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The route towards sustainable production of ethylene glycol from a renewable

resource, biodiesel waste: A Review

Article  in  Catalysis Science & Technology · January 2019

DOI: 10.1039/C8CY02035C

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Catalysis
Science &
Technology
MINI REVIEW

The route towards sustainable production of

Cite this: Catal. Sci. Technol., 2019,
ethylene glycol from a renewable resource,
9, 567 biodiesel waste: a review
Shalini Kandasamy, Shanthi Priya Samudrala * and Sankar Bhattacharya

Ethylene glycol (EG) is a commodity chemical commercially produced via oxidation of the petrochemical-
based resource, ethylene. It has direct usage in antifreeze applications besides being an intermediate prod-
uct of the downstream production line of plastics such as polyethylene terephthalate (PET). EG can also be
produced via a sustainable route utilizing a renewable bio-resource called glycerol, a waste from the bio-
diesel industry. Hydrogenolysis of this biomolecule with the aid of heterogeneous catalysis causes selective
C–O and C–C cleavages which result in the production of EG. This review covers the i) mechanisms of EG
production, ii) homogeneous catalysis and iii) heterogeneous catalysis in EG production, performed in both
batch and continuous flow reactor systems. The role of transition metal and noble metal catalysts in glyc-
Received 1st October 2018, erol conversion and selectivity towards EG is critically analysed in this paper. In addition to that, the reac-
Accepted 27th December 2018
tion conditions such as pH, temperature, and pressure as well as the reactor type that favours EG produc-
DOI: 10.1039/c8cy02035c
tion are also discussed in detail. On weighing the advantages of heterogeneous catalysis in the sustainable
production of EG, various techniques have been proposed to improve the efficiency and feasibility of the
rsc.li/catalysis current methods.

1. Introduction tion) from the biodiesel industry whose release is expected to

reach 10 billion litres worldwide in 2020, according to the U.
Living in a greener environment has now become a need S. Department of Energy.3 Discarding glycerol as a waste is
rather than just a desire. Hence, reducing the carbon foot- costly and not preferable as it has high potential for conver-
print has become an individual and societal responsibility sion into value-added chemicals due to its unique structural
where the reduction of carbon dioxide (CO2) emission is now properties. Besides this, glycerol is also produced as a by-
considered a high priority. The environmental carbon foot- product in soap manufacturing during the saponification
print can be significantly reduced through the world's shift process or steam splitting (hydrolysis process) as well as a
from fossil fuel to renewable energy sources such as biomass main product in the biological fermentation process.4,5
for energy generation and chemical production. The concept Hence, for the past few years, the research community has
of integrated bio-refinery involves green technologies where turned their focus on the catalytic conversion of glycerol into
renewable biomass is converted to biofuels such as bio- value-added derivatives such as fuel additives, chemicals, sol-
ethanol and biodiesel.1 Biodiesel is typically produced vents and polymers.
through catalysed transesterification of vegetable oil, animal Glycerol can be valorised through various chemical modi-
fat or waste into long-chain mono alkyl esters. When metha- fications such as hydrogenolysis,6 dehydration,7
8,9 10 11
nol is used as the alkyl chain alcohol, the process results in acetalization, oxidation, etherification and steam
the production of fatty acid methyl esters (FAME), which are reforming.12 Glycerol hydrogenolysis is one of the highly
generally recognised as biodiesel. studied chemical modifications where glycerol molecules are
The efficiency of biodiesel production is dependent on the reacted with hydrogen either in the liquid or gas phase to ob-
careful handling of by-products (such as crude glycerol, oil tain various products. The valuable chemicals that are pro-
pressed cakes, short chain fatty acids, excess methanol, duced through glycerol hydrogenolysis include dihydric alco-
soaps, impurities and occasionally washing water from purifi- hols [1,2-propanediol (1,2-PD); 1,3-propanediol (1,3-PD);
cation) released from this esterification process.2 Glycerol is ethylene glycol (EG)], monobasic alcohols [1-propanol;
the major by-product (10 weight percent of overall produc- 2-propanol; ethanol; methanol] and alkanes such as propane,
ethane and methane (as shown in Fig. 1) depending on the
Department of Chemical Engineering, Monash University, Clayton, Australia. extent of hydrogenation.13 Each of these chemicals is
E-mail: [email protected] synthesised through a specific reaction route, and extensive

This journal is © The Royal Society of Chemistry 2019 Catal. Sci. Technol., 2019, 9, 567–577 | 567
Mini review Catalysis Science & Technology

Fig. 1 Schematic diagram of glycerol hydrogenolysis to produce dihydric and monobasic alcohols as well as alkanes.

