Fuel 103 (2013) 980–986

Contents lists available at SciVerse ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Etherification of glycerol for improved production of oxygenates

Nagabhatla Viswanadham ⇑, Sandeep K. Saxena
Catalysis and Conversion Process Division, CSIR-Indian Institute of Petroleum, Dehradun 248 005, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" High oxygenate yields are obtained

on zeolite catalyzed ter-butylation of
glycerol.
" Porosity rather than acidity of
zeolites greatly influenced the
oxygenate production activity.
" N-BEA, with its additional
mesoporosity exhibited higher
selectivity and stability in oxygenate
production.
" Higher DTBG formation is
advantageous for production of
diesel miscible oxygenate with less
TBA consumption.

a r t i c l e i n f o a b s t r a c t

Article history: Various resin and zeolite based catalysts are prepared, characterized and evaluated for their catalytic per-
Received 7 May 2012 formance towards the etherification of glycerol with tertiary butyl alcohol. Resin based catalysts exhib-
Received in revised form 11 June 2012 ited higher glycerol conversions and ether selectivities at relatively lower reaction temperature (75 °C)
Accepted 12 June 2012
than the zeolite based catalysts (90° to 110 °C) but the zeolite based catalysts performed better in terms
Available online 27 June 2012
of stability in activity to produce high amounts of di-tertiary butyl (DTBG) and tri-tertiary butyl ether
(TTBG) of glycerol (oxygenate stock). Though acidity is important for the etherification reaction, the zeo-
Keywords:
lites exhibiting better porosity rather than acidity could yield higher oxygenate. The presence of inter-
Zeolites
Acidity
crystalline meso-pores in N-BEA further improved the oxygenate production and time-on-stream activity
Pore volume of the catalyst. At optimized catalyst parameters and reaction conditions, Nano-beta (N-BEA) zeolite cat-
Glycerol alyst exhibited above 95% conversion of glycerol with more than 45% and 54% selectivities to DTBG and
Oxygenate TTBG, which are potential blending stocks for diesel.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction value addition, etherification stands best as it produces oxygenate

Recently, bio-diesel is emerging as a competitive alternative to
the traditional fossil fuel based diesel by virtue of its properties
such as lubricity, high flash point, close heat combustion, viscosity,
limited exhaust emissions and superior cetane number [1–4].
However, the unavoidable formation of huge glycerol bi-product
limits the fuel yields. Moreover, the glycerol component in bio-die-
sel polymerizes at high temperatures and part of it oxidizes to give
toxic acrolein. Among the various chemical routes for glycerol
⇑ Corresponding author. Tel.: +91 135 2525856; fax: +91 135 2660202.
E-mail address: nvish@iip.res.in (N. Viswanadham).
blending stock for diesel to improve the total yields and quality of
diesel by reducing emissions through decreasing viscosity and
cloud points [5–9].
Generally, the isobutylene produced by steam cracking of high
boiling petroleum fractions or mixture of saturate hydrocarbons
is used for etherification [10–13]. However, the usage of isobutyl-
ene is expensive and needs additional step of purification to sepa-
rate it from the C4 mixture either by sulfuric acid extraction or by
using molecular sieves. Another drawback of using butylene is its
dimerization activity to produce undesired di-enes and poly oligo-
mers that affect the alkylate yields and catalyst stability [14,15].
The immediate striking option is to use bio-alcohols such as

0016-2361/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2012.06.057
 N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986 981

Table 1
Physico chemical properties of various catalysts.

Catalysts SiO2/Al2O3 Form Acidity BET surface area (m2/g) Pore volume (cm3/g) Structure stability (°C) Swollen properties (cm3/g)
Water Glycerol
A-15 – H 4.7a 53 0.40 120 1.02 1.13
A-35 – H 5.2a 50 0.35 150 1.01 1.27
MOR 16 H 1.48b 400 0.26 800 – –
BEA 25 H 0.88b 450 0.56 800 – –
USY 6 H 0.92b 614 0.30 800 – –
N-BEA 25 H 0.90b 565 0.78 800
a
Acidity (meq H+/g catalyst) determined by titration method.
b
Acidity (mmol ammonia/g catalyst) determined by micro-calorimetric method.

