View Article Online

Green
View Journal

Chemistry
Cutting-edge research for a greener sustainable future
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: G. M. Lari, G.
Pastore, C. Mondelli and J. Perez-Ramirez, Green Chem., 2017, DOI: 10.1039/C7GC02610B.

Volume 18 Number 7 7 April 2016 Pages 1821–2242 This is an Accepted Manuscript, which has been through the

Green Royal Society of Chemistry peer review process and has been
accepted for publication.
Chemistry
Cutting-edge research for a greener sustainable future Accepted Manuscripts are published online shortly after
www.rsc.org/greenchem

acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.

You can find more information about Accepted Manuscripts in the

author guidelines.

Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1463-9262 standard Terms & Conditions and the ethical guidelines, outlined
CRITICAL REVIEW
in our author and reviewer resource centre, still apply. In no
G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.

rsc.li/green-chem
 Page 1 of 15 Please do notChemistry
Green adjust margins
View Article Online
DOI: 10.1039/C7GC02610B

Green Chemistry

ARTICLE

Towards sustainable manufacture of epichlorohydrin from

Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

glycerol using hydrotalcite-derived basic oxides

Green Chemistry Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
Giacomo M. Lari, Giorgio Pastore, Cecilia Mondelli* and Javier Pérez-Ramírez*
Commercial two-step processes to convert glycerol into epichlorohydrin are more benign compared to the predominant
industrial route starting from propene in terms of materials requirements and CO2 emissions. Still, the use of alkali
hydroxides in stoichiometric amounts in the second reaction, i.e., the dehydrochlorination of the dichloropropanol
intermediate, leads to the formation of large amounts of salt wastes, thus limiting the greenness of the technology. Here,
we show for the first time that the latter transformation can be selectively conducted in the gas phase in the presence of a
heterogeneous hydrotalcite-derived mixed oxide of Al and Mg. Upon reaction, the lamellar solid is rehydrated to a
hydrotalcite-like compound, which can effectively activate the alcoholic group of dichloropropanol owing to its strong
Brønsted basic character and moderately high surface area. In-depth characterisation of the porous, compositional,
structural and acid/base properties demonstrates that the HCl formed during the reaction causes the progressive
exchange of interlayer OH groups by Cl atoms, thus gradually diminishing the reactivity of the material. Facile calcination
restores the original mixed oxide structure and is shown to enable three equivalent consecutive reaction runs. Since the
HCl evolved along with water upon regeneration can be recycled in the first step of the process, i.e., glycerol
hydrochlorination, our approach paves the way for a waste-free and more atom efficient biobased epichlorohydrin
production process.

i.e. a facility where the triol is valorised into higher-value

Introduction
The upgrading of vegetable oils, which substantially comprises
their transesterification to produce biodiesel, has a low
profitability compared to the conventional refining of
petroleum to fuels and base chemicals.[1] This is not merely
due to the small difference between the price of the product
and the cost of the feedstock, but relates to the fact that
glycerol, the main by-product of the transesterification
process, is obtained in greater quantities than the cosmetic,
food and pharmaceutical industries are able to absorb and
must, largely, be disposed of as a waste.[2] Thus, the economic
and environmental footprint of a biodiesel plant would benefit
from the establishment of an associated glycerol biorefinery,
[3]
chemicals. Many conversion paths have been proposed to
obtain compounds retaining the C3 backbone, such as lactic
acid and lactates, diols, carbonates, ethers, esters and
[4]
epichlorohydrin. The latter, which is conventionally
[5]
produced starting from propene, has a world market of ca.
–1
2 Mt y and a very broad application range. Before the
biodiesel production introduced burgeoning amounts of cheap
glycerol in the market, this molecule was the key intermediate
[6]
in the most relevant industrial route to the triol. Nowadays,
epichlorohydrin is mainly used as a (co-)monomer in the
preparation of epoxy resins and as an intermediate in the
manufacture of other polymers (e.g., polyesters), explosives
[7]
and commodities.

This journal is © The Royal Society of Chemistry 2017 Green Chem., 2017, 00, 1-3 | 1

Please do not adjust margins

 Please do notChemistry
Green adjust margins Page 2 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry

Scheme 1. Preparation of epichlorohydrin from glycerol by hydrochlorination to dichloropropanols followed by hydroxide-mediated epoxide formation and undesired thermally-
induced isomerisation of epichlorohydrin to chloroacetone.

[8]
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

The processes proposed for the synthesis of this epoxide halides, which were transformed into metal halides during the
[19]
from glycerol are based on two reaction steps (Scheme 1) and reaction but could be regenerated by calcination at 823 K.

Green Chemistry Accepted Manuscript

some of them have been industrially applied up to a scale of In this work, mixed oxides of magnesium and aluminum
−1 [9]
100 kt y , as, for example, the Solvay’s Epicerol process. obtained by thermal activation of hydrotalcite-like compounds
Notably, this company highlighted the milder ecologic impact (HTlcs) are introduced as efficient solids for the gas-phase
of their technology compared to the fossil fuel-based route in conversion of dichloropropanols to epichlorohydrin. The
view of the inferior requirement for materials and CO2 superiority of these basic solids is identified by evaluation of
[8]
emissions. The first transformation comprises the acid and basic compounds with variable strength. The
chlorination of liquid glycerol with HCl gas, which is bubbled selectivity towards epichlorohydrin is maximised by tuning the
through the reactor, in the presence of a catalyst, typically an temperature as well as the concentration and strength of the
[10]
organic carboxylic acid. After reaction, the mixture mostly basic sites through variation of the Mg/Al ratio and the
contains various isomers of monochlorinated and activation conditions of the HTlc, which offers insights into
dichlorinated species. Upon separation, the first class of structure-mechanism-activity relations. Since the testing of the
molecules is recycled back to the hydrochlorination reactor best performer over prolonged reaction times evidences
along with unconverted glycerol, while the second is fed to a pronounced decrease in activity, the origins of this decay are
second reactor, typically a reactive-distillation unit, where an unraveled and a facile strategy to restore the original level is
inorganic base is added to deprotonate the residual hydroxyl demonstrated. Lastly, qualitative conclusions are drawn on the
group. This induces ring closure, which forms the epoxide and environmental and economic advantages of using a
is associated with the elimination of HCl. The catalyst applied heterogeneous rather than a homogeneous base in a glycerol-
in the first step can be recovered easily by distillation or to-epichlorohydrin process.
[9,10]
filtration, depending on its physical state. In contrast, the
conventional stoichiometric bases, like aqueous solutions of
[9]
NaOH, KOH or Ca(OH)2, used in the second reaction lead to
the formation of salt by-products. Furthermore, based on the
nature of the alkaline compound, the salt can be soluble in the
product feed, hence increasing the difficulty and the cost of its
[11]
separation as well as posing serious corrosion issues to the
[12]
units downstream of the reactor. Accordingly, to attain a
greener glycerol-based production of epichlorohydrin further
developments are required to meet to principles of waste
reduction, atom economy and use of regenerable chemicals.
Highly instrumental to this purpose would be the introduction
[13]
of a heterogeneous reactant.
Based on the mechanism and the nature of the homogeneous
[14]
alkaline compounds, solid bases such as alkali oxides,
[15] [16]
hydrotalcites or basic zeolites are expected to be most
suited for the reaction. Nevertheless, it cannot be excluded
that this transformation can proceed through different
pathways, in analogy to the dehydrochlorination-
oligomerisation of alkyl chlorides, which is mediated by acid
sites.[17] While a catalytic material is preferable, the
identification of a suitable system appears as a challenging
endeavor. Indeed, hydrochloric acid is generated, which,
obviously, interacts with basic sites in a strong manner,[18]
likely leading to activity loss by poisoning. Focusing on a solid
reactant, reusability would be a highly relevant parameter.
This property has been demonstrated for basic metal oxides
(CaO, MgO) applied to the dehydrohalogenation of alkyl

