Mini review

A Review on Different Solid Acid Catalysts and the Parameters Used in

Etherification of Glycerol

Fatimah Azzahrah Mohd Fairuz , Noraini Hamzah

1,* 2,*

1 Faculty of Applied Sciences, Universiti Teknologi MARA, UiTM, Shah Alam 40450, Selangor,
Malaysia
2 Faculty of Applied Sciences, Universiti Teknologi MARA, UiTM, Shah Alam 40450, Selangor,
Malaysia
*Email: [email protected] , [email protected]

Nowadays, biodiesel is one of the rising alternatives and renewable fuels that has caused a major
expansion of renewable energy usage. In biodiesel industry, glycerol would be a major by-product
from the processing. Review on glycerol conversion will be beneficial to the industry in order to
avoid market saturation thus increase profits for biodiesel production. Hence, if biodiesel output
profits eventually increase, it will cause the industry to become more competitive. Other than that,
glycerol waste will be reduced if the industry actively made changes or keep getting new
alternatives on how to control the glycerol production. Glycerol can be treated through various
chemical processes to convert it into value-added product. In this review paper, etherification has
been chosen as the process to convert glycerol as it is one of the most extensively utilized
techniques with the support of solid acid catalysts. Acid catalysts are frequently employed in
industry for petrochemical reactions, precision chemical synthesis, and biomass conversions. The
replacement of typical liquid acids with solid acid catalysts is receiving a lot of attention in order to
conform with the concepts of green and sustainable chemistry. In comparison to homogeneous acid
catalysts, heterogeneous acid catalysts have been deemed to be more effective due to the presence
of acid sites with variable strengths of Bronsted or Lewis acidity. It's also valuable as a solid acid
catalyst. It was proven in previous studies that solid acid catalysts have attracted a lot of attention
because of their ease of separation from the product, high reusability and regeneration potential,
insensitivity to free fatty acid content, and many more. Apart from that, findings indicated that
adding a co-catalyst, bimetal synergism, metal oxides, controlling the acidity of molecular sieves,
and immobilised mobile liquid were all important techniques in controlling the stability of solid
acid catalysts and preventing deactivation. The reaction parameters will be compared to know the
most effective solid acid catalyst in the process of etherification of glycerol and findings shows that
Amberlyst-15 gives the best condition in all of the reviewed parameters.

Keywords: etherification; glycerol; solid acid catalyst; structural stability; chemical stability;
parameters.
1. INTRODUCTION

In this era of globalization, increased transportation fuel supply, combined with the
environmental concerns and declining crude oil supplies, has caused a major expansion of
renewable energy usage. Biodiesel is one of the rising alternatives and renewable fuels that has been
treated with growing interest and those whose production potential has been well established in
recent years to cover the declining fossil fuels (Ashnani et al., 2014). Despite the fact that global
biodiesel production was projected to hit a high capacity, it fell short of expectations and grew at a
slower pace.
According to Chong et al. (2020), from the production of biodiesel, glycerol would be a major
by-product from the processing, accounting for around 10% (w/w). In other words, for every gallon
of biodiesel produced, 1.05 pounds of glycerol is produced as by-product. Figure 1 shows the
forecast of glycerol that was produced, from 2001 until 2026. The trend of glycerol production
shows an increased from 0 to 3500 million litres and is expected to reach until 4000 million litres
in 2026 (Chong et al., 2020). Furthermore, the independent production of glycerol in order to
supply not only damaged the biodiesel industry's economic viability, but also contributed to
environmental challenges such as waste disposal and pollution (Chilakamarry et al., 2021).

Figure 1. Global glycerol production growth

Source : (Chong et al., 2020)
Glycerol has the chemical names of propane-1,2,3-triol, 1,2,3-trihydroxypropane, 1,2,3-
propanetriole, glycerin, glyceritole, and glycyl alcohol, according to IUPAC (Chong et al., 2020).
The crude glycerol usually formed from the transesterification of biodiesel, and it is found in the
glycerol phase with a variety of other materials including soaps, remaining catalyst, water, and
esters developed during the process. There are various methods on how to convert the crude
glycerol such as combustion, animal feeds, composting and the biological conversion to value-
added products. However, those methods only applicable to that of large companies and refineries
since they have a sufficient equipment to proceed with the process. Glycerol does have various
catalytic conversion by using heterogeneous catalyst such as esterification, etherification,
etherification, hydrogenolysis, acetalization etc. Hence, glycerol formation is a major issue in the
biodiesel production chain, posing new challenges to its long-term value (Monteiro et al., 2018) and
necessitating the exploration of several new routes to turn it into added-value items. As response,
etherification is a promising way to commodify glycerol by dehydration of an alcohol into ethers. In
addition, the conversion of glycerol by etherification reaction may use either homogeneous catalyst
such as Na 2 CO 3 (Vahdatzaman, 2017) or heterogeneous catalyst like zeolites (Cannilla et al., 2020)
or Amberlyst-15 (Pico et al., 2013). Specifically, ethers obtained from refined glycerol through
etherification can be used to make a variety of derivative products, including pharmaceutical
intermediates, detergents, non-ionic surfactants, coating and paint additives, and liquid fuel
additives.
Majority of the research had concentrated on a few heterogeneous acid catalysts since these
reactions provide the most reusability which can be used for multiple times and results in maximum
recovery after reaction. The reasons of avoiding a homogeneous catalyst in this research is because
it is difficult to separate the product from the catalyst since the catalyst and the reactant are in the
same phases (Chong et al., 2020). Hence, although homogenous liquid acids have good catalytic
activity, they have a number of drawbacks, including inability to be recycled, equipment corrosion,
the creation of a huge volume of waste water and pollution, and so on (Liu et al., 2020). Due to the
drawbacks of the homogeneous catalyst, this review will be focusing on solid acid catalyst which is
heterogeneous. Solid-acid catalysts have been used in many industrial processes because solid acids
can overcome the limitations of liquid acids, and they've gotten a lot of attention recently because
the catalytic function of solid acids is derived from the Brönsted and Lewis acidic sites on the solid
surface, which have catalytic activity (Liu et al., 2020).
In this review paper, the research questions that will be discussed are advantages and
disadvantages of solid acid catalyst also the techniques used to improve stability of the catalysts.
Other than that, the type of solid acid catalysts that were used for etherification of glycerol were
listed to look at the differences of reactant and the product. Besides, the parameters of solid acid
catalyst used to get high yield of conversion in etherification of glycerol were compared in terms of
reaction time, temperature effect, catalyst loading and molar ratio. Finally, the best solid acid
catalyst that were used in etherification of glycerol will be chosen according to its highest
percentage of glycerol conversion.