ethanol and butanol as glycerol etherifying agent [16–18]. How- the viscosity and pH, followed by its drying at room temperature
ever, the ethanol reaction is mainly aimed to produce mono ter- over night and calcination at 550 °C for 4 h [25].
tiary butyl ether of glycerol (MTBG) that is further processed for
the production of high octane oxanes and oxalones useful for gas-
2.1.2. Extrudate preparation
oline blending [19–21]. The tertiary butylation of glycerol is aimed
Shaping of all the powder samples was carried out by mixing
to produce di-tertiary butyl ether (DTBG) and tri-tertiary butyl
zeolite with pseudo boehmite (neutral alumina) binder in 3:2 zeo-
ether (TTBG) as they can directly blend to diesel. When compared
lite: binder weight ratio, followed by peptizing it using 3 vol.% gla-
to the isobutylene the price and handling of tertiary butyl alcohol
cial acetic acid. Wet extrusion of the resultant paste was carried
(TBA) is cheaper and unlike the refining originated isobutylene TBA
out through a 2 mm diameter size metallic syringe and the drying
is a bio-origin as it is produced from starch or lignocellulosic bio-
is conducted at room temperature overnight followed by treating
mass or wheat/straw fiber.
at 100 °C for 7 h and calcination at 500 °C for 4 h.
The resins of Amberlyst 15 (A-15) and Amberlyst 35 (A-35) type
with their acidity, reticulate structure and pore volume have been
reported to exhibit good etherification activity. But very little is re- 2.2. Characterization of catalysts
ported about the performance of these resins towards TBA etheri-
fication of glycerol and their selectivity towards the preferential The BET surface area and pore volume measurements of cata-
production of DTBG and TTBG [22–24]. Zeolites with their system- lysts were carried out on ASAP 2010, Micromeritics Instruments
atic pore size and tunable acidity may be potential candidates to
produce high yields of DTBG and TTBG, but, the information
regarding this aspect is scarce in the literature.
Considering all the above mentioned facts, two resin catalysts
(A)
and various zeolite based catalysts have been chosen for etherifica-
INTENSITY (CPS)

tion of glycerol with TBA in the present study. The catalytic prop-
erties responsible for production of oxygenate (DTBG + TTBG) have N-BEA
been studied with a special attention to the preferential production
of DTBG as it involves less TBA consumption as compared to TTBG.

2. Experimental BEA

2.1. Chemicals and catalysts

Glycerol (99%) and tertiary butyl alcohol (99%) were obtained 5 10 15 20 25 30 35 40 45 50 55 60

from Merck Chemicals. Amberlyst-15 (A-15) and Amberlyst-35 2θ
(A-35) were procured from Rohm and Hass, US. The three zeolites,
beta (BEA), mordenite (MOR) and ultra-stable Y (USY) are obtained 0.04
in powder form from the Sud-Chemie India Ltd., where as the (B)
nano-crystalline BEA (N-BEA) has been synthesized in laboratory.
0.03
TCD SIGNAL (a.u.)