2 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 3 of 15 Please do notChemistry
Green
Green Chemistry
Experimental
Materials
γ-Al2O3 (Alfa Aesar, 99.997% metals basis), MgO (Strem
Chemicals, 99.5%), a USY zeolite in protonic form with a bulk
Si/Al ratio of 405 (Zeolyst, USY) and a Y zeolite in sodium form
with a bulk Si/Al ratio of 2.6 (Zeolyst, CBV100) were used as
received.
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
Two Mg- and Al-based HTlcs with a nominal Mg/Al ratio of
x = 2 and 4 (coded as HTx) were prepared by co-precipitation
3
at pH 10. 500 cm of a x·0.25 M and 0.25 M aqueous solution
of Mg(NO3)3·6H2O (Riedel-de Haen, >99%) and Al(NO3)3·9H2O
(Sigma-Aldrich, >98%), respectively, were added dropwise to
3 3
600 cm of 2 M aqueous Na2CO3 (Sigma-Aldrich, >99.5%) at a
3 −1
rate of 3.5 cm min while magnetically stirring (500 rpm) at
ambient temperature. A 40 wt.% NaOH (Sigma-Aldrich, 97%)
solution was simultaneously added dropwise to keep the pH at
10. The obtained slurry was aged at 333 K for 6 h under
3
stirring. After filtering and washing (3 times, 200 cm of
deionised water each time), the precipitate was dried at 333 K
for 18 h. Mixed metal oxides were obtained by calcination of
−1
the HTlcs at 673-973 K (ramp rate = 5 K min ) for 5 h. These
samples were labelled as HTx-cy, where y is the calcination
temperature expressed in K.
An alkaline-activated USY zeolite with basic character (USY-AT)
was synthesised by adding 3.3 g of a high-silica USY zeolite
3 −1
(Si/Al = 405, Zeolyst) to 100 cm of a 0.1 M methanolic (Sigma-
Aldrich, 99.8%) solution of NaOH. After stirring for 10 min at
room temperature, the solid was filtered and washed with
3 [20]
methanol (3 times, 100 cm each time).
An alkali-activated Y zeolite (Y-AT) was prepared in two steps.
Firstly, a zeolite Y (Zeolyst, CBV100) was dealuminated at 373 K
3
in a 0.15 M solution of H4EDTA (Fluka, >99%, 15 cm per gram
of zeolite) for 24 h, recovered by filtration, washed with
3
deionised water (3 times, 30 cm per gram of zeolite) and dried
at 338 K for 16 h. Thereafter, the solid obtained was treated in
3
0.05-0.2 M aqueous NaOH (30 cm per gram of zeolite) at
338 K for 30 min, using an Easymax 102 setup (Mettler
Toledo). After quenching in an ice bath and filtering, the
3
zeolite was washed with deionised water (3 times, 30 cm per
[21]
gram of zeolite) and dried at 338 K for 16 h.
3
MgO/USY was prepared by dry impregnation. 4 cm of a
0.25 M aqueous solution of Mg(NO3)2·6H2O (Fluka, 99%) were
added dropwise to 4 g of the USY zeolite at room temperature.
The sample was dried at 338 K overnight and calcined at 823 K
−1 [18]
(5 K min ) for 5 h.
Characterisation
The elemental composition of the materials was determined
by X-ray fluorescence spectroscopy (XRF) using an Orbis Micro
XRF instrument equipped with a Rh source operated at 35 kV
and 500 mA. N2 sorption at 77 K was conducted using a
Micromeritics TriStar analyser. Prior to the measurements, the
solids were degassed at 573 K under vacuum for 3 h. Powder
X-ray diffraction (XRD) was performed using a PANalytical
This journal is © The Royal Society of Chemistry 2017
Please do not adjust margins
adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE
X'Pert PRO-MPD diffractometer with Ni-filtered Cu Kα
radiation (λ = 0.1541 nm), acquiring data in the 10-60° 2θ
range with an angular step size of 0.05° and a counting time of
2 s per step. Al magic angle spinning nuclear magnetic
27
resonance ( Al MAS NMR) spectroscopy was conducted in a
Bruker Avance 700 spectrometer operated at 182.4 MHz using
4-mm ZrO2 rotors spun at 10 kHz. Spectra were acquired
accumulating 512 scans using a pulse length of 1 ms, a recycle
delay of 1 s and solid (NH4)Al(SO4)2 as a reference
(δ = 0.00 ppm). Temperature-programmed desorption of
carbon dioxide (CO2-TPD) and temperature programmed
Green Chemistry Accepted Manuscript
oxidation with O2 (TPO) were carried out using a Micromeritics
Autochem II chemisorption analyser coupled with a MKS Cirrus
2 quadrupole mass spectrometer. For the first measurements,
3 −1
the samples (0.05 g) were treated in a He flow (20 cm min )
at 373 K for 2 h. Afterwards, CO2 (50 pulses, 1 cm each pulse)
3 −1
carried by He (10 cm min ) was adsorbed at 323 K, followed
by He purging at the same temperature for 1 h. CO2 desorption
3 −1
was performed using a He flow of 10 cm min and monitored
−1
in the 323-973 K range (10 K min ). The concentration of basic
sites (CB), expressed as mmol of CO2 per gram, was obtained
by multiplying the area of the desorption curve by a calibration
factor obtained from the decomposition of known amounts of
Na2CO3 (Sigma-Aldrich, >99.5%) and dividing it by the mass of
the sample. Upon TPO, the samples (0.05 g) were treated in a
3 −1
He flow (20 cm min ) at 373 K for 2 h. Thereafter, the
temperature was lowered to 323 K and the flow composition
3 −1
and rate modified to 10 vol.% O2 in He and 10 cm min ,
respectively. The sample was heated up to 973 K (10 K min )
while monitoring the gases evolved. The chlorine and the
carbon contents of the used solids were determined by
elemental analysis using a LECO CHN-9000 instrument.
Transmission electron micrographs (TEM) were acquired using
a FEI Talos F200A instrument operated at 200 kV.
Testing
The gas-phase dehydrochlorination (Aldrich-Fine Chemicals,
98%) was studied at ambient pressure using a continuous-flow
fixed-bed reactor setup (Microactivity Reference, PID
Eng&Tech) comprising: (i) a syringe pump for the admission of
the 10 wt.% aqueous solution of the reactant, (ii) a mass flow
controller for feeding N2 (PanGas, 99.99%), (iii) a tubular
quartz reactor (12 mm internal diameter) equipped with a frit
to support the heterogeneous bed and a thermocouple to
monitor its temperature and heated in an oven and (iv) a