studies have been performed in previous years to deduce the 2 (Fig. 2). EG is proven to be the most pervasive petro-
mechanisms involved and determine the specific catalysts chemical equivalent when making allowance for the market
used to maximise the product selectivity. However, much of of glycerol-derived diols due to its usage as a coolant with
the research focus is directed to the production of 1,2-PD antifreeze properties.18,19 Moreover, the use of glycerol-
and 1,3-PD with less emphasis on EG synthesis. derived EG has the potential to increase substantially due to
Ethylene glycol (EG) is one of the commodity chemicals the low cost of production with an expanding operational
that has been attracting increasing interest and is commer- scale as well as the regulations related to the use of EG in
cially produced from the petrochemical based resource ethyl- food applications.15
ene, as shown in route 1 (Fig. 2). The production process in- Hence, a methodical summary of the overall reported data
volves catalytic oxidation of ethylene, followed by subsequent is necessary to further analyse the technique of increasing se-
hydrolysis of the intermediate product, ethylene oxide (EO). lectivity towards EG in glycerol hydrogenolysis. This review
The conventional manufacturing process of EG utilizes the provides a detailed picture of the mechanisms involved in EG
Shell EO Technology.14 EG is an intermediate monomer with production, the catalysts used for the synthesis and the spe-
various applications as the only mass-produced solvent from cific reaction conditions involved in the process.
the ethylene downstream production chain.15 Besides that, it
has long been used in polyethylene terephthalate (PET) plas- 2. Glycerol hydrogenolysis
tic production and is currently being studied for methanol
production.16 EG is a green solvent with growing environ- Glycerol is a 3C molecule with three OH groups in it. Hence,
mental benefits.17 It can now be produced through a sustain- hydrogenolysis of this compound results either in the cleav-
able process called glycerol hydrogenolysis, as shown in route age of one OH group coupled with the addition of one

Fig. 2 Production of EG using route 1: conventional petrochemical-based non-sustainable pathway and route 2: renewable resource-based sus-
tainable pathway.

568 | Catal. Sci. Technol., 2019, 9, 567–577 This journal is © The Royal Society of Chemistry 2019
Catalysis Science & Technology Mini review

hydrogen atom (dehydration–hydrogenation) or the removal intermediates via C–C cleavage at OHC–COH.29,30 While hy-
of one H2O molecule with the addition of one H2 molecule drogenation of 2-hydroxy acetaldehyde on the metal surface
(dehydrogenation–dehydration–hydrogenation).20 The cleavage results in EG and CO, the hydrogenolysis of formaldehyde
of the OH group from the first carbon produces 1,2-PD while forms methanol. Further hydrogenation of both CO and
the removal of the OH group from the second carbon results methanol results in the production of methane on the metal
in 1,3-PD.21,22 1,2-PD has various applications as a feedstock surface while hydrogenation of EG produces ethanol.31
for the preparation of polyester resins in film and fibre man- On the other hand, in glycerol hydrogenolysis performed
ufacture, as an antifreeze for breweries and the dairy indus- on transition metal catalysts such as Cu catalysts, the glycer-
try, as an inhibitor of mold growth in the pharmaceutical in- aldehyde intermediate undergoes a poor decarbonylation re-
dustry and as an emulsifier in the food industry.23 On the action on the metal surface, resulting in trivial C–C cleavage
other hand, 1,3-PD is utilised by many industries ranging due to low catalytic activity. Alternatively, the intermediate
from carpet fibre, paints, polymers, adhesives, textiles, degrades to form EG and CO directly on the metal surface via
cleaning products to cosmetics and personal care items.24,25 the retro-Claisen route. The CO that is formed through this
EG is synthesised through the cleavage of the OH group from route is then converted to CO2 via the water gas shift reac-
the first carbon followed by C–C cleavage. Further hydro- tion.32 In short, studies reported previously suggest that the
genolysis will result in the production of monobasic alcohols dehydrogenation mechanism over the noble metal catalyst is
and alkanes.26 highly favoured for the formation of EG.

3. Homogeneous catalysis for EG

2.1. Mechanism of EG production
production
EG is generally produced via the dehydrogenation–dehydra-
tion–hydrogenation mechanism which occurs under alkaline Homogeneous catalysts have been traditionally used in glyc-
conditions.27 Since the dehydrogenation route is kinetically erol hydrogenolysis for almost 30 years. In 1987, a patent was
more favourable than the dehydration route, it is assumed to filed on aqueous phase hydrogenolysis of glycerol to produce
be the major or dominant reaction route for glycerol hydro- propanediols over a mixture of rhodium complex and
genolysis performed on a supported noble metal catalyst.27,28 tungstic acid under pressurised hydrogen conditions.33 Ap-
Typically, glycerol dehydrogenates on the noble metal surface proximately four years later, Braca and his research team de-
to form glyceraldehyde as an intermediate for EG and C1 veloped an anionic ruthenium iodocarbonyl complex as a se-
products. This intermediate either undergoes decarbonyl- lective homogeneous catalyst for glycerol hydrogenolysis with
ation on the noble metal surface to directly produce EG and selectivity up to 90% towards n-propanol and its ethers.34
CO via C–C scission at OHC–CO (as shown in Fig. 3) or en- Later, another new palladium-based catalyst in a water–sulfo-
dures retro-aldol condensation on the basic sites (of the lane mixture was established by Shell Oil which also showed
support) to form 2-hydroxy acetaldehyde and formaldehyde selectivity towards n-propanols and 1,3-PD.35 Besides that,

Fig. 3 Mechanism of EG production over noble and transition metal catalysts.