2. GLYCEROL

Glycerol is a type of alcohol that can be obtained from excess glucose and can be transformed
into long chain fatty acids and esterified with the three hydroxyl groups. Glycerol is considered as
an intermediary in carbohydrate and lipid metabolism in biological systems. In some publications, it
is also referred to as glycyl alcohol or glycerin.
Figure 2 shows the structure of glycerol with three carbon atoms and three hydroxyl groups,
glycerol is a trihydroxy sugar alcohol. It can be illustrated as a triol with hydroxy groups
substituting for propane at positions 1, 2, and 3. It is an organic polyol molecule with the IUPAC
designation 1, 2, 3 – Propanetriol due to the presence of numerous hydroxyl groups and carbon
atoms.
 Figure 2. Molecular structure of glycerol.

Glycerol is a colorless, odorless, viscous liquid with a pleasant taste. Glycerol has a melting
point of roughly 18°C and a boiling point of 290°C, though it can disintegrate at those temperatures.
Aside from that, the capacity of the polyol groups to establish hydrogen bonds with water molecules
allows it to be miscible with water indefinitely. Glycerol is soluble in 11 times ethyl acetate and 500
times ether (Mustafa et al., 2021). On the other hand, benzene, chloroform, carbon tetrachloride,
carbon disulfide, petroleum ether, and oil are insoluble in it. Glycerol is also a mildly acidic
substance that can react with alkaline hydroxide.

2.1 Conversion of glycerol

Conversion involves a chemical reaction production process in which the product undergoes
chemical transformation, i.e., the product differs chemically from the raw ingredients. The majority
of conversions in chemical manufacturing processes are made up of a series of phases, each
involves changing the product in some form. In the case of glycerol, the conversion is important in
some way in order to maintain the revenue and to avoid glycerol waste (Chozhavendhan et al.,
2019).
The necessity to convert glycerol arises from the fact that increased biodiesel production
will result in an excess supply of glycerol, which is regarded as having a low commercial value due
to its poor quality. Due to the properties and potentials of glycerol, efforts to convert it into higher-
value products are increasing, which will enhance the overall economies of production of biodiesel
(Nda-Umar et al., 2019).
There are many ways to convert the glycerol that has been used in previous studies such as
fermentation, esterification, hydrogenolysis, dehydration, oxidation, etherification and many more
(Pradima et al., 2017). The list has been listed as in Figure 3. As an example, the esterification of
glycerol over bio-carbon samples acquired by partial carbonization yielded good yields of diacetin
and triacetin in only 2 hours, which was particularly visible in the esterification of glycerol over
bio-carbon samples for the production of fuel additives (Malaika et al., 2021). Other than that,
according to Wang et al. (2020), chemical transformation of glycerol to 1,3-PDO via
hydrogenolysis has outstanding properties over fermentation in terms of high glycerol content in the
feedstock, continuity of the operation, and scalability. In contrast, a previous study shown that the
catalytic performance of gold–palladium alloy catalysts for glycerol oxidation was researched, and
it was discovered that alloying Pd with Au significantly improves the selective oxidation of
glycerol, and the most active catalysts were formed using a sol–immobilization method (Dimitratos
et al., 2009).
For instance, high tert-butyl ethers from glycerol etherification might reduce the use of
typical gasoline additives like methyl-tert-butyl ethers and ethyl-tert-butyl ethers, which are
hazardous to the environment due to their low recyclability and petrochemical source (Lopez-
Suarez et al., 2021). This review will be focusing on applying etherification as the reaction to
convert glycerol into value-added products.

Biochemical Paths

Cyclization Glycerol carbonate,

Acetals, Glycidol

Dehydration Acrolein

Esterification Mono and poly

esters
Glycerol
Etherification Mono and poly
ethers

Oligomerization Polyglycerols

Hydrogenolysis 1,3-propanediol,
1,2-propanediol

Reforming Syngas

Figure 3. Chemical process of converting glycerol.

Source: (Pradima et al., 2017)

2.2 Etherification of glycerol

Etherification is a process where ethers formed by dehydration of alcohol. Etherification is

one of the most extensively utilized techniques for converting glycerol into a value-added product.
Ether product have been used as medicinal intermediates, non-ionic surfactants, and oxygenated
fuel additives in the past (Veiga et al., 2017). In the past study, one of the most promising ways to
utilize glycerol is through the etherification reaction (Marinho et al., 2020). Other than that, in the
researches of Veiga et al. (2018), one example of etherification of glycerol with alcohol (t-butyl
alcohol) was shown. Because of their low viscosity, t-butyl ethers of glycerol were used as gasoline
additives as a result of their research. Glycerol ethers di-tert-butyl and tri-tert-butyl can be
combined directly with diesel or biodiesel. The example of reaction mechanism of etherification of
glycerol with tert-butyl alcohol is shown in Figure 4 with the presence of solid acid catalyst.
 Figure 4. Reaction mechanism of etherification of glycerol with tert-butyl alcohol; mono ethers (1-MTBG,
2-MTBG), di-ethers (1,3-DTBG, 1,2-DTBG), tri-ether (1,2,3-TTBG
Source: (Estevez et al., 2016)

3. CATALYST

A catalyst is a substance that speeds up chemical reactions without being changed or

consumed in the process. Catalyst is one of crucial elements in the chemical industry. According to
Kakaei et al. (2019), catalytic processes were used to make over 90% of the chemicals produced in
the industry. Generally, catalyst was divided into two categories which are homogeneous and
heterogeneous catalyst, and it is commonly used in the industry.

3.1 Homogeneous Catalyst

The introduction of an aqueous phase catalyst into an aqueous solution containing reactants
in the same phase is known as homogeneous catalysis. The catalyst may be altered during the
reaction, but unlike heterogeneous catalysis, the homogeneous catalyst is frequently has very high
selectivity once the reaction is completed. According to Taipabu et al. (2021), although
homogeneous alkaline and acid catalysts (e.g., CH 3 ONa, H2 SO 4) have several benefits, such as
higher production, low cost, and quicker response rate, they require a neutralization process,
wastewater generation, equipment corrosion (especially for H2 SO 4 ), and complexity in catalyst
restoration and product purification. In addition, industries have discovered that glycerol may be
polymerized to produce value-added products using homogeneous catalysts; however, the use of
these homogeneous catalysts has economic constraints because extracting the catalyst from the
polymer is a difficult and expensive procedure (Vahdatzaman, 2017). Lastly, when compared to
heterogeneous catalysts, homogeneous catalysts yield higher glycerol conversions but worse
selectivity to diglycerol and triglycerol (Bookong et al., 2015).