condenser kept at 273 K. 0.1-0.5 g of material (0.2-0.5 mm
particle size, 3-12 mm bed thickness) were loaded into the
reactor and the system was heated to the desired temperature
3 −1
(403-673 K) under a N2 flow of 100 cm min . Thereafter, an
aqueous dichloropropanol solution (5-10 wt.%) was admitted
for 0.5-3 h. In order to verify the theoretical possibility to
vaporise dichloropropanol under the reaction conditions, the
physical state of the dichloropropanol-water mixture was
calculated for solute concentrations ranging from 0 to 100
wt.% and between 273-473 K based on the UNIFAC model and
using the RGibbs function in Aspen Plus V8.6.
Green Chem., 2017, 00, 1-3 | 3
 Please do notChemistry
Green
ARTICLE
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
Fig. 1. Dichloropropanol conversion and epichlorohydrin selectivity in the presence of different materials. T = 473 K, P = 1 bar, t = 0.5 h and WHSV = 6 h−1.
Liquid samples were collected from the condenser every
15 min, which were analysed using an HP 6890 gas
chromatograph equipped with an HP-5 capillary column and a
flame ionisation detector. Quantification was achieved based
on the absolute peak areas. Calibration curves were measured
in the 0.5-10, 0.5-7 and 0.5-3 wt.% ranges for 1,3-dichloro-2-
propanol, epichlorohydrin and chloroacetone, respectively.
The calibration response factor of unknown compounds was
assumed to be the same as that of epichlorohydrin.
The conversion of the substrate was calculated as the number
of moles of substrate reacted divided by number of moles of
substrate fed and the selectivity towards the product i as the
number of moles of product formed divided by the total
number of moles of products, according to the following
equations, where the subscripts 0/1 refer to the reactor
inlet/outlet mixture:
Xdichloropropanol = (ndichloropropanol,0 - ndichloropropanol,1) / ndichloropropanol,0
Si = ni,1 / (ndichloropropanol,0 - ndichloropropanol,1)
The carbon balance was calculated as the ratio between the
number of moles of products and the number of moles of
glycerol fed and was always higher than 90%. The
experimental error, determined by three repetitions of
selected runs, was within 5%, which allowed excluding the
occurrence of bypass phenomena in the experiments applying
the thinner beds
Results and discussion
Evaluation of solid acids and bases
Since the identification of a suitable solid for the
dehydrochlorination of dichloropropanol to epichlorohydrin is
here tackled for the first time, a diverse set of materials was
selected for assessement. In analogy with the stoichiometric
homogeneous reactants commonly used in the established
liquid-phase processes, part of the compounds comprised solid
bases of different nature and strength. Specifically, they
included earth-alkali oxides (MgO), alkali-activated zeolites
[20]
(USY-AT) and HTlc in as-synthesised form, i.e., layered
double hydroxides with formula
2+ 3+ m+ 2+
[Mg nAl m(OH)2(n+m)] [CO3 ]m/2·H2O (here with n = 4 and m =
2, HT2), or in calcined state, i.e., Mg-Al mixed oxides (here
4 | Green Chem., 2017, 00, 1-3
Please do not adjust margins
adjust margins Page 4 of 15
View Article Online
DOI: 10.1039/C7GC02610B
Green Chemistry
Green Chemistry Accepted Manuscript
calcined at 823 K, HT2-c823). These materials have a strong
Lewis-, strong Brønsted-, weak Brønsted- and strong Lewis-
basic character, respectively. γ-Al2O3 and a zeolite Y in its
sodium form with a bulk nominal Si/Al ratio of 2.6 were chosen
as representative strong and weak Lewis acids, in this order.
Strong Brønsted acidity was featured in an ultra-stable Y
zeolite in protonic form with a bulk nominal Si/Al ratio of 405
(H-USY). Finally, to assess the relevance of the co-presence of
acidity and basicity, 1.1 wt.% of MgO was supported on the H-
USY zeolite (MgO/USY) and the zeolite Y was modified by an
alkaline treatment in 0.15 M NaOH (Y-AT). The porous and
acid/base properties of these solids are in line with those
reported in the literature for analogous materials (Table 1 and
Table S1 in the ESI).[15,18,20,21] All of the systems were tested in
a continuous-flow fixed-bed reactor kept at 473 K by feeding
an aqueous dichloropropanol solution (5 wt.%) along with an
inert carrier for 0.5 h (Fig. 1 and Table S2). Solids possessing
Brønsted and Lewis acidity generally displayed very low
activity (<1% dichloropropanol conversion) and selectivity
towards epichlorohydrin (<15%). This behaviour was
rationalised by the capability of acid sites to catalyse
dehydration and oligomerisation reactions, leading to
fouling,[22] which was evidenced by the black colour assumed
by the white powders upon the test and confirmed by CHN
analysis (up to 8 wt.% C, Table S1). In addition to the
generation of carbonaceous species, chloroacetone was
formed as a by-product with a selectivity up to 25%. The poor
performance of solid acids improved through the
incorporation of basic sites. In fact, the dichloropropanol
conversion increased from 0.5 and 1.0% to 2.2 and 3.8% over
Y-AT and MgO/USY, respectively, and the epichlorohydrin
selectivity raised to ca. 50% over both solids. However, coke
was still produced in a significant amount in these two cases
(4-5 wt.% C), due to the marked acidity retained by the zeolites
upon their modification. Superior epichlorohydrin yields were
attained over purely basic solids, except for USY-AT. Indeed,
MgO, the HTlc and the mixed Mg-Al oxide displayed a
conversion of 5, 6 and 8% and an epichlorohydrin selectivity of
ca. 30, 70 and 80%, respectively. Notably, coke formation was
limited over these materials (<3 wt.% C).
Design of Mg-Al mixed oxides
This journal is © The Royal Society of Chemistry 2017
 Page 5 of 15 Please do notChemistry
Green adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
Green Chemistry ARTICLE