This journal is © The Royal Society of Chemistry 2019 Catal. Sci. Technol., 2019, 9, 567–577 | 569
Mini review Catalysis Science & Technology

low-pressure hydrogenolysis of glycerol has also been tion was carried out in a liquid phase batch reactor, optimiz-
reported over various noble and transition metal based ing the Cu/Zn atomic ratio, temperature and pressure for
homogeneous catalysts where it showed significant selectivity maximum conversion and selectivity towards the desired
towards propylene glycols.36 products.38 It was reported that a higher Cu/ZnO ratio
Although glycerol hydrogenolysis using homogeneous cat- resulted in the lower conversion of glycerol but increased se-
alysts resulted in good conversion and selectivity towards lectivity towards EG.
products, it also displayed several inadequacies wherein sepa- The glycerol conversion and selectivity were highly depen-
ration or recovery of the catalyst was difficult in a liquid dent on the particle size of the catalyst, where smaller Cu
phase reaction. Hence, the catalyst cannot be reused, besides (∼26.3 nm) and ZnO (13.3 nm) were preferred for this reac-
being expensive, making it economically less attractive. More- tion. Besides that, for the catalysts with a Cu/Zn atomic ratio
over, homogeneous catalysts are also reported to be corrosive greater than one, both atomic species were observed to in-
and toxic, increasing the environmental concerns for the us- crease in size after the reaction. Particle size is affected by
age of this process.37 Hence, in the search for a greener and several factors which include pH and pre-reduction. For in-
cheaper glycerol hydrogenolysis process, heterogeneous cata- stance, basic pH (12) is generally favoured for higher glycerol
lysts were later developed and are still being studied for conversion and EG selectivity as it resulted in smaller particle
batch and continuous flow reactions. size due to the higher surface potential of ZnO and Cu parti-
cles. An acidic component in the catalyst tends to result in
4. Heterogeneous catalysis for EG bigger particle size, subsequently affecting the reaction to-
wards the desired product.38 Similarly, pre-reduction of the
production Cu–ZnO catalyst by H2 helps to reduce the particle size by
Heterogeneous catalysts have dual functionality in glycerol discouraging aggregation of Cu particles and hence brings
hydrogenolysis. First is the acid–base functionality involving about a slight improvement in the conversion and selectivity.
the removal of the –OH group which is performed by either On the other hand, a reaction temperature increase (453–
metal oxides or acidic/basic supports. The second functional- 513 K) also played a vital role in increasing both glycerol con-
ity is the oxidation–reduction for the addition of hydrogen version and EG selectivity. This is due to the varying rate of
which is executed by the metal components of the catalyst intrinsic adsorption/desorption and transformations of
through the hydrogen activation process. Hence, heteroge- dehydrated glycerol intermediates on Cu and ZnO surfaces.
neous catalysts are usually categorized based on metal selec- While low temperature favours the adsorption of the interme-
tion, which is either a transition metal or a noble metal. diates causing a higher rate of decomposition, high tempera-
ture promotes desorption that leads to the breaking of C–O
and C–C bonds, increasing EG selectivity.38
4.1. Transition metal catalysts Besides temperature, the batch reaction system recently
4.1.1. Copper (Cu) based catalysts. Various transition tested with the Cu/ZnO catalyst is also proven to be affected
metal catalysts have been studied for selective hydrogenolysis by hydrogen pressure, glycerol concentration and metallic
of glycerol. Among them, copper (Cu)-based catalysts are one copper's surface area.39 The study revealed that the actual re-
of the extensively explored catalysts for this reaction in both action scheme is much more complicated than the readily ac-
batch and continuous processes, as shown in Table 1. A de- cepted dehydration–hydrogenation mechanism. Unlike the
cade ago, Shuai Wang and Haichao Liu38 had developed a Cu mechanism suggested a decade ago, the new study with vary-
catalyst supported on ZnO via a co-precipitation method. ing hydrogen pressure on the Cu/ZnO catalyst recommended
Their findings suggested that the catalyst possesses dual that the dehydrogenation of glycerol to glyceraldehyde occur
functionality, where the acidic ZnO surface favours or initi- first as discussed in section 2.1.39 This glyceraldehyde inter-
ates glycerol dehydration to acetol and glycidol intermediates mediate can either directly yield 1,2-PD or produce EG via the
while hydrogenation takes place on the Cu surface. The reac- retro-Claisen route, depending on the relative reaction rates.

Table 1 Glycerol conversion and selectivity towards EG under various Cu based catalysts

Catalyst name Reactor Temp. (°C) Pressure (bar) Conversion (%) Selectivity (%) Ref.
Cu–ZnO Batch 240 42 55 10 38
Cu–ZnO Batch 200 54 17.3 7.7 39
Cu–Cr (Ba) Batch 240 52 45 5 40
35% Cu/MgO Batch 210 45 96.6 5.1 41
18.5% Cu/SiO2 (3% P) Batch 220 50 — 15.4 42
Cu/Al2O3 (Ag) Fixed bed 200 1 94.3 3.6 43
Cu/Al2O3 100 20.8
Cu/TiO2 Fixed bed 300 1 100 15.3 44
Cu/ZnO 95 9
Cu/ZnO/TiO2 Fixed bed 280 1 100 35 45
5% Cu/SBA-15 Fixed bed 220 1 90 2 46

570 | Catal. Sci. Technol., 2019, 9, 567–577 This journal is © The Royal Society of Chemistry 2019
Catalysis Science & Technology Mini review