3.2 Heterogeneous Catalyst

Heterogeneous catalysis occurs when the catalyst introduced is in a different phase than the
reactant. The catalyst in heterogeneous catalysis usually provided a surface on which the reactants
are momentarily adsorbed. Adsorption and desorption occurred in this reaction, making catalyst
regeneration easier to achieve. According to Gholami et al. (2015), glycerol conversion to higher
oligomers such as diglycerol has been successfully achieved using mesoporous catalysts as
heterogeneous catalysts. The catalytic activity of alkaline earth metal oxide catalysts was shown to
be enhanced by the surface basicity of the catalyst. Furthermore, mesoporous solids are noteworthy
because of their structure, which is predicted to improve reaction selectivity, and because they are
unlikely to dissolve as easily in hot glycerol as alkali carbonates and hydroxides (Gholami et al.,
2015). Heterogeneous catalyst also has this feature which is easy to separate and it is reusable
although the catalyst may require reactivating treatment. Nandiwale et al. (2014) discussed the
reaction catalyzed by various zeolites in previous research, and they found the H-beta zeolite to be a
reusable solid for selective manufacture of glyceryl mono-ethers from n-butanol, with a glycerol
conversion of 55%. In addition, using commercial pure glucose as a carbon precursor, a
hydrothermal carbonization technique resulted in a cost-effective way to manufacture mono-
disperse carbon sphere catalysts that are very active in terms of glycerol conversion and
substantially hinder the formation of oligomers (Frusteri et al., 2016).

4. SOLID ACID CATALYST

Solid acid catalyst is a solid with acidic characteristics on their surfaces that act as catalysts in
the same way that liquid acids like sulfuric acid and hydrochloric acid do. Solid acids were applied
in a wide range of industrial chemical processes, from petroleum refining's largest chemical
process, catalytic cracking, to the synthesis of numerous fine compounds (Hattori & Ono, 2014).
The acidic properties of a solid acid catalyst (such as type, strength, distribution, and concentration),
which have been thoroughly explored using various analytical and spectroscopic approaches, are
known to govern its catalytic activity and selectivity (Zheng et al., 2016).

4.1 Advantages of Solid Acid Catalysts

According to Zheng et al. (2016), solid acid catalysts, contrary to typical homogeneous
catalysis, are recognised to be ecologically friendly and have been widely used in sophisticated
petrochemical processes due to their acid-base catalysed activity. Solid acids were said to be less
corrosive and more selective than liquid acids, and they may be conveniently isolated from a
chemical system for later use (Liu et al., 2018). In a wide range of acid-catalysed processes,
heteropoly acids, metal oxides, sulfonated metal oxides, phosphates, and strongly acidic resins have
exhibited good catalytic activity and increased reusability (Sirsam et al., 2016).
 The following are the other benefits of using solid-acid catalysts: even in the presence of
acid species, insensitive to FFA material, easy separation of the catalyst from the reaction products,
and reduction of corrosion problem (Ali et al., 2017). Other than that, majority of relatively new
solid acid catalysts are centred on a silica support because it provides outstanding chemical
stability, a large surface area, and easy access to reactive centres, as well as the ability to support
organic substituents to their surface to provide heterogeneous solid acid sites (Sirsam et al., 2016).
In comparison to homogeneous acid catalysts, heterogeneous solid acid catalysts have been found to
be more effective due to the presence of acid sites with varied strengths of Bronsted or Lewis
acidity (Faruque et al., 2020). Furthermore, the ability of solid acid catalysts to sterically prevent
water from solvating the catalytic active sites aids in decreasing catalyst degradation and product
contamination due to simple separation from the process (Mansir et al., 2017). Finally, Mansir et al.
(2017) also added the solid acid catalyst's hydrophobic surface prevents polar by-products (water
and glycerol) from deactivating the active sites, allowing oily hydrophobic molecules to adsorb
selectively to the catalyst surface. However, there are also some drawbacks of solid acid catalysts
which because of its low catalytic activity, the solid acid catalyst takes longer to achieve the
maximum conversion rate (Faruque et al., 2020) while Mansir et al., (2017) stated that the use of
solid acid catalyst in a reaction requires high temperature. Other than that, solid acid catalysts seem
to be more costly to produce due to their complicated preparation techniques. The advantages and
disadvantages of solid acid catalysts from previous studies has been listed in Table 1.

Table 1. Advantages and disadvantages of solid acid catalysts

Advantages References Disadvantages References

Insensitive to the amount (Ali et al., 2017) Low catalytic activity (Faruque et al., 2020)
of FFA and water in the
oil
Separation of catalyst (Mansir et al., Long reaction time needed (Faruque et al., 2020)
from product is simple 2017)
High reusability and (Sirsam et al., Require higher cost (Bagnato et al., 2017)
regeneration potential 2016)

Reduce corrosion problem (F. Liu et al., Use high temperature (Mansir et al., 2017)
2018)

Ability of solid acid (Mansir et al.,

catalysts to sterically 2017)
prevent water from
solvating the catalytic
active sites