Based on its remarkable performance, the Mg-Al oxide was
selected for further development. Since such compound was
obtained from a hydrotalcite-like precursor, it was conceived
to vary its properties by altering the composition of the
starting double layered hydroxide. Thus, an additional sample
was prepared with a Mg/Al ratios of 4 (HT4). A ratio lower than
2 was excluded, since for this value it is not feasible to attain a
solid with pure hydrotalcite structure, while a ratio higher than
4 was irrelevant, since it leads to materials with limited ion-
[23]
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
in agreement with previous literature (Table 1). The XRD
patterns of the solids show the typical reflections of a
rhombohedral (3R) layered double hydroxide structure
(Fig. 2a), which are shifted to lower 2θ values due to the
expansion of the unit cell size caused by the higher Mg
[24]
content. TEM confirmed the platelet-like structure of the
crystals (Fig. 3a), which exhibit extensive intergrowth and are
27
oriented in a random fashion. All of the Al MAS NMR spectra
display a signal centred at 10 ppm, indicating the octahedral
[15a]

exchange properties. The actual metal ratio in the as- (Oh) symmetry of the Al centres (Fig. 2b). The basicity of
synthesised samples was close to the nominal value and, in all the HTlcs was probed by CO2-TPD (Fig. 2c). For all samples, the

Green Chemistry Accepted Manuscript

2 −1
cases, the surface area was comprised between 70-80 m g ,

Table 1. Characterisation data of the HTlcs and the mixed metal oxides thereof derived.

Sample Molar Mg/Ala Crystalline Vporec SBETd CBe Tdesf Tdecf Cg

- phase(s)b cm3 g−1 m2 g−1 µmol g−1 K K wt.%
HT2 1.97 HT 0.47 81 85 404 623 0.9
HT4 3.52 HT 0.42 65 89 395 595 0.4
HT2-c823 1.82 MMO 0.58 197 600 532 - 1.0
HT4-c673 3.31 HT+MMO 0.45 148 412 473 650 0.3
HT4-c823 3.50 MMO 0.60 223 482 573 - 1.0
HT4-c973 3.52 MMO 0.58 203 355 536 - 1.1
a
XRF. b XRD. HT = hydrotalcite, MMO = mixed metal oxide. c Volume of N2 adsorbed at p/p0 = 0.98. d Total surface area, BET method. e Concentration of basic sites,
CO2-TPD. f Temperature corresponding to the maximum of the desorption (des) and decomposition (dec) peaks in the CO2-TPD profiles. g Carbon content of the used
materials, elemental analysis.

This journal is © The Royal Society of Chemistry 2017 Green Chem., 2017, 00, 1-3 | 5

Please do not adjust margins

 Please do notChemistry
Green adjust margins Page 6 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

Green Chemistry Accepted Manuscript

Fig. 2. (a,d) XRD, (b,e) 27Al MAS NMR and (c,f) CO2-TPD profiles of the (a,b,c) as-synthesised HTx and (d,e,f) calcined HTx-cy materials. JCPDS 22-700 and 87-0653 comprise the
reference diffractograms used for the assignment of the HTlc and the mixed metal oxide phases, respectively.

curves evidence a low-intensity peak with maximum at
−1
ca. 400 K, indicating the presence of few (<80 mmol g ) weak
basic sites, which is accompanied by a second, very
pronounced signal peaking between 600-700 K, which was
produced by the decomposition of interlayer carbonates. The
area of this second contribution is larger for HT2 than for HT4,
in line with the greater Al substitution and, thus, capacity of
accommodating interlayer anions. After calcination at 823 K,
the two samples possessed the same Mg/Al ratios as the
corresponding starting HTlcs (Table 1) and ca. 2.5-3.5 times
2 −1
higher surface area (150-220 m g ). Their diffractograms
almost exclusively comprise two relatively broad reflections at
43 and 62° 2θ (Fig. 2d), which indicate the transformation of
the double layered hydroxide into a mixed oxide retaining the
[15]
layered structure (Scheme 2). Platelet-like crystals were
visualised by TEM (Fig. 3b), which also highlighted an increased
disorder, i.e., an augmentation of intercrystalline
mesoporosity. The latter is in line with the higher surface area
27
(Table 1). Al MAS NMR spectroscopy revealed that about one
third of the Al atoms changed their environment upon
calcination attaining a tetrahedral geometry (Td) (Fig. 2e),
which is generally quite distorted considering the broad shape
of the resonance at 80 ppm, and that, based on the
appearance of a peak at 18 ppm, about half of the remaining
octahedral sites became highly distorted (C3v). The density of
basic centres of the calcined samples underwent a ca. 8-fold
increase (Fig. 2f and Table 1) and was maximal for HT2-c823.
Still, although preserving sites of mild and moderate strength,
HT4-c823 possessed the strongest centres (Tdes > 773 K).
To modify the characteristics of the mixed oxide, we also
considered the thermal treatment of the starting HTlcs, tuning
its temperature. Thus, HT4 was additionally calcined at 673
and 973 K. The use of milder conditions led to an only partial
decomposition of the hydrotalcite to the mixed oxide, as
demonstrated by the surface area, which was intermediate
between that of the precursor and that of the mixed oxide
obtained upon calcination at 823 K, by the detection of
unconverted precursor by XRD (Fig. 2d) and by the coexistence

6 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 7 of 15 Please do notChemistry
Green adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
Green Chemistry ARTICLE

of octahedral and distorted octa- and tetrahedral species
27
according to Al MAS NMR spectroscopy. After calcination at
973 K, only a mixed oxide phase was evidenced in the
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
diffractogram, which featured sharper peaks than those for
the other two samples, suggesting a moderate increase of the
crystallite size due to sintering at high temperatures.