Besides that, the effect of glycerol concentration on the reac- catalytic material synthesised via a continuous co-
tion proved that higher water content or lower glycerol con- precipitation method combining both ZnO and TiO2 as the
centration typically favours EG formation. Moreover, the ex- promoter and support, respectively, has reported the highest
periment conducted on the Cu/ZnO catalyst with a constant selectivity towards EG (35%). In addition to that, mesoporous
amount of copper surface area suggested that the catalytic support materials such as SBA-15 have also been studied for
system is also severely hindered by transport limitations, vapour phase glycerol hydrogenolysis. The results revealed
according to the Madon–Boudart criterion.39 As compared to that SBA-15 isn't suitable for the production of EG due to the
previously reported data38 on Cu/ZnO, the recent study39 acidic nature of the material in line with the observations
exhibited lower activity due to the decreased reaction temper- made at the liquid phase reactions performed with various
ature and increased reaction pressure, leading to a drop in Cu-based materials.46
both glycerol conversion and EG selectivity as observed in 4.1.2. Nickel (Ni) based catalysts. Nickel based catalysts
Table 1. are the second most used transition metal catalysts in the
Cu metal has also been studied on other supports such as study of glycerol hydrogenolysis. Most of the reactions
Cr2O3, MgO and SiO2 for liquid phase glycerol hydro- performed with these catalysts use batch reactors as shown
genolysis. With the same reaction temperature and elevated in Table 2. RANEY® Ni has been reported to have a good
pressure, the Cu–Cr catalyst has resulted in slightly reduced glycerol conversion and selectivity towards EG under opti-
activity and selectivity towards EG although it has been pro- mum conditions (200 °C, 80 bar). The efficiency of this mate-
moted by barium ions as shown in Table 1.40 Besides that, rial is reported to increase with reaction temperature and hy-
the Cu/MgO catalyst with 35% metal loading has so far been drogen pressure; however, it drops after a certain reaction
reported to be the best Cu based catalyst for glycerol conver- time. The catalytic performance as well as the reaction kinet-
sion in a batch reactor, although the selectivity towards EG is ics acquired through the parameter estimation method sug-
the lowest.41 On the other hand, the most recent publication gests a two-site Langmuir–Hinshelwood model for this
on liquid phase glycerol hydrogenolysis performed in the catalyst.47
batch reactor has revealed that the SiO2 supported Cu catalyst Ni catalysts have been studied with various support mate-
has now recorded the highest selectivity of 15% towards EG rials in a batch reactor including NaX zeolite, carbon and
as the support material is promoted by 3% of phosphorus Al2O3. The Ni/NaX zeolite catalyst has been characterized to
ion.42 These suggest that high reaction temperature, low have strong acid sites which favour high glycerol conversion,
pressure, and increased metal loading as well as good sup- which on the other hand hamper EG selectivity.48 In 2005, a
port and promoter selection will eventually result in an in- patent was filed on glycerol hydrogenolysis in a batch reactor
creased glycerol conversion and EG selectivity when the reac- studying a bimetallic Ni–Re catalyst supported on a carbon
tion is performed in a liquid phase batch reactor using the material.49 The reaction carried out on Ni–Re/C at 230 °C and
Cu based catalyst. 41.4 bar resulted in only 68% conversion and 18% selectivity
Glycerol hydrogenolysis has also been reported in continu- towards EG, proving the better performance of the monome-
ous flow fixed-bed reactors using Cu catalysts. The overall tallic supported Ni/NaX zeolite catalyst48 than the bimetallic
comparison between batch and fixed bed reactors suggests one.49 Recently, a group of researchers reported a Ni
that continuous flow reactors are better for this reaction as supported SiO2–carbon composite material for this reaction.
they have resulted in the maximum conversion of glycerol up Although the reaction was carried out at a higher tempera-
to 100% in the presence of the Cu catalyst reacted at ambient ture (260 °C) than any other reported ones, the efficiency of
pressure or as low as one bar, as demonstrated in Table 1. the material was still insufficient compared with previously
Cu supported on Al2O3 (ref. 44) is so far proved to be a good reported data.50
catalytic material for vapour phase glycerol hydrogenolysis The Al2O3 support material has been reported several
with supreme conversion (100%) and 20.8% selectivity to- times previously with the incorporation of Ni as the main or
wards EG, which is a higher value than that of the best one of the active components of the catalyst in a batch reac-
reported catalyst (35% Cu/MgO) in a batch reactor.41 Besides tor. Of these, both the bimetallic Cu–Ni (1 : 1) on γ-Al2O3 and
that, another study reported on the Cu/Al2O3 catalyst proves the most recently reported Ni–caesium (Cs)–silicotungstic
that low temperature and promoter loading such as silver acid (SiW) supported Al2O3 catalyst were found to be quite in-
(Ag) on the support material cause a significant loss of the ef- efficient in glycerol hydrogenolysis despite being tested un-
ficiency of the catalytic material regarding both glycerol con- der comparable reaction conditions.51,52 These prove that the
version and selectivity towards EG.43 This proves that pro- promoter added to the first metal is extremely important in
moter selection is very crucial in glycerol hydrogenolysis for catalyst synthesis as the promoter exhibits a significant im-
driving the reaction to the desired route. pact on the performance of the catalytic material, whereas in
Other Cu based support materials which have been stud- the case of Ni, the presence of Cs drastically affected the effi-
ied for vapour phase hydrogenolysis of glycerol include TiO2 ciency of the material in driving the reaction. In 2016, Seretis
and ZnO with comparable conversion yet reduced EG selectiv- & Tsiakaras developed a new catalytic material incorporating
ity to the Cu/Al2O3 catalyst when the reaction was performed 65% Ni onto a SiO2 modified Al2O3 support which is now
under optimum conditions.44 However, the new Cu based recognised as the best Ni-based material for glycerol