BEA
2.1.1. Synthesis of nano-crystalline BEA zeolite (N-BEA)
In a typical procedure of N-BEA synthesis, sodium ion-free
homogenous gel was obtained by sequential mixing of silica source 0.02
(Tetraethyl orthosilicate, TEOS, Merck) to quaternary ammonium
salt (Tetraethyl ammonium hydroxide, Merck) followed by drop
N-BEA
wise addition of alumina source (Aluminum oxide, Merck) at be- 0.01
low room temperature (0–2 °C) with vigorous stirring of the mix-
ture for 8 h followed by leaving it at room temperature for 40 h for
hydrolysis. The gel thus obtained was heated at 80 °C to evaporate
0
water and ethanol formed during the hydrolysis of TEOS and the 0 200 400 600 800
resultant viscous gel was treated at 140 °C for 2 days in a Teflon
TEMPERATURE (°C)
lined autoclave at autogenous pressure. Recovery of solids from
this highly stable suspension was obtained by centrifuging at a Fig. 1. Properties of micro and nano-crystalline BEA zeolites. (A) X-ray diffraction
very high speeds and times after diluting with water to lower patterns and (B) TPD patterns.
982
(A)
140
QUANTITY ADSORBED Cm3 /g STP
(C)
120
100
80
0.0 0.2 0.4
RELATIVE PRESSURE (P/P° )
Fig. 2. Structural and adsorption properties of zeolites. (A and B) SEM images and (C and D) adsorption–desorption isotherms of BEA and N-BEA respectively.
Inc., Norcross, GA, USA, using N2 gas. The acidity of the resin cata-
lysts is measured by the well known base titration method, where
as that of zeolite catalysts is measured by Micro-calorimetric
ammonia adsorption studies using a Tian-Calvet type heat-flow
micro-calorimeter (C-80 model, Setaram, France). The detailed acid
strength distribution trends of BEA and N-BEA have been measured
by Temperature programmed desorption (TPD) of ammonia using
Micromeritics 2750 pulse chemisorption system. The resin cata-
lysts were also measured for their swelling properties for the
adsorption capacity of water as well as glycerol. The morphology
and structural identification of the samples were conducted on
Quanta 200f SEM instrument, Netherland and Rigaku Dmax IIIB,
XRD instrument with Cu Ka radiation.
2.3. Reaction and product analysis
The etherification reaction was carried out in two types of reac-
tors; (1) batch reactor and (2) fixed bed reactor (continuous flow
reactor). In batch reaction studies 5 g of glycerol and 16.1 g TBA
placed along with 0.38 g catalyst in the reactor and out gassed.
The reaction was conducted at 60–90 °C at autogenous pressure
with continuous stirring. In fixed bed reactor studies 5.0 g catalyst
was loaded in 30 ml capacity reactor and the reaction is conducted
with continuous flow of TBA and glycerol mixture in 76:24 g/g
(4:1 M) ratio. The reaction was conducted at 110 °C, 5.0 bar with
N2 as carrier gas (flow 16.0 L/h) where as the weight hourly space
velocity (WHSV) of the reaction mixture is varied from 0.5 to 2.0.
The reaction product was cooled and separated into gaseous and
liquid products in a high-pressure separator. The conversion and
product yields were analyzed by gas chromatography-mass spec-
N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986
(B)
500
(D)
400
300
200
100
0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
RELATIVE PRESSURE (P/P° )
trometry using 5890 series II GC and 5972 series mass selective
detector.
3. Results and discussion
3.1. Physico-chemical properties of catalysts
Both the resin catalysts exhibited comparable properties in
terms of surface area and water swelling capacity but the acidity,
glycerol retention capacity and thermal stability of A-35 is better
than the corresponding A-15 catalyst (Table 1). Among the zeolites,
the MOR exhibited the highest acidity of 1.48 mmol/g catalyst, fol-
lowed by Y zeolite (0.92 mmol/g) and BEA (0.88 mmol/g). However,
Y zeolite exhibited high surface area, while BEA and N-BEA showing
higher pore volume. The X-ray diffraction patterns shown in Fig. 1
suggest that both BEA and N-BEA samples are having the frame-
work structure of Beta zeolite. Further, the N-BEA exhibited struc-
tural identity and comparable acidity with BEA as confirmed by
XRD patterns (Fig. 1A) and TPD patterns (Fig. 1B). The SEM images
of the BEA and N-BEA samples shown in Fig. 2A suggest that the
zeolite crystal size has been successfully brought down from mi-
cro-meter range (5 lm) of BEA to nano-meter range (50 nm)
of N-BEA. The morphology of the crystals is also changed from elon-
gated hexagonal in BEA to near spherical structures in N-BEA. Thus,
the nano-meter range small crystals of N-BEA with near spherical
morphology are expected to create intercrystalline voids falling in
the range of mesopores in the N-BEA which is indeed observed from
the sorption isotherms of N-BEA (Fig. 2B). Here the closed symbols
represent the adsorption curves, while open symbols denote the
 N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986 983

Table 2
Glycerol etherification performance on various catalysts.