Green Chemistry Accepted Manuscript

This journal is © The Royal Society of Chemistry 2017 Green Chem., 2017, 00, 1-3 | 7

Please do not adjust margins

 Please do notChemistry
Green adjust margins Page 8 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

Green Chemistry Accepted Manuscript

Scheme 2. Generation of the Mg-Al mixed oxide by calcination of a HTlc, its modification upon use in the dichloropropanol-to-epichlorohydrin reaction and its subsequent
regeneration by calcination.

The two new sets of samples were tested in the
dehydrochlorination of dichloropropanol under the same
conditions applied in the initial evaluation of materials except
for the temperature, which was decreased to 423 K with the
purpose of boosting the selectivity towards epichlorohydrin.
Since the boiling point of dichloropropanol is 450 K, a phase
diagram for the dichloropropanol-water mixture was
calculated to verify that the reactant would be present as a
vapour at this temperature and at 403 K, which is the mildest
condition applied in the testing in this study. For the
concentration employed, the plot (Fig. S1 in the ESI) suggests
that this is fulfilled, since both mixture components are in the
gas phase above 373 K. With respect to the HTlcs, HT4 showed

Fig. 4. (a) Yield of epichlorohydrin, chloroacetone and other by-products upon

conversion of dichloropropanol in the presence of HTx and HTx-cy materials. (b)
Fig. 3. TEM images of the HT4 precursor and of the calcined HT4-c823 material in its Epichlorohydrin yield as a function of their specific surface area. T = 423 K, P = 1 bar, t =
fresh, used and regenerated forms. 0.5 h and WHSV = 6 h−1.

8 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 9 of 15 Please do notChemistry
Green adjust margins
Green Chemistry
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
Fig. 5. Dichloropropanol conversion and selectivity towards epichlorohydrin and
chloroacetone in the presence of HT4-c823 as a function of (a) temperature and (b)
weight hourly space velocity. T = 423 K, P = 1 bar, t = 0.5 h and WHSV = 6 h−1.
an only slightly lower conversion and epichlorohydrin
selectivity than the newly evaluated HT2 (5 versus 6% and 70
versus 75%, respectively, Fig. 4a and Table S2). A noticeable
boost in activity and selectivity was observed over all calcined
solids, which were maximised over HT4-c823 (20%
dichloropropanol conversion, 90% epichlorohydrin selectivity).
It should be noted that these two parameters are linked, i.e., a
higher selectivity is achieved at a higher conversion level. This
was explained by the fact that the concentration of
chloroacetone, the main by-product, was equal in all tests,
suggesting that its rate of formation is not influenced by the
nature of the solid and is likely generated through a thermally-
driven pathway. By analogy with the decomposition of other
epoxides,[25] it was hypothesised that this by-product arises
from the thermal isomerisation of epichlorohydrin.
This journal is © The Royal Society of Chemistry 2017
Please do not adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE
Experiments conducted heating the latter at 673 K confirmed
the formation of the ketonic product with a yield of 78%.
Minor quantities of coke were found on all the solids after
reaction (Table 1). Since no dependence of these amounts on
acid/base or textural properties was observed, thermal
mechanisms might be held responsible for its formation.
Comparison of the dichloropropanol conversion over the
various mixed oxides with the type of their basic sites did not
unveil any correlation, while their surface area appeared as a
better descriptor for activity (Fig. 4b), hinting at the active-site
accessibility, rather than its nature, as the most relevant
Green Chemistry Accepted Manuscript
parameter.
Optimisation of the reaction conditions
In view of the superior epichlorohydrin yield obtained in the
presence of HT4-c823, the influence of the reaction
parameters on the performance was investigated using this
sample. In the 403-673 K range, the dichloropropanol
conversion increased monotonously with the temperature
(Fig. 5a). The only exception was observed at 403 K, since an
unexpectedly high conversion was observed. This was
explained by the occurrence of capillary condensation in the
micropores (vide infra) of the material and to the consequently
altered diffusion and reaction kinetics. In contrast, the
selectivity towards the desired product, epichlorohydrin, was
comprised between 80 and 100% below 423 K and rapidly
decreased between 423-573 K, approaching 0% at the highest
temperature. In line with these results, the reactant was
thermally decomposed in blank tests in an amount that
corresponds to only 2 and up to 20% in the 403-423 K and 423-
673 K ranges, respectively (Fig. S2). The selectivity trend for
chloroacetone was exactly opposite to that of epichlorohydrin,
i.e., the formation of the ketonic compound was negligible at
low temperatures and almost exclusive at high temperatures.
These results indicate that a temperature of 423 K, as applied
in the evaluation of Mg-Al-based solids, was optimal to
maximise the selectivity towards the desired product.
An increase of the space velocity through the application of a
lower mass of solid base led to a pronounced decrease in the
conversion and a slight drop of the selectivity towards
epichlorohydrin (Fig. 5b). The latter observation is in
agreement
Green Chem., 2017, 00, 1-3 | 9
 Please do notChemistry
Green adjust margins Page 10 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry

Table 2. Characterisation data of used and regenerated HT4-c823 samples upon three consecutive reaction cycles.

HT4-c823 sample Molar Mg/Ala Crystalline Vporec SBETd CBe Tdesf Clg Cg
- phase(s)b cm3 g−1 m2 g−1 µmol g−1 K wt.% wt.%
Fresh 3.50 MMO 0.60 223 482 573 - -
Used #1* 3.25 HT+MMO 0.47 125 6 - 10.7 0.9
Calcined #1 3.41 MMO 0.51 205 425 540 0.9 0.0
Used #2* 3.38 HT+MMO 0.42 110 8 - 10.0 1.1
Calcined #2 3.45 MMO 0.52 199 409 545 1.1 0.0
Used #3* 3.32 HT+MMO 0.44 112 5 - 11.3 0.9
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

Calcined #3 3.38 MMO 0.50 195 397 500 0.8 0.0

Used+ 1.81 HT+MMO+others 0.41 89 2 - 12.1 0.6

Green Chemistry Accepted Manuscript

Calcined 1.75 MMO+others 0.47 145 227 473 6.2 0.0
a
XRF. b XRD. HT = hydrotalcite, MMO = mixed metal oxide. c Volume of N2 adsorbed at p/p0 = 0.98. d Total surface area, BET method e Concentration of basic sites, CO2-
TPD. f Temperature corresponding to the maximum of the desorption (des) and decomposition (dec) peaks in the CO2-TPD profiles. g Carbon content of the used
materials, elemental analysis. * T = 423 K, P = 1 bar and WHSV = 6 h−1. + T = 398 K, P = 1 bar and WHSV = 6 h−1.