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Mini review Catalysis Science & Technology

Table 2 Glycerol conversion and selectivity towards EG under various Ni-based catalysts

Catalyst name Reactor Temp. (°C) Pressure (bar) Conversion (%) Selectivity (%) Ref.
RANEY® Ni Batch 200 80 70 40 47
Ni/NaX Batch 200 60 86 11 48
5% Ni–3.33% Re/carbon Batch 230 41.4 68 18 49
Ni/SiO2–carbon 095 Batch 260 20 56 <7 50
Cu–Ni (1 : 1)/γ-Al2O3 Batch 210 45 59.3 <4.9 51
Ni–Cs4SiW/Al2O3 Batch 240 60.7 23.1 29.5 52
65% Ni/SiO2–Al2O3 Batch 220 60 >90 <10 53
2.5 g of 65% Ni/SiO2 Al2O3 Batch 240 33.5 90.6 >40 54
Ni/SiO2 Fixed bed 220 30 73.2 30.4 55
20% Cu/Al2O3 100 —
20% CuNi/Al2O3 Fixed bed 250 40 95 56
20% CuNi/ZSM-5 90
20% Cu/ZSM-5 88

hydrogenolysis in a batch reactor.53 The catalyst has resulted catalytic activity with a moderate EG selectivity of 15% al-
in more than 90% conversion of crude bio-glycerol, and the though the glycerol conversion reported was only 50% under
selectivity towards EG has been significantly improved up to optimum conditions (325 °C, 60 bar).57
40% when the reaction conditions were optimised to have in-
creased temperature and catalyst weight as well as decreased
hydrogen pressure as observed in Table 2.54 4.2. Noble metal catalysts
Although Ni-based catalysts have been explored quite well 4.2.1. Ruthenium (Ru) based catalysts. Ruthenium (Ru)
in batch reactors, very limited research has been conducted based catalysts are the most comprehensively studied noble
on these catalysts in a continuous flow reactor for glycerol metal catalysts for glycerol hydrogenolysis especially with
hydrogenolysis. Huang et al. have reported a Ni supported well-reported selectivity towards EG in a batch reactor. Ap-
SiO2 catalyst in a fixed bed reactor for the first time, where proximately ten years ago, the initial stages of reactivity test-
they achieved about 73% conversion and 30% selectivity to- ing were performed using a commercial carbon supported Ru
wards EG.55 Recently, Freitas and his group have reported a catalyst at mild reaction temperature in a highly pressurised
Cu–Ni bimetallic catalyst supported on Al2O3 and ZSM-5 (80 bar) system.58 The testing revealed that Ru/C is the best
which has exhibited extraordinary efficiency in glycerol con- catalytic material with good selectivity (68%) towards EG com-
version in a fixed bed reactor. Although the presence of Ni on pared to SiO2 and Al2O3 support materials. Besides that, it
ZSM-5 has an impact on the efficiency of the material, it does was also reported that Ru is the most active metal in
not affect the Al2O3 support compared to the competitive Cu converting glycerol to glycols, with high selectivity towards EG
metal. Hence, the Cu supported Al2O3 catalyst is still proven eventually resulting in methanol formation, compared to the
to be the best catalytic material so far for glycerol hydro- equally competitive platinum (Pt) catalyst that favours the
genolysis in a continuous flow reactor system for temperature production of propylene glycol.59 The addition of base pro-
and hydrogen pressure ranges of 250 to 350 °C and one to 40 moters such as NaOH and CaO does not result in a significant
bar.44,56 effect on the reactivity of the Ru catalyst, unlike the Pt cata-
4.1.3. Molybdenum (Mo) and tungsten (W) based catalysts. lyst. However, the high pH of both catalysts brought about by
Glycerol hydrogenolysis with molybdenum (Mo) and tungsten the promotion of base compounds pointedly resulted in the
(W) supported catalysts has been conducted in a continuous production of lactic acid via glycerol hydrogenolysis. Hence, it
flow fixed bed reactor. The result suggests that the alumina was proposed that the formation of EG via C–C cleavage of
supported Mo and W catalysts contain higher Brønsted acidic glycerol occurs via a metal catalysed reaction on Ru whereas
sites than the silica supported ones, and hence they showed in the case of Pt, it occurs through a base catalysed reaction.59
higher glycerol conversion up to 50% at 250 °C and 60 bar. A Ru supported on activated carbon (AC) catalyst tested in a
Conversely, under similar conditions, the EG selectivity on continuous flow system with double the reaction pressure (80
the silica-supported Mo (28%), and W (27%) catalysts was bar) than the previously reported data (40 bar) revealed that
higher than that on the alumina supported ones (12% and high pressure suppresses glycerol conversion with a minimal
17%, respectively). Further, the increase in temperature up to impact on EG selectivity.60 Also, the Ru/AC catalyst prepared
325 °C caused better conversion of glycerol for both alumina using chloride precursors was reported to have a much smaller
(65% & 70%) and silica (45% & 50%) supported Mo and W particle size and result in better EG selectivity compared to the
catalysts, respectively; however, it significantly decreased the ones prepared from the nitroxyl nitrate precursor or treated
EG selectivity to 15% or lower. This is because higher temper- with nitric acid. This is because nitric acid treatment or the ni-
ature caused excessive C–C cleavage and resulted in increased trate precursor generates oxygenated groups on the carbon sur-
monoalcohol (methanol, ethanol, 1-propanol and 2-propanol) face, increasing the surface acid (–COOH) groups that partici-
production. In comparison, the W/SiO2 catalyst showed better pate in the transformation of glycerol into 1,2-PD.60