4.2 Stability of Solid Acid Catalysts

 Solids with acidic characteristics on their surfaces act as catalysts in the same way that
liquid acids like sulfuric acid and hydrochloric acid do. Chemical processes become more
productive and environmentally benign when solid acid catalysts are used (Liu et al., 2020). The
stability of the catalysts can be divided into two point of views which are structural stability and
chemical stability. The structure of a catalyst may change at high temperatures, and many structural
parameters such as surface area, pore size, pore volume, and pore distribution may change
respectively (Khamzin et al., 2018).
According to Liu et al. (2020)’s research, a co-catalyst might be introduced to prevent
migratory microcrystals from collapsing into larger, less active ones. By improving the heat
resistance, poison resistance, mechanical strength, and service life of the primary catalyst, the
additional co-catalyst may improve its activity and selectivity. Vivier & Duprez. (2010), for
example, modified SO 42- / ZrO2 using rare earth oxide and alumina, finding that the catalyst co-
modified by Yb2 O3 - Al 2 O3 had the better esterification on the catalytic performance and had
reduced SO 42- face loss, resulting in a more stable catalyst. Aside from introducing a co-catalyst,
Wang et al. (2020) achieved bimetal synergism by using a citric acid complexation-impregnation
approach to create perovskite-type oxide (PTO) on a LaFe O3-supported Ni–Co bimetallic catalyst
and used it for hydrogen production by steam reforming of ethanol. The results of the experiments
showed that the catalyst had a high selectivity and was very stable in terms of hydrogen production.
Besides, chemical reactions that lead to a decrease in the active sites and specific surface
area of the catalyst, and eventually deactivation, are referred to as catalyst chemical stability.
Coking deactivation and poison adsorption inactivation are two prevalent chemical deactivation
methods. The chemical stability of solid acid catalysts is tightly related to acidity parameters (e.g.,
acid site, acidity, acid quantities) based on two chemical deactivation mechanisms (Liu et al., 2020).
The metal oxides ZrO2, TiO 2, and SnO 2 strengthened the interaction between the active metal Mo
and the supported alumina, according to Badoga, (2015)’s research. The catalyst with SnO 2 required
the highest reduction in temperature. The NH 3 -TPD results revealed that adding metal oxides to the
catalyst increased its acid strength, resulting in increased stability and catalytic performance, as well
as the prevention of coking. While Fan et al. (2006), used steam treatment and citric acid treatment
to alter the acidity of the HZSM-5 molecular sieve, demonstrating the effect of citric acid therapy
on zeolite steam dealumination. Citric acid treatment was also able to restore the pore structure of
steam-treated molecular sieves, as well as the number and strength of various acid sites, to their
original levels. This research laid the groundwork for increasing HZSM-5's physical and chemical
stability.
Immobilized mobile liquids are another technique to prevent deactivation and improve
chemical stability. Sabyrov et al. (2017) loaded and uniformly dispersed phosphotungstic acid on a
metal-organic frameworks (MOF), and the resulting catalyst was utilised to hydroisomerize n-
hexane using Bronsted acid sites. The findings show that the higher the phosphotungstic acid
loading amount, the higher the concentration and strength of the acid site, preventing or slowing
chemical deactivation through coking or poisoning. The factors that contribute to improve the
stability of the catalysts has been listed in Table 2.
Table 2. Techniques used to improve stability of solid acid catalysts

Techniques References

Structural Stability Adding co-catalyst (Vivier & Duprez, 2010)

Bimetal Synergism (Wang et al., 2020)

Chemical Stability Adding metal oxides (Badoga, 2015)

Control acidity of molecular (Fan et al., 2006)

sieves
Immobilized mobile liquids (Sabyrov et al., 2017)

5. TYPE OF SOLID ACID CATALYST USED IN ETHERIFICATION OF GLYCEROL

Various research has been done on the use of solid acid catalyst towards etherification of
glycerol. Cannilla et al. (2020) reported that commercial BEA-zeolites catalysts that has been
studied for the glycerol etherification process along with n-butanol as the reactant. It was claimed
that at a glycerol conversion of around 75%, a yield to di- and tri-butyl glycerol ethers as high as
10% is observed. At 180°C, with a butanol/glycerol molar ratio of 4, a catalyst quantity of 30 wt%
in relation to glycerol, and a reaction period of at least 6 hours, improved catalytic activity was
found. On the other hand, another types of zeolites was used in the research of Veiga et al. (2017),
which the best results for glycerol conversion were achieved by H-Beta and USY-650-L-2 zeolites,
which resulted 74% and 75% in tert-butyl alcohol tests and 81% and 67% in ethyl alcohol testing,
respectively. It was discovered that zeolites' features such as hydrophilicity/hydrophobicity, acidity,
and texture, which are all affected by the Si/Al molar ratio, have an impact on catalytic activity
(Veiga et al., 2017).
Next, research by Magar et al. (2017) used Mont-clay catalysts in their research of glycerol
etherification with tert-butyl alcohol to give ether products. Mont-clay catalysts has been
commercialized as useful solid acid catalyst in the industry. The results shows that Mont-KSF/O
actively accelerated the etherification reaction and total glycerol conversion obtained was 27% with
a 1:20 molar ratio of glycerol to TBA in 6 hours at 110°C. This is due to its greatest acidity as
determined by ammonia-TPD (Mont-KSF/O > Mont-K-10 > Mont-Al) amongst those tested
catalysts. Despite its reduced surface area when compared to other catalysts, the Mont-KSF/O
catalyst seemed to have the highest glycerol conversion compared to other samples due to Bronsted
acidic sites having the highest acidity (Magar et al., 2017).
Finally, Amberlyst-15 has been extensively researched for the etherification of glycerol
among the two solid acid catalysts listed above. Amberlyst-15 is a strong acidic catalyst that was
designed specifically for heterogeneous acid catalysis of many different organic reactions.
Esterification (acetates, acrylates, fatty acid esters), Etherification (MTBE, ETBE, TAME), Phenol
alkylation, Condensation, and Hydrolysis are some of the areas where the catalyst has been widely
employed (Dow Chemical, 2018). This catalyst has microporous pore structure that can easily
facilitate the reactants towards the hydrogen ion sites.
According to Lemos et al. (2017), Amberlyst-15 had a substantially larger mesopore volume
and size than Beta zeolite and niobic acid, which were both composed by micro and mesopores in
the study. In the etherification of glycerol with tert-butyl alcohol, the inclusion of a solid acid
catalyst (ion exchange commercial resin Amberlyst, A-15) has a beneficial effect since it allows the
reaction equilibrium to shift towards the synthesis of diethers (Dominguez et al., 2019). Since
Amberlyst-15 is a heterogeneous catalyst, the separation was easily done as in Roze et al. (2013) ‘s
study which Amberlyst-15 and Amberlyst-36 catalysts were easily separated after washing with
water, ethanol, and drying at 110 °C. Furthermore, the recycled catalysts showed the same catalytic
activity as new catalysts (Roze et al., 2013). Pico et al. (2013) stated that A-15 was chosen as the
best catalyst above Amberlite 200 and Amberlite IRC50 because of its higher acidity and better
textural qualities, which result in higher activity in glycerol etherification. Amberlyst-15 and
Amberlite 200 yielded the same conversion of glycerol which is 50% but Amberlite IRC50 yielded
lower conversion. This might be because Amberlite IRC50 has a very low apparent surface area as
well as a very low acidity (Pico et al., 2013). Hence, the lack of porous structure growth and a low
acidity value will lead to a low catalytic activity of the catalyst. Table 3 shows the list examples of
solid acid catalysts that has been used from previous research for etherification of glycerol with its
products and percentage of glycerol conversion.

Table 3. Solid acid catalyst used in etherification of glycerol.