Catalyst Reaction temperature (°C) Reaction time (h) Glycerol conversion (wt.%) Ethers selectivity
Mono Di Tri
Batch reactor studies
Pressure = Atmospheric, TBA: GLY = 4:1 M ratio
A-15 75 1 98.6 14.2 45.6 40.2
A-15 75 2 98.2 38.8 40.6 20.6
A-15 75 3 97.6 58.8 38.6 2.6
A-15 75 5 95.4 67.2 32.8 –
A-15 60 4 97.7 95.9 4.1 –
A-15 75 4 96.6 66.2 33.8 –
A-15 90 4 97.8 94.2 5.8 –
A-15a 75 1 93.2 69 28.4 2.6
b
A-15 75 1 95.8 56.7 34.8 8.5
A-15c 75 1 97.4 33.6 40.6 25.8
A-15d 75 1 94 14.4 45.8 39.8
A-35 75 1 99.4 29.2 40.2 30.6
A-35 75 2 99.0 60.8 25.4 13.8
A-35 75 3 98.4 79.4 18.8 1.8
A-35 75 5 96.2 92.8 7.2 –
A-35 60 4 98.6 94.9 4.1 –
A-35 75 4 97.5 91.5 8.5 –
A-35 90 4 97.7 94.8 5.2 –
MOR 90 4 66.1 99.4 0.6 –
USY 90 4 100.0 100.0 – –
BEA 90 4 96.7 81.8 18.2
BEA 90 8 96.5 39.4 44.2 16.4
BEA 90 16 96.4 40.5 57.7 1.8
BEA 90 24 95.2 42.8 56.6 0.6
N-BEA 90 4 98.4 75.6 21.8 2.6
N-BEA 90 8 98.2 30.3 48.9 20.8
N-BEA 90 16 98.0 33.6 50 16.4
N-BEA 90 24 97.6 34.2 51.6 14.2
Fixed bed reactor studies
Pressure = 0.49 Megapascal (5.0 kg/cm2), TBA: Glycerol = 4:1 M ratio
BEA 110 4 87.2 31.8 57.6 10.6
BEA 110 4 89.6 25.0 55.6 19.4
BEA 110 4 91.4 5.9 43.3 50.8
BEA 110 4 95.8 4.0 44.6 51.4
N-BEA 110 4 89.8 20.6 52.8 26.6
N-BEA 110 4 94.8 15.6 49.8 34.6
N-BEA 110 4 97.8 2.0 44.8 53.2
N-BEA 110 4 98.6 0.8 45.2 54.0

TBA: Gly. molar ratio: a = 1:1, b = 2:1, c = 3:1, d = 4:1.

desorption curves. The open loop observed at 0.9–1.0 P/P0 of
N-BEA clearly envisions the presence of mesopores.
However, the difference in crystal size of BEA catalyst is not ex-
pected to make any difference in acidity as the initial gel composi-
tion taken for the synthesis of N-BEA catalyst is similar to that of
the BEA catalyst. The experimental data given in Table 1 also re-
veals the comparable acidity of N-BEA (0.90 mmol/g) with the
BEA catalyst (0.88 mmol/g). To further analyze the acidity in de-
tailed manner, TPD patterns are recorded for both the samples.
As shown in Fig. 1B, the samples exhibit almost similar desorption
patterns and is in accordance with their equal framework Si/Al ra-
tios. In addition to this, the N-BEA catalyst exhibited better proper-
ties in terms of higher surface area and pore volume perhaps due to
the easy accessibility of the adsorptive gases through the mesop-
ores during the surface area measurements, and these properties
are expected to facilitate the bulky molecular transformations in-
volved in glycerol etherification and the facile diffusion of the mol-
ecules during the reaction.
3.2. Etherification reaction studies
All the resin and zeolite based catalysts are studied for their
glycerol etherification performance in the batch reactor on all the
catalysts. The best catalysts identified in this study are further
evaluated in fixed bed reactor to explore the possibility of improv-
ing the product selectivities towards diesel miscible oxygenates,
namely, DTBG and TTBG.
3.2.1. Batch reactor studies
Since the aim of the present work is to produce DTBG + TTBG
mixture, the empirical equation suggests the TBA: Glycerol (Gly.)
ratio of 2–3 is suitable for this reaction. Since, TBA in the reaction
mixture is always higher than 1, the conversions are calculated
based on the glycerol concentration in the reactant and in the
product. Table 2 contains the conversion and product selectivities
of three ethers MTBG, DTBG and TTBG over the A-15 catalyst at
various TBA:Gly. ratios. The glycerol conversion is more than 90%
at all the reaction conditions. As expected, the MTBG is decreased
with simultaneous formation of DTBG and TTBG. The DTBG forma-
tion is not following the theoretical expectations, as the highest
amount of DTBG (34 wt.%) is observed at TBA:Gly. ratios 3 and 4
but not at 2. Further increase TBA concentration could not improve
the higher ether selectivities rather a slight decrease in glycerol
conversion is observed at TBA:Gly. ratio of 5 envisions the revers-
ible formation of glycerol from the ethers in presence of water at
this condition.
The performances of two Amberlyst catalysts are also studied at
various reaction temperatures, where, the glycerol conversions are
always >95% at all the reaction temperatures on both the catalysts
with MTBG being the major product, followed by DTBG with no
984 N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986