572 | Catal. Sci. Technol., 2019, 9, 567–577 This journal is © The Royal Society of Chemistry 2019
Catalysis Science & Technology Mini review

Metal loading is among the various other factors affecting catalyst. In contrast, a reasonable selectivity towards EG was
the glycerol conversion and selectivity towards EG using the also established by the monometallic Ru/TiO2 catalyst com-
Ru/AC catalyst. The literature shows that a precise metal pared to the bimetallic Ru–Cu/TiO2 when the reactions were
loading (for instance, 2.4%) significantly improves glycerol performed in a relatively low pressure (25 bar) batch
conversion up to three-fold although it affects the EG selectiv- reactor.69
ity.61 The usage of a solid acid catalyst as a co-catalyst in glyc- The influence of acidity on Ru based catalytic materials
erol hydrogenolysis, on the other hand, considerably affects causes them to gain better strength to degrade glycerol. How-
both the glycerol conversion and EG selectivity, depending on ever, it eventually leads to excess C–C cleavage and hence re-
the concentration, by providing a synergistic effect on the re- sults in methane formation instead of favouring EG produc-
action. Reasonable catalytic activity is measured when both tion.67 The bimetallic Ru–Re/Al2O3 catalyst, on the other
metal and acid sites were kept at a minimum level.62 The hand, is capable of degrading the glycerol molecule twice as
modification of the Ru/AC catalyst with ionic liquid (IL), cho- much as the acidity does although no improvements towards
line chloride coupled with the zincIJII) chloride promoter, EG selectivity was seen when the reactions were performed
resulted in a better glycerol conversion than the solid acid under similar conditions. This Ru–Re metal combination was
catalyst although it showed poor selectivity towards EG. This also reported to work best on the Al2O3 support material
could be due to the selection of lower reaction temperature compared to SiO2, ZrO2, TiO2, H-β and H-ZSM5.68 Hence, it
(100 °C) than the usual range of 160–220 °C, resulting in a can be concluded that monometallic Ru nanoparticles work
slower reaction rate or incomplete reaction.63 best on ZrO2 and TiO2 supports while the bimetallic Ru cata-
Ru supported on carbon nanotubes (CNTs) was first devel- lyst performs better with the support of Al2O3.
oped and tested for glycerol hydrogenolysis by Wang.64 The Recently, glycerol hydrogenolysis has been tested on a few
findings suggested that the glycerol hydrogenolysis reaction Ru based catalysts in a continuous flow fixed bed reactor at
catalysed by these Ru nanoparticles is structure sensitive and atmospheric pressure by Pavan et al.72 Their findings suggest
the particle size highly influences the glycerol valorisation as that at a reaction temperature of 230 °C, both Ru/γ-Al2O3 and
well as the selectivity towards glycols.64 A recent study Ru/TiO2–ZrO2 prepared via a deposition–precipitation (DP)
reported that Ru/CNTs causes better conversion but results method resulted in good reactivity. It was also reported that
in poor EG selectivity compared to Ru/AC when the reactions for the Ru catalyst supported on γ-Al2O3, the metal loading
were performed under similar conditions.65 In comparison, significantly affects the pore volume, diameter, and surface
as a monometallic catalyst, Ru/AC performs better than Ru/ area of the catalyst, reflecting a good correlation with the ac-
CNTs, whereas graphite and KL-zeolites were often reported tivity in the hydrogenolysis reaction.72 A recent study
as supports with negative outcome.61,65 However, the Ru–Fe conducted on the same catalyst with niobium oxide (Nb) as a
bimetallic catalyst tested for glycerol hydrogenolysis has promoter proved that the addition of the Nb metal signifi-
shown a different pattern, in which Ru–Fe/CNTs causes cantly reduced the glycerol conversion as well as the selectiv-
higher conversion up to 86% than Ru–Fe/AC although the se- ity towards EG. The synergistic effect of Ru–Nb has omi-
lectivity towards EG was slightly lower.66 These prove that the nously stabilized the boehmite structures of the catalyst and
impregnation of the second metal has a high influence on resulted in a well dispersed, stable system with less coke de-
the catalytic properties of the Ru based catalyst in a batch position. However, the reaction with such a stable catalytic
reactor. system was reported to be poor at elevated pressure and tem-
Al2O3 is another support material studied for Ru based perature.75 On the other hand, the Ru supported on TiO2–
catalysts for glycerol hydrogenolysis in a pressurised batch re- ZrO2 binary oxide was reported to have better glycerol conver-
actor. The Ru/γ-Al2O3 catalyst is reported to have better selec- sion up to 52% compared to the previously reported Al2O3.
tivity towards EG than Ru/m-ZrO2 although they result in The researcher claims that the metal loading and dispersion
comparable glycerol conversion.27 However, a decline in reac- as well as the catalyst preparation method significantly affect
tion temperature and pressure by 20 °C and 10 bar, respec- the glycerol conversion and selectivity towards various
tively, could result in a drastic change in this scenario, as the products.73
monometallic Ru/ZrO2 has been reported to have a 3.6 fold In comparison, the catalyst prepared via the wet impreg-
increase in glycerol valorisation in a batch reactor compared nation method showed better selectivity towards EG than
to the Al2O3 supported catalyst.70 Also, this monometallic those prepared via the DP or microemulsion (ME) method.
ZrO2 supported Ru nanoparticle is proven to be a better cata- Moreover, the strong and weak acid sites of the Ru/TiO2–ZrO2
lytic material than the bimetallic Ru–Co/ZrO2. A recent study catalyst were proven to contribute to the selective formation
on the Ru/ZrO2 catalyst modified by lanthanum (La) proved of 1,2-PD and 1,3-PD, which on the other hand, explains the
that the new material has significantly improved the glycerol reason behind hindrance of EG production.73 The meso-
reaction rate to 11.3 mmol gcat−1 h−1 with 55% maximum se- porous Ru/MCM-41 prepared via the ME method is so far
lectivity towards EG at 20% glycerol feed and short (two reported to be the best heterogeneous catalyst for the glycerol
hours) reaction time.71 This remarkable catalytic activity was hydrogenolysis reaction performed in a fixed bed reactor
caused mainly by the formation and well dispersion of Ruδ− compared to SiO2 and carbon supports as well as the previ-
particles as well as the surface acidity and alkalinity of the ously reported Al2O3 and TiO2–ZrO2 supports. At a reaction