Catalyst Reactant Product Glycerol References

conversion, %
BEA-zeolites Glycerol and n- Di- and tri-butyl 75 (Cannilla et al.,
butanol glycerol ethers 2020)

H-Beta and USY-650- Glycerol with tert- Monoethers and 74 and 75 (Veiga et al.,
L-2 zeolites butyl alcohol and diethers 2017)
ethyl alcohol
Mont-clay catalysts Glycerol with tert- Mono ethers, di and 27 (Magar et al.,
butyl alcohol tri-tert butyl 2017)
glycerol ethers
Amberlyst-15, Glycerol and tert- Mono ethers and 50 (Pico et al.,
Amberlite 200 and butyl alcohol diethers 2013)
Amberlite IRC50
Amberlyst-15 Glycerol and tert- Mono ethers, di 96 (Huang & Kim,
butyl alcohol ethers and tert 2015)
glycerol ethers
Cesium exchanged Glycerol and tert- Glycerol ethers 88 (Srinivas et al.,
tungstophosphoric acid butanol 2016)
6. REACTION PARAMETERS IN ETHERIFICATION OF GLYCEROL BY USING
SOLID ACID CATALYSTS

Optimization is a method used in chemicals processing to tackle the challenge of

minimizing or maximizing an optimal solution that connects the variable to be optimized with the
growth and developmental variables. Many characteristics, such as reaction time, catalyst
concentration, temperature effect, molar ratio, and others, are often used to determine the
optimization variables in the etherification process.

6.1 Reaction Time

It was reported by Huang & Kim. (2015) that the highest conversion of glycerol with tert-
butyl alcohol through etherification was approximately 96.0% to 97.0% at 5 to 6 hours with the use
of Amberlyst-15 catalyst, then began to decrease by approximately 80 percent at 60 hours. Based on
the results of the experiment, the reaction shows that reaction time does affect the conversion yield
and it must be set between 5 and 8 hours to obtain the maximum yield of glycerol ethers (Huang &
Kim, 2015). Compared to the research of Nandiwale et al. (2014), the maximal conversion of
glycerol was 55% and selectivity of methyl ethers were reached almost 98% at a reaction time of 4
hours over a H-beta zeolite catalyst. As a result, the etherification reaction was shown to have an
optimum reaction time of 4 hours.
However, upon converting glycerol with a Cesium exchanged tungstophosphoric acid
catalyst, the conversion was strong yet after 30 minutes, indicating that the catalyst was energetic,
but the selectivity for higher ethers was only 25%. Because the di- and tri-ether products are
generated through repetitive etherification processes, glycerol conversion and selectivity towards
higher ethers climbed as reaction time increased from 30 to 60 minutes, whereas mono-ether
selectivity declined. Within 60 minutes of reaction time, maximum glycerol conversion and
selectivity toward higher ethers were reached. The selectivity for higher ethers remained consistent
as the reaction time increased, indicating that the reaction had reached equilibrium after 60 minutes
(Srinivas et al., 2016).
From the study of Cannilla et al. (2020), with zeolite assisting as catalyst, glycerol
conversion improves from 28.5% (6 hours) to 61.1% (15 hours), and from 85.8% (6 hours) to
89.7% (15 hours) at 473 K. This data shows that reaction time has a substantial impact on reaction
kinetics, and that a 6 h reaction time is insufficient to reach the maximal yield. Yet, as the
temperature rises (to 200 °C), the synthesis of glycerol polymers and side products becomes more
important. Table 4 shows the differences in reaction time and percentage of glycerol conversion on
different solid acid catalysts for etherification of glycerol. To conclude, the reaction time shows that
different type of catalysts will gives different reaction time, and it will influence the percentage of
glycerol conversion.
Table 4. Reaction time and percentage of glycerol conversion on different solid acid catalysts in
etherification of glycerol.

Catalyst Reactant Reaction Time Glycerol References

(hr) conversion (%)
Amberlyst-15 Glycerol and tert- 6 97 (Huang & Kim,
butyl alcohol 2015)

H-beta zeolite Glycerol and n- 4 55.0 (Nandiwale et al.,

butanol 2014)

Cesium exchanged Glycerol and tert- 1 88.0 (Srinivas et al.,

tungstophosphoric butanol 2016)
acid
BEA-zeolites Glycerol and n- 15 89.7 (Cannilla et al.,
butanol 2020)

6.2 Temperature effect

With increasing reaction temperature, glycerol conversion increased. In the study of Huang
& Kim. (2015), de-etherification process occur which grew increasingly essential as the reaction
temperature was increased, prevented glycerol from being completely transformed at high
temperatures. Secondary reactions were also aided by a higher temperature. The percentage of
glycerol conversion increased as the temperature rose. On the other hand, as the temperature rose,
the disproportionation of glycerol ethers occurred as a side reaction. At 343 K, 97.0% of the
maximum glycerol conversion was found, as well as the highest selectivity of higher ethers which is
30.3%. This leads to the conclusion that temperature has an impact on the reaction in the following
ways: enhancement of side reactions and variations in reaction viscosity (Huang & Kim, 2015). The
effect of temperature towards conversion and selectivity using Amberlyst-15 catalyst was depict in
Figure 5.

Figure 5. The effect of temperature on glycerol conversion and selectivity of ethers product.
 Source: (Huang & Kim, 2015)
Besides, in the reaction of etherification of glycerol with n-butanol to the selective synthesis
of mono-butyl-glycerol ether (ME), it was demonstrated that as the reaction temperature increased
from 413 K to 453 K, the glycerol conversion increased from 30% to 72%, and the selectivity
towards mono-butyl-glycerol ether (ME) increased from 91% to 98% (Nandiwale et al., 2014).
However, the mono-butyl glycerol ether selectivity was shown to decrease as the temperature was
increased, as reported in Table 5.

Table 5. The effect of reaction temperature on glycerol etherification.

Temperature (K) Glycerol Selectivity (%)

conversion
(%) Mono-butyl glycerol Di-butyl
ether glycerol ether
413 30.2 91.4 8.1

423 44.5 93 5.3

433 55 98 1.2

443 63.4 81.3 15.6

453 72 63.2 32.6

Source: (Nandiwale et al., 2014)

