol conversion and 93.9% DHA selectivity [34].
increasing Ni loadings. Ni(2.5)/SiO2(200) and Ni(5.0)/SiO2(380) Fig. 6 shows XRD patterns: K-FER presented high-intensity peaks char­
reached the highest selectivity to EG in the liquid fraction, with low acteristics of the orthorhombic crystalline structure of ferrierite [35];

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L. Ferrari et al.
Fig. 4. TEM images for SiO2 and Ni impregnated on SiO2 catalysts.
Fig. 5. Glycerol conversion (X), selectivity to DHA (S), and DHA yield (Y), for different catalysts. Reaction conditions: 70 ◦ C, 0.1 MPa, 30 ml 20 wt% glycerol aqueous
solution, pH 2, 600 ml min− 1 airflow, and 6 h-on-stream.
after Pt impregnating the crystalline structure of support remained,
appearing strong peaks at 39.0◦ and 45.5◦ , which were assigned to Pt.
After adding Bi on Pt/K-FER, the intensity of peaks decreased, appearing
a well-defined peak at 27.2◦ , corresponding to Bi. Pt/C did not display
peaks assigned to Pt while Pt-Bi/C showed them. Then, catalysts selec­
tive to oxidizing glycerol to DHA present peaks corresponding to Pt in
the XRD patterns.
DHA is widely used in the cosmetic industry to formulate artificial
tans, and its industrial production is mainly the biotransformation of
pure glycerol in aqueous solution with Gluconobacter oxydans; this mi­
crobial process requires times up to 70 h, reaching 40% maximum yield,
and having a high production cost [36]. A stringent requirement in this
microbiological process was that the product concentration was kept
below a critical threshold level in order to avoid the irreversible product
inhibition [14]. Advances in the conventional manufacturing by mi­
crobial oxidation of glycerol to DHA, its high demand, and the sustained
high prices open the route to the introduction of industrial DHA catalytic
syntheses [36]. The current industrial production by bio-fermentation is
not satisfactory; therefore a more efficient production process is needed
to overcome the market deficit; the DHA production by glycerol aerobic
catalytic oxidation in the liquid phase, although it is still in the lab-scale
phase, shows some routes with a robust commercial application,
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Catalysis Today 394-396 (2022) 247–255
identifying promoted Pt nanoparticles, as Pt-Bi and Pt-Sb supported on
carbon and mesoporous materials, and Au nanoparticles supported on
CuO and ZnO, among the most promising catalysts for high DHA yield
processes [37]. Finally, DHA is a key compound for the synthesis of
several fine chemicals and pharmaceuticals and it can be also consider as
a versatile building block to obtain high added-value compounds; the
isomerization of DHA for the production of lactic acid and alkyl lactates
using zeolites containing ruthenium oxide nanoparticles, was reported
[38]. A project to scaling up the glycerol to DHA process and to make the
market study is starting.
Table 3 displays catalytic behavior of Cu/Al2O3 during the selective
oxidation of glycerol to lactic acid, in liquid phase. These catalysts were
active and selective to lactic acid at 1.4 MPa, reaching Cu(30)/Al2O3 the
best performance with 99.8% glycerol conversion and 86.5% selectivity
to lactic acid. Fig. 7 shows TPR profiles of Cu/Al2O3 catalysts with
different Cu loadings; sample having 14.5 wt% Cu displayed two well-
defined reduction peaks indicating the presence of both α and β pha­
ses of Cu, agreeing with previous results [39]. Increasing Cu loading, the
low-temperature reduction peak did not practically change while the
second one increased, shifting to higher temperature. The larger the Cu
loading, the higher the lactic acid yield; then, sites corresponding to the
β-phase of Cu could be related to that catalytic performance.
L. Ferrari et al. Catalysis Today 394-396 (2022) 247–255

Fig. 6. XRD patterns of K-FER and Pt and Pt-Bi impregnated on K-FER.