This journal is © The Royal Society of Chemistry 2019 Catal. Sci. Technol., 2019, 9, 567–577 | 573
Mini review Catalysis Science & Technology

Table 3 Glycerol conversion and selectivity towards EG under various Ru based catalysts

Catalyst name Reactor Temp. (°C) Pressure (bar) Conversion (%) Selectivity (%) Ref.
Ru/C Batch 160 80 >25 50 58
Ru/C Batch 200 40 20 68 59
Ru(Cl)/AC Batch 180 80 11 62 60
2.4% Ru/AC Batch 220 52 58 29 61
Ru/C + IER acid Batch 180 60 25 43.8 62
2Ru/AC [+ IL (choline chloride) & zincIJII) chloride] Batch 100 20 30.7 11.4 63
Ru/CNT Batch 180 80 28 35 65
Ru2Fe1/AC Batch 200 40 53.8 31 66
Ru2Fe1/CNT 86 23.5
Ru/γ-Al2O3 Batch 200 60 18.7 34.5 27
Ru/Al2O3 + HZSM5 Batch 160 80 23.7 29.4 67
Ru/Al2O3 + Re2(CO)10 Batch 160 80 53.4 29.3 68
2.5Ru/TiO2 Batch 200 25 19.1 41 69
Ru/ZrO2 Batch 180 50 67.5 29.8 70
2% Ru–1.0% La/ZrO2 Batch 190 60 10.4 55 71
3% Ru/γ-Al2O3 Fixed-bed 230 1 35 23 72
3% Ru/TiO2–ZrO2 Fixed-bed 230 1 52 9 73
3% Ru/MCM-41 Fixed bed 280 1 70 25 74
2% Ru–1% Nb/Al2O3 Fixed bed 258 45 28.7 13.9 75

temperature of 280 °C and atmospheric pressure, the catalyst glycerol with 6.3% EG selectivity. The reaction is extremely
resulted in the highest reported conversion of glycerol of temperature sensitive in which the glycerol conversion
70% with 25% selectivity towards EG, as shown in Table 3. dropped to as low as 9.8% when the temperature was
Hence, it can be concluded that MCM-41 is a stable support maintained at 180 °C as C–O cleavage began at this point. Be-
for Ru based catalysts with significantly high activity for sides that, the EG conversion noticeably rose upon increasing
hydrogenolysis of glycerol.74 In comparison, 3% Ru loading the temperature to 240 °C as excessive C–C cleavage was
is also seen to be the best metal content for this reaction re- favoured upon reaching this point.78 Besides that, it was also
gardless of the choice of the support material. confirmed that the bimetallic Pd catalyst is superior to the
4.2.2. Platinum (Pt), palladium (Pd) & iridium (Ir) based monometallic one for glycerol hydrogenolysis due to the high
catalysts. Platinum-based catalysts are one of the least studied activity and selectivity towards EG as Pd serves as the pro-
catalysts for the glycerol hydrogenolysis reaction. So far, there moter (platform for the retro-aldol reaction). Another study
are two reported data on the batch reactor and one on the fixed conducted on the bimetallic Pd catalyst with various metal
bed reactor with selectivity towards EG. Generally the Ni/γ- combinations reported that the Pd–Ni catalyst is the best
Al2O3 catalysed glycerol hydrogenolysis results in the produc- combination as the interaction has resulted in moderate cata-
tion of 1,2-PD. However, the modification of this catalyst with a lytic activity (89%) and high selectivity (22%) towards EG at
small amount of Pt (0.03 Pt/Ni molar ratio) has promoted the 220 °C and 60 bar. However, the Pd–Co, Pd–Fe and Pd–Zn
formation of the Pt–Ni alloy surface which on the other hand catalysts still result in better glycerol conversion than Pd–Ni
elevated the conversion to EG and methane via hydrocrack- despite the low EG selectivity.79
ing.76 Besides that, glycerol hydrogenolysis performed with the Ir based catalysts are the least preferred materials for glyc-
Pt2–Fe/Al2O3 catalyst in a batch reactor has resulted in a maxi- erol hydrogenolysis. The reaction has been performed in a
mum conversion of 62.4% with only 5.3% EG selectivity at 240 batch reactor at 200 °C and 24.8 bar using Ir supported on
°C and 26.2 bar. The study also proved that bimetallic Pt–Fe SiO2, γ-Al2O3 and ZrO2. The maximum glycerol conversion
showed better catalytic activity than the monometallic Pt/Al2O3 achieved was only 8.3% by the ZrO2 support, followed by
as the metal interaction has resulted in the generation of new γ-Al2O3 and SiO2. In addition to that, the EG selectivity
catalytic sites.77 On the other hand, glycerol hydrogenolysis reported over the γ-Al2O3 supported Ir catalyst was as low as
performed with 2Pt/H-mordenite in a fixed bed reactor has 3.2%, proving the low capacity of this material to catalyse the
resulted in up to 94.9% glycerol conversion with 25% selectivity reaction.80
towards EG at a reaction temperature of 215 °C and one bar
pressure.22 In contrast with the reaction in the batch reactor, 5. Conclusion
the monometallic Pt catalyst was reported to have better cata-
lytic properties and EG selectivity compared to the bimetallic EG is one of the highly valuable commodity chemicals pro-
Pt–Cu catalyst22 tested in a fixed bed reactor. duced via glycerol hydrogenolysis. It is produced via a dehy-
The Pd catalysed glycerol hydrogenolysis reaction has drogenation–dehydration–hydrogenation mechanism which
been tested and reported in batch reactors only. The bimetal- involves the selective cleavage of C–O and C–C bonds of the
lic Pd/Fe catalyst used for the reaction carried out at 210 °C glycerol molecule. Heterogeneous catalysis involving transi-
and 5 bar He pressure has resulted in 100% conversion of tion metal and noble metal catalysts plays a vital role in the