The formation rate of di-butyl glycerol ether (secondary ether) was greater than that of
mono-butyl glycerol ether at higher reaction temperatures of 433 K. Thus, the optimum reaction
temperature for glycerol etherification was 433 K, with a 55% glycerol conversion and a 98%
selectivity toward mono-butyl glycerol ether.
Next, the effect of reaction temperature on glycerol conversion with a Cesium exchanged
tungstophosphoric acid catalyst in the temperature range of 353 K-383 K was examined (Srinivas et
al., 2016). At 353 K, glycerol conversion was only 66%, with a 20% selectivity toward higher
ethers. The conversion of glycerol climbed to 91% as the temperature increased to 373 K, and
selectivity to higher ethers improved from 27% to 43%. However, the production of polymeric
products was seen when the reaction was carried out above 383 K. Isobutene dimerization may have
produced these by products.
Lastly, the effect of temperature was investigated for etherification of glycerol by using the
BEA type zeolites, BH50: 1 SiO2-0.01 Al2 O3 -0.1Na 2 O-0.2TEA-10H2 Owhere TEA is
tetraethylammonium hydroxide. The temperature range was chosen between 413 K and 473 K. The
catalytic activity improves as the reaction temperature rises, resulting in a high glycerol conversion
of up to 26 % at 453 K and 85.2 % at 473 K. Simultaneously, the selectivity of 1-ME (mono
glyceryl ether) falls from 83.7 % at 413 K to 49.9% at 473 K, with a minor increase in selectivity of
1,3-DE (di-butyl glyceryl ether) up to 11.7 % at higher temperatures. Because of steric constraints,
the selectivity to tri-butyl glyceryl ether was quite low. The comparison of the effect of temperature
and selectivity towards mono-glycerol ether between different solid acid catalysts in etherification
of glycerol was listed in Table 6.
Table 6. Effect of temperature on glycerol conversion with different solid acid catalysts in etherification of
glycerol.

Catalyst Temperature (K) Glycerol Selectivity (%) References

Conversion (%)

Amberlyst-15 343 97 30.3 (Huang & Kim,

2015)

H-beta zeolite 433 55 98 (Nandiwale et al.,

2014)

Cesium exchanged 373 91 43 (Srinivas et al.,

tungstophosphoric 2016)
acid
BH50 resin (BEA 473 85.2 49.9 (Cannilla et al.,
type zeolites) 2020)

6.3 Catalyst loading

A substance that enhances the rate of a chemical reaction without undergoing any permanent
chemical change is known as a catalyst loading. In the research of Nandiwale et al. (2014), the
catalyst loading was changed between 7% and 10 wt% glycerol. Hence, the glycerol conversion was
raised from 19% to 29%. However, the glycerol conversion was unaffected by changes in catalyst
loading from 10% to 20%. Increased catalyst loading up to 15% may have increased glycerol
conversion and selectivity towards mono-glycerol ether. It was concluded that the 15% catalyst
loading was found to be the most effective. While in the study of Magar et al. (2017), gives the
result of almost completed glycerol conversion with percentage of 98% by using Mont KSF/O
catalyst which is a type of montmorillonite clay solid acid catalyst.
Besides, Cannilla et al. (2020), has proven in their research that increasing the amount of
catalyst from 10% to 20% by weight doubles the glycerol conversion, reaching a value close to
58%. BEA-type zeolites, (BH50) catalyst was utilized as a catalyst in this study. As a result of
raising the catalyst concentration (30 wt%), the conversion rate rises to 73.1 %. This shows that
increasing the catalyst loading favors glycerol etherification with n-butanol while also increasing
the amount of glycerol conversion.
Huang & Kim. (2015), research looked at the impacts of different catalyst amounts by
changing the Amberlyst-15 loading in terms of the glycerol weight percentage. At the lowest and
maximum catalyst loading levels examined in this study, both glycerol conversion and product yield
were low and high respectively. Conversion differences between 5.0% and 10.0%, on the other
hand, were not as significant. The best results, however, were obtained with a 7.5 wt% glycerol
injection, which showed the highest percentage of glycerol conversion at 96%. Therefore, the
highest percentage of glycerol conversion was demonstrated by Mont KSF/O catalyst whish is 98%.
The comparison of effect of catalyst loading towards glycerol conversion by using different solid
acid catalysts have been summarized in Table 7.
Table 7. Effect of catalyst loading on glycerol conversion between different solid acid catalysts in
etherification of glycerol.

Catalyst Catalyst Loading Glycerol Conversion References

(wt%) (%)

H-beta zeolite 15 29 (Nandiwale et al., 2014)

Mont KSF/O catalyst 27.17 98 (Magar et al., 2017)

BEA-type zeolites 30 73.1 (Cannilla et al., 2020)

(BH50)

Amberlyst-15 7.5 96 (Huang & Kim, 2015)

6.4 Molar ratio

When the molar ratio is smaller than 8, Huang & Kim. (2015) research demonstrates that an
increase in the molar ratio leads to an increase in their impacts on total concentration of ethers. At
the lowest molar ratio measured (Glycerol/TBA= 1:2), ether concentration was practically
nonexistent. The influence of the molar ratio on this reaction can be explained by the viscosity of
the reaction mixture. The greater viscosity resulted in less mass transfer between the phases when
the TBA/glycerol ratio was low. Mass transfer grew easier when the ratio was raised, and the
maximum concentrations were reached when the molar ratio was 8. As a result, the ideal molar ratio
should be set between 4 and 8 (Huang & Kim, 2015). The influence of the molar ratio on the yield
of ethers was shown in Figure 6.
Figure 6. Influence of the molar ratio on the yield of ethers

Source: (Huang & Kim, 2015)

 The H-beta zeolite catalyst's efficiency for glycerol etherification was further investigated
by altering the n-butanol content in the feed by research of Nandiwale et al. (2014). The conversion
of glycerol rose from 19% to 27% as the molar ratio of glycerol to n-butanol was increased from 1:6
to 1:9. There was no change in glycerol conversion as the molar ratio was increased above 1:9.
Regardless of the amount of n-butanol in the feed, mono-butyl glycerol ether had the same
selectivity (97%). Hence, the optimal molar ratio of glycerol to n-butanol 1:9.
Apart from that, according to Srinivas et al. (2016) research, the molar ratio of glycerol to
tert-butanol is a crucial parameter for obtaining high glycerol conversion and selectivity towards
higher ethers. According to the findings, glycerol conversion rose from 75% to 91% as the mole
ratio of glycerol to tert-butanol increased from 1:6 to 1:12. However, increasing the mole ratio from
1:12 to 1:15 did not result in a substantial increase in glycerol conversion. The decrease in
selectivity can be explained by the fact that higher tert-butanol concentrations obstruct the
etherification reaction by blocking active areas on the catalyst surface.
Finally, Cannilla et al. (2020) research analyzed the effect of the glycerol/butanol ratio by
employing BH25 resin (BEA type zeolites) as a catalyst. The findings show that raising the
glycerol/butanol molar ratio from 1:3 to 1:8 reduces glycerol conversion by 30%. The catalyst
dilution in the reaction medium most likely has a negative effect on the chemical kinetics, hence the
ideal molar ratio is 1:3 mol/mol. The yield to di- and tri-ethers is 2.9% when employing this ratio,
compared to only 1.8% when using a ratio of 1:8 mol/mol. Table 8 summarizes the differences of
molar ratio and glycerol conversion over different solid acid catalysts for etherification of glycerol.