120 120
(A) Tri Di Mono Gly.Conversion Tri Di Mono Gly. Conversion
100
(A)

ETHER SELECTIVITY
90
ETHER SELECTIVITY

80

60 60

40

30
20

0
0
0 4 8 12 16 20 24 28
0 1 2 3 4 5 6
TIME (h) TIME (h)

120 120

(B) Tri Di Mono Gly.Conversion Tri Di Mono Gly.Conversion

100
(B)

ETHER SELECTIVITY
ETHER SELECTIVITY

90
80

60
60

40

30
20

0
0 0 4 8 12 16 20 24 28
0 1 2 3 4 5 6
TIME (h)
TIME (h)
Reaction Conditions : Temperature =90 ° C,
Reaction Conditions : Temperature =75°C,
Pressure = Atmospheric, TBA : Gly. Molar ratio = 4:1
Pressure = Atmospheric, TBA: Gly. = 4:1
Fig. 4. Time-on-stream selectivity to glycerol ethers on zeolite based catalysts. (A)
Fig. 3. Time-on-stream etherification performance of resin catalysts. (A) Amber-
BEA catalyst and (B) N-BEA catalyst.
lyst-15 and (B) Amberlyst-35 catalyst.

TTBG in the product at 4 h reaction time (Table 2). But DTBG is the
most desired product for obtaining diesel-miscible-ether with low
TBA consumption, the highest DTBG selectivity of 33.8% observed
at 75 °C on A-15 catalyst seems to be the suitable condition. Below
this reaction temperature (60 °C) the ineffective conversion of
MTBG resulted in the low formation of DTBG with almost negligi-
ble amount of TTBG. Higher reaction temperature (90 °C) also
caused the inferior product quality with lower DTBG formation,
perhaps due to the reversible conversion of TTBG to form MTBG
in presence of water.
In order to understand the aspect of reaction time on the prod-
uct equilibrium, the selectivities of all three ethers have been re-
corded at 1 h interval up to 5 h reaction time on both the
catalysts. The data shown in Fig. 3 indeed displays the formation
of TTBG and DTBG at 1 h and whose concentrations decrease con-
tinuously and the concentration of TTBG attained zero levels at 3 h
reaction time on both the catalysts. The decrease in DTBG concen-
tration is minimal on A-15 (Fig. 3A) which exhibits better perfor-
mance in retaining the DTBG selectivity. The MTBG concentration
is continuously increased with reaction time that envisions the
reversible conversion of TTBG to DTBG and MTBG. However, the
phenomenon is more prominent in case of A-35 (Fig. 3B) perhaps
due to the fast decline in catalytic activity of this resin catalyst in
presence of water. The possibility of using zeolites at higher reac-
tion temperatures is explored at this stage so as to minimize the
water effect.
As shown in Table 2, all the zeolite based catalysts, except MOR,
exhibited >90% glycerol conversion. The lower conversion obtained
on MOR, in spite of its higher acidity, can be ascribed to the narrow
pore size of the channels and their poor accessibility to the reac-
tants towards bulky etherification reaction in MOR. The USY cata-
lyst exhibited high conversion but the selectivity is solely towards
the MTBG and not even the traces of higher ethers i.e., DTBG and
TTBG are observed on this catalyst. The formation of DTBG along
with considerable selectivity to TTBG is observed only in the case
of BEA and N-BEA catalysts. Among the various catalysts studied,
the BEA and N-BEA performed best (Table 2) and these catalysts
were studied in detailed manner to understand the factors govern-
ing the product selectivity.
In batch reactor studies, reaction time played a vital role in
determining the product selectivity (Fig. 4). BEA catalyst shows
product selectivity trend of MTBG >> DTBG > TTBG at 4 h reaction
time but it is changed to DTBG > MTBG > TTBG (Fig. 4A) at 8 h. Fur-
ther increase of reaction time caused decrease in TTBG to form
DTBG and MTBG. This product pattern supports the established
mechanism of conversion of MTBG to DTBG and TTBG up to the
8 h reaction time. Above this level, the reversible formation of
DTBG through hydrolysis of TTBG may be responsible for the de-
crease in TTBG. Similar trend in product selectivities is also ob-
served in case of N-BEA catalyst (Fig. 4B), but with a slight
variation. The main difference observed in this case is the presence
of TTBG even after 16 h reaction time. This may be due to the
 N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986 985