574 | Catal. Sci. Technol., 2019, 9, 567–577 This journal is © The Royal Society of Chemistry 2019
Catalysis Science & Technology Mini review

selective cleavage of this molecule towards the production of olites, and various metal oxides are readily used in numerous
EG. In general, transition metal catalysts are responsible for catalytic applications. However, there are some emerging
the glycerol conversion while the selection of noble metal cat- highly crystalline carbon-based nanomaterials with ordered
alysts is extremely crucial for the selectivity towards the EG pores such as mesoporous fullerene C60 and C70.92,93 These
molecule. The preference of transition metal catalysts for this materials are identified as new electrocatalysts with distinc-
reaction in the order of glycerol hydrogenolysis would be Cu tive functionalities by means of tuneable catalytic and
> Ni > W > Mo, whereas that of noble metal catalysts for EG electronic properties. Hence, these nanomaterials have the
selectivity would be Ru > Pt > Pd > Ir. While alkaline condi- potential to be explored for further energy applications.
tions, a mild temperature range (180–240 °C) and low pres- Besides glycerol, there are many other low-cost feedstocks
sure (ambient) are preferred for this reaction, a continuous being studied for the production of EG such as biomass, cel-
flow fixed bed reactor seems to produce better conversion and lulose and sugars. These materials are abundant in nature
selectivity towards the desired product. Hence, the tailoring of and reported to have a high atomic economy for the reaction
reaction conditions is extremely important in achieving the process, meeting the green chemistry requirements. In partic-
best glycerol conversion and selectivity towards EG. ular, the catalytic conversion of cellulose into EG has been
systematically studied by various research groups in which
6. Future considerations the high yield of EG (up to 75.4%) was achieved on an SBA-
15 supported Ni–W bimetallic catalyst.94 Besides that, a dura-
Glycerol hydrogenolysis can be further studied using various ble tungstic acid combined carbon supported Ru binary cata-
transition metal and noble metal combinations in which the lyst with high reusability (more than 20 times) has also been
synthesis of trimetallic catalytic materials81 should be ex- developed for the conversion of cellulose to EG with a yield
plored further to improve the selectivity towards EG. The key greater than 50%.95 Cellulose is valorised through a cascade
factors affecting the catalytic activity and selectivity would be reaction in which it is first hydrolysed by acid to form glu-
the choice of metals, percentage of metal loading, selection cose and water-soluble oligosaccharides. Then these mole-
of promoter and the catalyst preparation techniques. These cules undergo C–C cleavage to form glycolaldehyde over a
can be selectively altered for the production of EG from glyc- transition metal (typically tungsten) followed by the subse-
erol hydrogenolysis. The oxidation states of heterogeneous quent hydrogenation of the resulting molecule (by other tran-
metal or metal-oxide catalysts also play a vital role in glycerol sition metals) to produce EG.96 In addition to that, detailed
hydrogenolysis by affecting the catalyst activity or rate of re- reaction kinetics and mechanisms97 have also been reported
action. For instance, rhenium (Re) appeared in a range of oxi- thoroughly for the production of EG from cellulose. These to-
dation states (0, +2, +4, and +7) on the Pt–Re catalyst after re- gether paved the fundamentals for another promising and
duction by H2 which confers different Brønsted acidities to sustainable route for EG production via conversion of an-
the catalyst. Hence, it is important to study the effect of oxi- other renewable resource (cellulose), apart from glycerol.
dation states of various metal catalysts to obtain a high yield
of EG from glycerol hydrogenolysis.82 Conflicts of interest
Recently, the research focus on catalysis had branched out
into venturing the capacity of ionic liquids (ILs) and deep eu- There are no conflicts to declare.
tectic solvents. These are green solvents with various applica-
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