Table 8. Optimal molar ratio and glycerol conversion over different solid acid catalysts for etherification of
glycerol

Catalyst Optimal molar ratio Glycerol References

conversion
Glycerol/Reactant Ratio (%)
(mol/mol)
Amberlyst-15 Glycerol/TBA 1:2 96 (Huang &
Kim, 2015)
H-beta zeolite Glycerol/n-butanol 1:9 27 (Nandiwale
et al., 2014)
Cesium Glycerol/tert- 1:1 91 (Srinivas et
exchanged butanol 2 al., 2016)
tungstophosph
oric acid
BH25 resin Glycerol/butanol 1:3 29.6 (Cannilla et
(BEA type al., 2020)
zeolites)
7. CONCLUSIONS
Solid acid catalysts are green catalysts, according to the principle of "green chemical industry,
sustainable development", since it has high degree of reusability and may be used in a wide range of
chemical reactions. Subsequently, the advantages and disadvantages of solid acid catalyst have been
determined by comparing it to each other. Also, the addition of a co-catalyst and bimetal synergism
can overcome the structural stability of solid acids that are prone to sintering and heat deactivation.
The solid acids that are prone to coking and poisoning deactivation may be overcome by modifying
the acidity of the catalyst surface, in order to improve the chemical stability of the catalyst.
Parameters on the usage of various solid acid catalysts on etherification of glycerol have been
compared to differentiate the percentage of conversion yield. To conclude, Amberlyst-15 was
shown to be the most effective in terms of glycerol conversion percentage after a comparison of
factors (reaction time, temperature effect, catalyst loading, and molar ratio) with several solid acid
catalysts.

ACKNOWLEDGEMENTS
This review paper was prepared with the support of the author's supervisor, Assoc. Prof. ChM. Dr.
Noraini Hamzah and under the observation of School of Chemistry, Faculty of Applied Sciences,
UiTM Shah Alam.