with the fact that, since the residence time in the heated
section of the reactor was unaltered, the thermally-driven
generation of by-products was not affected.
The best performing material, HT4-c823, was tested over a
prolonged reaction time under the best conditions (423 K and
1.2 h−1). The initially high (ca. 60%) dichloropropanol
conversion was found to rapidly decrease to 15% during the
first hour (Fig. 6a). Similarly, the high epichlorohydrin
selectivity observed
in the first stage of the test diminished, in line with the fact
that chloroacetone and coke were generated at a constant
yield.
Characterisation of the used solid
In order to gain insights into the fate of the solid in the
reaction, the used HT4-c823 was characterised thoroughly.
Elemental analysis indicated a high chlorine content (10.7
wt.%, Table 2), which was comparable to the amount
effectively released upon formation of the epichlorohydrin and
chloroacetone products, which confirms the exclusive
participation of the mixed oxide as a solid reactant in the
conversion of dichloropropanol. From a structural viewpoint, a
portion of the material re-assumed the hydrotalcite structure
that characterised the precursor (Fig. 7a). It is well known that
upon contacting layered double hydroxide-derived oxides with
liquid water or with its vapour at 303-423 K the material
converts back into a HTlc featuring hydroxide instead of
carbonate anions.[26] Due to the smaller size of OH−, the

Fig. 6. Dichloropropanol conversion and selectivity towards epichlorohydrin in three consecutive reaction cycles with intermediate regeneration of HT4-c823at (a) T = 423 K,
P = 1 bar and WHSV = 1.2 h−1 and (b) T = 403 K, P = 1 bar and WHSV = 6 h−1.

10 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 11 of 15 Please do notChemistry
Green
Green Chemistry
interlayer spacing is lower than for the original material and
the reflections in the XRD pattern appear at slightly higher 2θ.
The presence of water in the reaction, the comparable
conditions and the shift in peak position (ca. 1.0 2θ) in the
diffractogram are consistent with the hydration of the mixed
oxide. Still, in view of the fact that HT2-c823 acquires chlorine
upon use, no metal chlorides are formed and the chlorine
− −
anion has a comparable size to OH , Cl species shall occupy
interlayer positions. Actually, it is supposed that the mixed
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
oxide is firstly converted into a rehydrated hydrotalcite, in
− −
which the OH species serve as basic sites for the reaction with
−
dichloropropanol and are progressively substituted by Cl ions
(Scheme 2). In analogy to these considerations, it is speculated
that carbonate species might have been at least partly
replaced by hydroxide species in HT2 and HT4 upon use and
that their inferior conversion level compared to mixed oxides
is likely due to the milder basicity of residual carbonates and
their lower surface area (Fig. 4 and Table 1). In line with the
structural changes, the surface area of HT4-c823 after reaction
diminished to an intermediate value between those
This journal is © The Royal Society of Chemistry 2017
Please do not adjust margins
adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE
determined for HT4 and HT4-c823 in fresh forms (Tables 1 and
2). TEM analysis evidenced that the layered organisation of the
solid was retained, although the morphology of the platelets
became less defined (Fig. 3c). In agreement with the
conversion of part of the aluminium sites from a tetrahedral or
distorted octahedral into an octahedral geometry, the signal at
27
18 ppm in the Al MAS NMR spectrum exhibited a
comparatively higher intensity (Fig. 7b). The CO2-TPD profile
indicated a small amount of residual basic sites (Fig. 7c). This
−
corroborates the predominance of neutral Cl anion over basic
OH species in the interlayer spaces (Scheme 2) and hints that
Green Chemistry Accepted Manuscript
the residual mixed oxide phase is located in the interior of the
particles. The difficulty of the reactant to reach the core of the
material explains the gradual loss in activity. Indeed, at the
beginning of the reaction, dichloropropanol can easily access
the basic sites present at the external surface, while, at later
stages, it has to diffuse into the pores to find unreacted sites. If
the reactant freely diffused in the solid, the conversion level
would stay at 100% and the reaction would last 1.15 h over
HT2-c823 under the conditions applied.
Green Chem., 2017, 00, 1-3 | 11
 Please do notChemistry
Green adjust margins Page 12 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

Green Chemistry Accepted Manuscript

27 27
Fig. 7. (a) XRD, (b) Al MAS NMR and (c) CO2-TPD profiles of the HT4-c823 material used at 423 K. (d) XRD, (e) Al MAS NMR and (f) CO2-TPD profiles of the HT4-c823 material
used at 403 K. JCPDS 22-700, 87-0653 and 01-1133 comprise the reference diffractograms used for the assignment of the HTlc, the mixed metal oxide and AlCl3 phases,
respectively.

(Fig. 7a). Accordingly, the surface area increased back to an only

Regeneration studies
In order to recover the original mixed oxide structure, the used
sample was subjected to calcination at 823 K, which was
effective in reducing the chlorine content to only less than
[19]
1 wt.%. Based on the chemical behaviour of metal chlorides,
it is put forward that the elimination of chlorine from the HTlc
generated in the reaction could follow two main mechanisms
involving molecular oxygen provided in the treatment or water
released by the solid upon heating:
[Mg8Al2(OH)20]Cl2.nH2O + 0.5O2 → Mg8Al2O11 + Cl2+(n+10)H2O
[Mg8Al2(OH)20]Cl2.nH2O → Mg8Al2O11 + 2HCl + (n+9)H2O
In the first case, the chloride ion is oxidised to elemental
chlorine, while along the second path HCl is produced through
an acid-base reaction. Since only HCl was detected by MS
analysis upon TPO of the used material (Fig. S3), the second
route was predominant. XRD confirmed the disappearance of the
hydrotalcite-like phase and the restoration of the mixed oxide
slightly lower value than for the fresh HT4-c823 sample (Table 2)
27
and Al MAS NMR indicated that the proportion between
aluminium sites with tetrahedral and octahedral geometry was
similar to that of the original material (Fig. 7b). Moreover, CO2-TPD
evidenced that the solid regained basicity (Fig. 7c). Notably, the
concentration of basic sites of the regenerated oxide is almost
equal to that of the starting material when relating the values to
their surface areas (Table 2). In addition, the mass and Mg/Al ratio
of the calcined sample were equivalent to the data measured for
the fresh solid, considering the amount of chlorine that remained in
the material, indicating that metals leaching was negligible.
Testing of the calcined sample produced analogous results to those
obtained in the first run (Fig. 6a), except for the slightly inferior
initial activity, which is in line with the moderately lower surface
area and basicity and the small amount of residual chorine
contained. Remarkably, calcination of the re-used material was
equally effective in regenerating the mixed oxide as the treatment