120
Step 1
Gly. Conversion Mono Di Tri Di+Tri HO
HO TBA
100 OH
(A) O
ETHER SELECTIVITY

HO H2O OH
80
Glycerol MTBG
60

2O

Step 2
(A)

ep

sH
St
TBA H2O

es
40

c
Ex
20 HO
O H2O
O O O
0 O
0 0.5 1 1.5 2 2.5 TBA
WHSV (h-1) TTBG Step 3 DTBG

120
Gly. Conversion Mono Di Tri Di+tri 100

100
(B)
ETHER SELECTIVITY

OXYGENATE YIELD (wt%)

80 75 (B)
60
50 BEA N-BEA
40

20
25 Oxygenate = Di+ tri ether
0
0 0.5 1 1.5 2 2.5
-1
WHSV (h ) 0
Reaction Conditions: 0 4 8 12 16 20 24 28 32 36
Temperature =110°C, Pressure = 5 kg/cm2, REACTION TIME (h)
TBA : Gly. Molar ratio = 4:1, Reaction time =8 h
Fig. 6. (A) Reaction pathways for the formation of ethers and (B) Time on stream
Fig. 5. Effect of WHSV on glycerol conversion and ether selectivity. (A) BEA catalyst stability performance of BEA and N-BEA catalysts.
and (B) N-BEA catalyst.