References
Ali, O. M., Mamat, R., Rasul, M. G., & Najafi, G. (2017). Potential of biodiesel as fuel for diesel
engine. In Clean Energy for Sustainable Development: Comparisons and Contrasts of New
Approaches.
Ashnani, M. H. M., Johari, A., Hashim, H., & Hasani, E. (2014). A source of renewable energy in
Malaysia, why biodiesel? Renewable and Sustainable Energy Reviews, 35, 244–257.
Badoga, S. (2015). Synthesis and characterization of NiMo supported mesoporous materials with
EDTA and phosphorus for hydrotreating of heavy gas oil. April, 334.
Bagnato, G., Iulianelli, A., Sanna, A., & Basile, A. (2017). Glycerol production and transformation:
A critical review with particular emphasis on glycerol reforming reaction for producing
hydrogen in conventional and membrane reactors. Membranes, 7(2).
Bookong, P., Ruchirawat, S., & Boonyarattanakalin, S. (2015). Optimization of microwave-assisted
etherification of glycerol to polyglycerols by sodium carbonate as catalyst. Chemical
Engineering Journal, 275, 253–261.
Cannilla, C., Bonura, G., Maisano, S., Frusteri, L., Migliori, M., Giordano, G., Todaro, S., &
Frusteri, F. (2020). Zeolite-assisted etherification of glycerol with butanol for biodiesel
oxygenated additives production. Journal of Energy Chemistry, 48, 136–144.
Chilakamarry, C. R., Sakinah, A. M. M., Zularisam, A. W., & Pandey, A. (2021). Glycerol waste to
value added products and its potential applications. Systems Microbiology and
Biomanufacturing, June.
Chong, C. C., Aqsha, A., Ayoub, M., Sajid, M., Abdullah, A. Z., Yusup, S., & Abdullah, B. (2020).
A review over the role of catalysts for selective short-chain polyglycerol production from
biodiesel derived waste glycerol. Environmental Technology and Innovation, 19, 100859.
Chozhavendhan, S., Karthiga Devi, G., Jayamuthunagai, J., Bharathiraja, B., Praveen kumar, R., &
Raman, J. K. (2019). Conversion of Glycerol to Valuable Products. In R. Pogaku (Ed.),
Horizons in Bioprocess Engineering (pp. 157–169). Springer International Publishing.
Dimitratos, N., Lopez-Sanchez, J. A., Anthonykutty, J. M., Brett, G., Carley, A. F., Tiruvalam, R.
C., Herzing, A. A., Kiely, C. J., Knight, D. W., & Hutchings, G. J. (2009). Oxidation of
glycerol using gold-palladium alloy-supported nanocrystals. Physical Chemistry Chemical
Physics, 11(25), 4952–4961.
Dominguez, C. M., Romero, A., & Santos, A. (2019). Improved etherification of glycerol with tert-
butyl alcohol by the addition of dibutyl ether as solvent. Catalysts, 9(4).
Dow Chemical. (2018). Product Data Sheet: AMBERLYST TM 15DRY Polymeric Catalyst. Product
Data Sheet, 177, 1–2.
Estevez, R., López, M. I., Jiménez-Sanchidrián, C., Luna, D., Romero-Salguero, F. J., & Bautista,
F. M. (2016). Etherification of glycerol with tert-butyl alcohol over sulfonated hybrid silicas.
Applied Catalysis A: General, 526, 155–163.
Fan, Y., Bao, X., Lin, X., Shi, G., & Liu, H. (2006). Acidity adjustment of HZSM-5 zeolites by
dealumination and realumination with steaming and citric acid treatments. Journal of Physical
Chemistry B, 110(31), 15411–15416.
Faruque, M. O., Razzak, S. A., & Hossain, M. M. (2020). Application of heterogeneous catalysts
for biodiesel production from microalgal oil—a review. Catalysts, 10(9), 1–25.
Frusteri, L., Cannilla, C., Bonura, G., Chuvilin, A. L., Perathoner, S., Centi, G., & Frusteri, F.
(2016). Carbon microspheres preparation, graphitization and surface functionalization for
glycerol etherification. Catalysis Today, 277, 68–77.
Gholami, Z., Abdullah, A. Z., Gholami, F., & Vakili, M. (2015). Modified silica-based
heterogeneous catalysts for etherification of glycerol. AIP Conference Proceedings, 1669.
Hattori, H., & Ono, A. Y. (2014). Solid Acid Catalysis.
Huang, R., & Kim, E. Y. (2015). Catalytic synthesis of glycerol tert-butyl ethers as fuel additives
from the biodiesel by-product glycerol. Journal of Chemistry, 2015.
Kakaei, K., Esrafili, M. D., & Ehsani, A. (2019). Introduction to Catalysis. Interface Science and
Technology, 27, 1–21.
Khamzin, Y. A., Shiriyazdanov, R. R., Davletshin, A. R., Murzabekova, A. B., Yakupov, N. V., &
Shadrina, A. E. (2018). Application of Oxidative Regeneration of Zeolite-Containing Catalysts
to Solid-Acid Alyklation of Isobutane by Olefins. Chemistry and Technology of Fuels and
Oils, 54(3), 278–284.
Lemos, C. O. T., Rade, L. L., Barrozo, M. A. D. S., Fernandes, L. D., Cardozo-Filho, L., & Hori, C.
E. (2017). Optimization of Catalytic Glycerol Etherification with Ethanol in a Continuous
Reactor. Energy and Fuels, 31(5), 5158–5164.
Liu, F., Huang, K., Zheng, A., Xiao, F. S., & Dai, S. (2018). Hydrophobic Solid Acids and Their
Catalytic Applications in Green and Sustainable Chemistry. ACS Catalysis, 8(1), 372–391.
Liu, S., Zhu, M., & Iqbal, M. (2020). Research Progress on Stability of Solid Acid Catalysts.
Catalysis Surveys from Asia, 24(3), 196–206.
Lopez-Suarez, F. E., Riveros-Riveros, D. M., Cesteros, Y., & Salagre, P. (2021). Raw glycerol re-
valuing through etherification with isobutylene: process design and techno-economical
assessment. Journal of Industrial and Engineering Chemistry, 94, 159–165.
Magar, S., Kamble, S., Mohanraj, G. T., Jana, S. K., & Rode, C. (2017). Solid-Acid-Catalyzed
Etherification of Glycerol to Potential Fuel Additives. Energy and Fuels, 31(11), 1227–1277.
Malaika, A., Ptaszyńska, K., & Kozłowski, M. (2021). Conversion of renewable feedstock to bio-
carbons dedicated for the production of green fuel additives from glycerol. Fuel,
288(September).
Mansir, N., Taufiq-Yap, Y. H., Rashid, U., & Lokman, I. M. (2017). Investigation of heterogeneous
solid acid catalyst performance on low grade feedstocks for biodiesel production: A review.
Energy Conversion and Management, 141, 171–182.
Marinho, C. M., Marcos, M. A., & Hori, C. E. (2020). Optimization of glycerol etherification with
ethanol in fixed bed reactor under various pressures. Energy, 207, 118301.
Monteiro, M. R., Kugelmeier, C. L., Pinheiro, R. S., Batalha, M. O., & da Silva César, A. (2018).
Glycerol from biodiesel production: Technological paths for sustainability. Renewable and
Sustainable Energy Reviews, 88(November 2016), 109–122.
Mustafa, N. R., Spelbos, V. S., Witkamp, G., Verpoorte, R., & Choi, Y. H. (2021). Solubility and
Stability of Some Pharmaceuticals in Natural Deep Eutectic Solvents-Based Formulations. 1–
18.
Nandiwale, K. Y., Patil, S. E., & Bokade, V. V. (2014). Glycerol Etherification using n-Butanol to
Produce Oxygenated Additives for Biodiesel Fuel over H-Beta Zeolite Catalysts. Energy
Technology, 2(5), 446–452.
Nda-Umar, U. I., Ramli, I., Taufiq-Yap, Y. H., & Muhamad, E. N. (2019). An overview of recent
research in the conversion of glycerol into biofuels, fuel additives and other bio-based
chemicals. Catalysts, 9(1).
Pico, M. P., Rosas, J. M., Rodríguez, S., Santos, A., & Romero, A. (2013). Glycerol etherification
over acid ion exchange resins: Effect of catalyst concentration and reusability. Journal of
Chemical Technology and Biotechnology, 88(11), 2027–2038.
Pradima, J., Kulkarni, M. R., & Archna. (2017). Review on enzymatic synthesis of value added
products of glycerol, a by-product derived from biodiesel production. Resource-Efficient
Technologies, 3(4), 394–405.
Roze, M., Kampars, V., Teivena, K., Kampare, R., & Liepins, E. (2013). Catalytic Etherification of
Glycerol with Alcohols. Material Science and Applied Chemistry, 28(28), 67.
Sabyrov, K., Jiang, J., Yaghi, O. M., & Somorjai, G. A. (2017). Hydroisomerization of n-Hexane
Using Acidified Metal-Organic Framework and Platinum Nanoparticles. Journal of the
American Chemical Society, 139(36), 12382–12385.
Sirsam, R., Hansora, D., & Usmani, G. A. (2016). A Mini-Review on Solid Acid Catalysts for
Esterification Reactions. Journal of The Institution of Engineers (India): Series E, 97(2), 167–
181.
Srinivas, M., Raveendra, G., Parameswaram, G., Prasad, P. S. S., & Lingaiah, N. (2016). Cesium
exchanged tungstophosphoric acid supported on tin oxide: An efficient solid acid catalyst for
etherification of glycerol with tert-butanol to synthesize biofuel additives. In Journal of
Molecular Catalysis A: Chemical (Vol. 413). Elsevier B.V.
Taipabu, M. I., Viswanathan, K., Wu, W., & Nagy, Z. K. (2021). Production of renewable fuels and
chemicals from fats, oils, and grease (FOG) using homogeneous and heterogeneous catalysts:
Design, validation, and optimization. Chemical Engineering Journal, 424(April), 130199.
Vahdatzaman, M. (2017). Novel Catalytic Etherification Reaction of Glycerol to Short-Chain
Polyglycerol. April.
Veiga, P. M., Gomes, A. C. L., Veloso, C. O., & Henriques, C. A. (2017). Acid zeolites for glycerol
etherification with ethyl alcohol: Catalytic activity and catalyst properties. Applied Catalysis
A: General, 548, 2–15.
Veiga, P. M., Veloso, C. O., Dias, A. G., & Henriques, C. A. (2018). Identification of Ethyl and t-
Butyl glyceryl ethers using gas chromatography coupled with mass spectrometry. Journal of
the Brazilian Chemical Society, 29(6), 1328–1335.
Vivier, L., & Duprez, D. (2010). Ceria-based solid catalysts for organic chemistry. ChemSusChem,
3(6), 654–678.
Wang, J., Yang, M., & Wang, A. (2020). Selective hydrogenolysis of glycerol to 1,3-propanediol
over Pt-W based catalysts. Chinese Journal of Catalysis, 41(9), 1311–1319.
Zheng, A., Li, S., Liu, S. Bin, & Deng, F. (2016). Acidic Properties and Structure-Activity
Correlations of Solid Acid Catalysts Revealed by Solid-State NMR Spectroscopy. Accounts of
Chemical Research, 49(4), 655–663.