12 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 13 of 15 Please do notChemistry
Green adjust margins
Green Chemistry
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
Scheme 3. Simplified flow sheet for (a) the conventional glycerol-to-epichlorohydrin
process and (b) the process herein introduced based on HTlc-derived oxides for the
second reaction, showing the reaction-regeneration units as well as the chlorine
recycling loop.
conducted after the first reaction (Table 2) and, accordingly, the
reaction data collected in the third test were comparable to those
of the second run (Fig. 6a).
Finally, since the epichlorohydrin selectivity was 15% higher at
403 K, HT4-c823 was assessed also at this 20-K lower temperature.
Under these conditions, the dichloropropanol conversion
progressively decreased reaching a similar level to that attained at
the end of the run at 423 K (Fig. 6b). In contrast, the selectivity
towards epichlorohydrin remained almost unperturbed at ca. 95%.
This is rationalised by the minor occurrence of the thermal
decomposition of the product to chloroacetone at 403 K. Analysis of
the used material uncovered substantial differences with respect to
the sample retrieved after the reaction at 423 K. In this case, the
mixed oxide phase was fully converted into a hydrotalcite-like
− reducing the material needs. Thirdly, the HCl evolved upon its
phase as well as AlCl3 (Fig. 7d). Thus, Cl ions formed upon reaction
− regeneration could be easily recycled in the dehalogenation of
not only exchanged OH species at interlayer positions but also
27
generated a metal salt. Al MAS NMR spectroscopy only detected
hexacoordinated Al sites (Fig. 7e), in line with the octahedral
geometry of this metal in the hydrotalcite and in AlCl3, and CO2-TPD
indicated a full depletion on the basicity (Fig. 7f), as expected from
the neutral nature of OH-free hydrotalcite and the metal chloride.
The distinct alterations underwent by the sample at 403 K are likely
due to the pronounced condensation observed on the solid
reactant at this temperature, suggesting that the transformation
took place in a liquid phase. Although the equilibrium diagram
indicates that a pure vapour phase should be present, capillary
condensation might have been induced by the surface rugosity
and/or the liquid mixture might not have fully vaporised due to
insufficient heat transfer rates during the short residence time in
the heated zone of the reactor. The first hypothesis is supported by
the application of the Kelvin equation.
௉ ିଶఊ௏೘ ௖௢௦ሺఏሻ
݈݊ ቀ௉ ቁ ൌ ௥ோ்
బ was achieved below 423 K, while the product thermally
When using the values typical of pure water in view of the diluted
nature of the system (i.e., a surface tension γ of 6·10−2 N m−1, a
molar volume Vm of 1.8·10−5 m3 mol−1, a contact angle θ of
0 degrees and a condensation pressure P0 of 2.2 bar), a liquid phase
is expected to form in pores with a diameter r smaller than ca.
6 nm, which are responsible for a significant fraction of the porosity
This journal is © The Royal Society of Chemistry 2017
Please do not adjust margins
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE
of HT4-c823 (Fig. S4). The presence of water greatly facilitates ion
migration within the solid, which helped the formation of more
[27]
thermodynamically-stable phases, i.e. aluminium chloride.
Calcination of this material converted the hydrotalcite phase into
the mixed oxide, but the latter produced very sharp reflections,
which is indicative of a severe increase of the particle size. XRD also
evidenced that AlCl3 remained in the material, in line with its
[27]
decomposition temperature in excess of 900 K. These findings
are in agreement with the only partial restoration of the surface
area and the still high Cl content in the sample (Table 2). The
basicity of the calcined solid was strongly inferior to that of the
Green Chemistry Accepted Manuscript
fresh mixed oxide in view of the enrichment in Mg of the system. In
line with the characterisation data, the initial activity of the calcined
solid was remarkably lower than that of the freshly prepared mixed
oxide. A subsequent regeneration-reaction cycle showed a further
deterioration of the performance. Accordingly, operation of the
mixed oxide in the gas phase is a prerequisite to attain stable
reaction-regeneration cycles. For this purpose, the well-known
memory effect of layered double hydroxides is another crucial
factor, since it enables the interconversion between hydrotalcite
and mixed oxide forms with minimal modification of their basic and
textural properties.[15] From a practical viewpoint, a continuous
production of epichlorohydrin can be realised operating two
reactors simultaneously, one dedicated to the desired
transformation and one to the regeneration of the solid base.
Overall, the use of a solid base in the gas phase in place of
homogeneous alkaline solutions allows the compliance of the
glycerol-to-epichlorohydrin process with three main green
chemistry principles. Firstly, the generation of a salt byproduct is
avoided, simplifying downstream purification and reducing waste
treatment efforts. Secondly, the solid reactant is regenerable,
glycerol to dichloropropanols (Scheme 3), maximising the atom
economy and the cost-related performance of the overall glycerol-
to-epichlorohydrin route. Additionally, it is worth noting that the
solid base shares an equivalent non-toxic nature to the
homogeneous counterpart.
Conclusions
In this study, a solid and recyclable base is introduced as
alternative to alkali hydroxides for the dehydrochlorination of
glycerol-derived dichloropropanol to epichlorohydrin. Upon
testing of compounds with variable acid/base properties,
Lewis-basic mixed oxides obtained from hydrotalcite-like
materials emerged as the best-performing solids. Their
selectivity pattern was found to be strongly influenced by
temperature, since total selectivity towards epichlorohydrin
decomposed to chloroacetone under harsher conditions.
Optimisation of the space velocity enabled epichlorohydrin
yields as high as 60%. Thorough characterisation enabled the
elucidation of the reaction mechanism. The latter involves the
initial formation of the actual active phase from the lamellar
mixed oxide, a rehydrated hydrotalcite, and the subsequent
progressive replacement of the hydroxide ions at the
Green Chem., 2017, 00, 1-3 | 13
 Please do notChemistry
Green adjust margins Page 14 of 15
View Article Online
DOI: 10.1039/C7GC02610B
ARTICLE Green Chemistry