conversion with 68% and 74% selectivity to lactic acid with 10% Pd/C
Table 3
and 5% Pt/C, respectively [40]; ii) PdOx and Pd0 nanoparticles well
Glycerol conversion (XG), selectivity to lactic acid (SLA), and lactic acid yield
dispersed on the functionalized activated carbon reaching 99% con­
(YLA) during the selective oxidation of glycerol in liquid phase, using Cu-
version with 46% lactic acid selectivity at 230 ◦ C and NaOH:glycerol
impregnated catalysts. Reaction conditions: 220 ◦ C, 1.4 MPa of N2, 50 ml of
10 wt% glycerol aqueous solution, 1.5 NaOH:Glycerol ratio, 0.67 g catalyst, and molar ratio of 1:1 [41]; iii) Ce and Co oxides prepared by
4.5 h-on-stream. deposition-precipitation or impregnation methods [42]; iv) bimetallic
Ni-Co supported on nanosized CeO2, achieving the highest yield to lactic
Catalyst XG (%) SLA (%) YLA (%)
acid (93%) at 160 ◦ C and 20 bar N2 [43]; and v) platinum-based cata­
Cu(6)/Al2O3 31.4 77.5 24.3 lysts evaluated under inert reaction conditions [18]. All these catalytic
Cu(15)/Al2O3 56.6 77.5 43.9
Cu(30)/Al2O3 99.8 86.5 86.3
systems worked in a basic medium (aqueous solution of NaOH), the base
accelerated the lactic acid formation by favoring the transformation of
pyruvaldehyde to lactic acid and by shifting the equilibrium toward
The chemical market makes clearly visible the potential of lactic acid lactic acid formation (the lactic acid concentration is reduced as a result
and its importance as a product in the chemical platform. The selective of Na-lactate formation) [44]. Comparing both catalytic and fermenta­
oxidation of glycerol into lactic acid were reported using several cata­ tive processes to convert glycerol to lactic acid, it can be mentioned that:
lysts: i) Pd or Pt on activated carbon (AC), achieving 99% glycerol i) although the fermentative process achieves high lactic acid yields

Fig. 7. TPR profiles of Cu impregnated on Al2O3 catalysts, with different Cu loadings.

253
L. Ferrari et al.
(90%), there are problems associated with fermentation, such as the
high cost of culture media due to the specific requirements of lactic acid
producing bacteria [45], product inhibition [46], and the purification of
products and residual calcium sulfate in economic and environmental
terms; and ii) the fermentative routes produce optically pure lactic acid
which can be polymerized into high molecular weight polylactic acid
(PLA) through a series of reactions [47], while catalytic routes produce
both enantiomers, leading to the formation of a stereocomplex PLA that
exhibits better properties compared to stereopure polymer forms [48].
Consequently, catalytic routes to produce lactic acid by selective
oxidation of glycerol have attracted increasing interest.
4. Conclusions
Selective reductions of glycerol in gas phase produced: 1) PG on Cu-
Ce/Al2O3 with 99.8% glycerol conversion, and 83.2% and 14.3% se­
lectivities to PG and acetol, respectively; and 2) EG on Ni/SiO2 reaching
100% glycerol conversion and 91% EG selectivity in the liquid fraction.
These selective reductions demand hydrogen, which is obtained by
steam reforming of glycerol using Ni/Al2O3 catalysts, producing as by-
products carbon oxides and methane, being possible to use the syngas
(hydrogen plus carbon monoxide) and methane as energetic com­
pounds. Selective oxidations of glycerol in liquid phase produced: 1)
DHA on Pt/K-FER, being the first active and selective monometallic
catalyst in this transformation, improving the catalytic behavior by
using Pt-Bi/K-FER, reaching 75.9% glycerol conversion and 93.9%
selectivity to DHA; and 2) lactic acid on Cu/Al2O3, with 99.8% con­
version and 86.5% selectivity to lactic acid. The original results were
protected and transferred to the productive sector; actually, one pilot
plant to produce 100 t/y of PG from glycerol but versatile to also obtain
acetol and/or EG is in the final building stage, while another one for
reforming glycerol to produce 8–10 m3 h− 1 of hydrogen which is needed
for those reduction processes is finished. Consequently, the high reac­
tivity of glycerol giving all these compounds and the possible integration
of the corresponding processes allow consider the co-product of bio­
diesel as a raw material to expand a biorefinery scheme.
CRediT authorship contribution statement
Lisandro Ferrari: Investigation, Conceptualization. Fernando
Tuler: Investigation, Conceptualization. Ezequiel Promancio: Investi­
gation. Leonardo Gusé: Investigation. Diego García Touza: Project
administration. Carlos Casas: Supervision. Raúl A. Comelli: Concep­
tualization, Writing – review & editing, Project administration,
Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
Authors acknowledge financial assistance of UNL, CONICET,
FONARSEC (Project 004-Biorefineries), and ASaCTeI (Project IP-2016-
020).
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