interlayer positions by chlorine ions. Simple calcination
appeared effective in restoring a mixed oxide phase with
equivalent porous, structural and basic properties and, thus,
reactivity to the starting solid after a first and second reuse.
Since this treatment releases HCl, a closed chlorine loop within
the whole glycerol-to-epichlorohydrin process was envisaged
when reutilising hydrochloric acid for the dehalogenation of
the triol (Scheme 3). Based on the absence of salt by-products
and the enhancement of the atom economy through HCl
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.
Franchini, M. Laura Dieuzeide, A. M. Duarte de Farias, N.
Amadeo, M. A. Fraga, Chem. Eng. J., 2015, 272, 108-118.
16 D. Verboekend, T.C. Keller, S. Mitchell, J. Pérez-Ramírez, Adv.
Funct. Mater. 2013, 23, 1923-1934.
17 M. Ibáñez, M. Gamero, J. Ruiz-Martínez, B. M. Weckhuysen,
A. T. Aguayo, J. Bilbao and P. Castaño, Catal. Sci. Technol.,
2016, 6, 296-306.
18 B. Puértolas, T. C. Keller, S. Mitchell and J. Pérez-Ramírez,
Appl. Catal., B, 2016, 184, 77-86.
19 G. Huang, G. Lu, J. Wang and J. Yu, J. Anal. Appl. Pyrolysis,
2011, 91, 159-164; (b) N. C. Christensen, US Pat. 2413292,

recycling, the new approach shown in this work holds potential 1946.
toward a greener preparation of epichlorohydrin from 20 G.M. Lari, K. Desai, C. Mondelli and J. Pérez-Ramírez, Catal.

Green Chemistry Accepted Manuscript

renewable resources. Sci. Technol., 2016, 6, 2706-2714.
21 G.M. Lari, B. Puértolas, M.S. Frei, C. Mondelli and J. Pérez-
Ramírez, ChemCatChem, 2016, 8, 1507-1514.
22 A. Aho, N. Kumar, K. Eränen, T. Salmi, M. Hupa and D. Y.
Acknowledgements Murzin, Process Saf. Environ. Prot., 2007, 85, 473-480.
This work was supported by the Swiss National Science 23 F. Cavani, F. Trifirò and A.Vaccari, Catal. Today, 1991, 11,
273-301.
Foundation (Project Number 200020-159760). Dr. S. Mitchell is 24 D. G. Cantrell, L. J. Gillie, A. F. Lee and K. Wilson, Appl. Catal.,
thanked for the TEM analyses and the microscopy centre of A, 2005, 287, 183–190.
ETH Zurich (ScopeM) is acknowledged for providing access to 25 R. R. Baldwin, A. Keen, R. W. Walker, J. Chem. Soc., Faraday
its faciliƟes. Trans. 1, 1984, 80, 435-456.
26 J. Pérez-Ramírez, S. Abelló, N. M. van der Pers, Chem. Eur. J.,
2007, 13, 870-878.
27 L. Catoire and M. T. Swihart, J. Electrochem. Soc., 2002, 149,
References 261-267.
1 (a) Y. Wang and C. Wu, Energ. Econ., 2012, 34, 2167-2181;
(b) E. L. Schultz, D. T. de Souza and M. C. T. Damaso, Chem.
Biol. Technol. Agric., 2014, 1, 1-7.
2 J. R. M. Almeida, L. C. L. Fávaro and B. F. Quirino, Biotechnol.
Biofuels, 2012, 5, 48.
3 M. J. Haas, A. J. McAloon, W. C. Yee and T. A. Foglia,
Bioresour. Technol., 2006, 97, 671-678.
4 M. Pagliaro, R. Cirimmina, H. Kimura, M. Rossi and C. Della
Pina, Angew. Chem. Int. Ed., 2007, 46, 4434-4440.
5 K. Weissermel and H.-J. Arpe, Industrial Organic Chemistry,
Wiley-VCH, Weinheim, 2008, pp. 267-312.
6 K. B. Cofer, US Pat. 2838574, 1958
7 (a) E. Ahad, US Pat. 4891438; (b) A. Harada, M. Furue and S.-
I. Nozakura, Polym. J., 1981, 13, 777-781; (c) A. R. Spurr, J.
Ultrastruct. Res., 1969, 1, 31-43.
8 W. J. Kruper, D. J. Schreck, K. L. Kearns, R. D. Varjian, M. E.
Jones, R. M. Campbell, B. D. Hook, J. R. Briggs and J. G.
Hippler, US Pat. 80888957, 2012.
9 P. Gilbeau, US. Pat. 755725, 2009; (b) P. Gilbeau, US Pat.
20120199786, 2012.
10 E. Santacesaria, R. Tesser, M. Di Serio, L. Casale and D. Verde,
Ind. Eng. Chem. Res., 2010, 49, 964-970
11 E. L. Ligero and T. M. K. Ravagnani, Chem. Eng. Process.,
2003, 42, 543-552.
12 S. C. Okoro, M. Montgomery, F. J. Frandsen and K. Pantleon,
Energy Fuels, 2014, 28, 6447–6458.
13 (a) P. T. Anastas and M. M. Kirchhoff, Acc. Chem. Res., 2002,
35, 686-694; (b) C. Len and R. Luque, Sust. Chem. Proc., 2014,
2, 1-10.
14 (a) R. Luque, L. Herrero-Davila, J. M. Campelo, J. H. Clark, J.
M. Hidalgo, D. Luna, J. M. Marinas and A. A. Romero, Energy
Environ. Sci., 2008, 1, 542-548; (b) J. M. Montero, M. A.
Isaacs, A. F. Lee, J. M. Lynam and K. Wilson, Surf. Sci., 2016,
646, 170-178.
15 (a) S. Abelló, F. Medina, D. Tichit, J. Pérez-Ramírez, J. C.
Groen, J. E. Sueiras, P. Salagre and Y. Cesteros, Chem. Eur. J.,
2005, 11, 728–739; (b) G. M. Lari, A. B. L. de Moura, L.
Weimann, S. Mitchell, C. Mondelli and J. Pérez-Ramírez, J.
Mater. Chem. A, 5, 16200-16211; (c) S. M. de Rezende, C. A.

14 | Green Chem., 2017, 00, 1-3 This journal is © The Royal Society of Chemistry 2017

Please do not adjust margins

 Page 15 of 15 Green Chemistry
View Article Online
DOI: 10.1039/C7GC02610B

Table of Contents Entry

Towards sustainable manufacture of epichlorohydrin from glycerol
using hydrotalcite-derived basic oxides
Giacomo M. Lari, Giorgio Pastore, Cecilia Mondelli and Javier Pérez-Ramírez
Published on 16 October 2017. Downloaded by Freie Universitaet Berlin on 17/10/2017 07:22:08.

Green Chemistry Accepted Manuscript

Regenerable hydrotalcite-derived Mg-Al oxide is an effective heterogeneous base to avoid waste
formation and enable halogen recycling in the glycerol-to-epichlorohydrin process.