better diffusion out of the TTBG in the mesopores of N-BEA catalyst
to avoid reversible conversion of TTBG.
Overall, the batch reactor studies suggest 8 h as optimum reac-
tion time for the maximum production of diesel blending oxygen-
ate stock (DTBG + TTBG).
3.2.2. Etherification studies in fixed bed (continuous flow) reactor
As shown in Fig. 5, both the catalysts exhibited similar trend in
glycerol conversion and selectivity towards individual ethers. The
glycerol conversions are always >95% and the catalysts exhibited
higher selectivity to DTBG and TTBG at lower WHSV up to 1 h 1.
Above this WHSV value, a sharp decline in TTBG along with in-
crease in MTBG and DTBG is observed. However the increase is
more pronounced in MTBG that resulted in the significant decrease
in oxygenate (DTBG + TTBG) selectivity from 96% to 68% (28 units).
This can be explained based on the optimum contact time required
for the formation of DTBG and TTBG products, where, 1 h 1 of
WHSV (1 h contact time) is observed to be optimum for the highest
production of oxygenates.
Though the two catalysts, BEA and N-BEA exhibited similar per-
formance trends, the curves shown in Fig. 5 suggests the better
performance of N-BEA over BEA in terms of retaining TTBG selec-
tivities at higher WHSV. For this catalyst, the decrease in TTBG
selectivity above 1 WHSV is minimal and this is also reflected in
minimal decline in selectivities of total oxygenates from 99 to 80
(19 units). Since, both BEA and N-BEA catalysts exhibit similar
acidity (Fig. 1B), the superior performance of the N-BEA may be as-
cribed to the presence of additional mesopores.
The superiority of N-BEA can be realized by comparing the
overall performance of BEA and N-BEA in fixed bed as well as
batch reactors (Table 2). The glycerol conversions are always
>95% on both the catalysts in both the reactors. However, there
is a significant difference in individual selectivities towards the
three ether products. The formation of diesel miscible TTBG and
DTBG is more in the fixed bed operation compared to the batch
reactor operation. The selectivity to DTBG is comparable in both
type of reactor operations, but considerable change is observed
in the selectivities of TTBG and MTBG. In batch reactor operation,
the TTBG selectivity is decreased with simultaneous increase in
MTBG selectivity. The differences in product selectivities can be
explained based on the reaction pathways proposed in Fig. 6A,
where the presence of bi-product water seems to be responsible
for the reversible hydrolysis of the glycerol ethers especially
TTBG, since the molecule has strain due to the closely arranged
bulky trt-butyl groups (step 4). The shift in selectivity from TTBG
to MTBG in batch reactor operation can be ascribed to the pres-
ence of huge amount of water bi-product stay in contact with
TTBG in batch reactor operation, which is not the case with con-
tinuous flow reactor. Hence, the continuous flow facilitated in
fixed bed operation gives advantage for the production of major
amount of DTBG along with TTBG, as this situation is desired
for obtaining diesel miscible oxygenate with less TBA
consumption.
3.2.3. Factors responsible for better performance of N-BEA catalyst
Surface area, pore volume, acidity and acid strength distribution
are the various catalytic properties that are expected to influence
986 N. Viswanadham, S.K. Saxena / Fuel 103 (2013) 980–986
the conversion and product selectivities in the zeolite catalyzed
reactions. It is interesting to see that highest acidity exhibiting
MOR catalyst could not give any better performance in etherifica-
tion reaction rather it performed much inferior to the BEA catalyst.
On the other hand the USY catalyst exhibited comparable acidity
and wider pore channels with BEA catalyst but the glycerol conver-
sion is only limited to the undesired MTBG. The higher glycerol
conversions and selectivity to bulky DTBG and TTBG observed in
case of BEA catalyst clearly envisions the suitability of wider pores
with higher pore volume of this zeolite for facilitating bulky molec-
ular transformations. The N-BEA catalyst containing comparable
chemical composition and acidity with BEA, but having additional
mesopores created by inter crystalline voids of nano-crystals fur-
ther improved the performance. The presence of additional mesop-
ores in N-BEA may make the pore system open for molecular
diffusion and easy accessibility of the acid sites to the reactant
molecules that are responsible for slow deactivation of the catalyst
and slower rate of decline in TTBG and glycerol conversion in this
catalyst. Because of this reason, the N-BEA catalyst also exhibited
improvement in stability with reaction time for the studied period
of 32 h (Fig. 6B). The total pore volume is also highest in N-BEA cat-
alyst followed by BEA catalyst that further envisions the major role
of porosity in facilitating glycerol etherification reaction. Though,
the acidity is important for the active site creation, the combina-
tion of wider pores and pore volume seems to be essential that
compliments for the efficient performance of the acid sites. Thus,
the recently progressing acid functionalized mesoporous materials
may be potential candidates for this reaction [26].
4. Conclusions
Catalytic properties were observed to influence glycerol etheri-
fication with TBA to produce diesel blending oxygenate
(DTBG + TTBG). Among the zeolitic properties, pore size and pore
volume have played vital role, as in the case of BEA and N-BEA cat-
alysts, in producing highly desired DTBG and TTBG (as high as 99%
selectivity at >95% glycerol conversion). The presence of bi-product
water influenced the reversible hydrolysis of TTBG to limit the
quality of the oxygenate product, while the affect of water is min-
imized in continuous flow (fixed bed) operation. Maximization
DTBG formation to obtain high quality oxygenate with less TBA
consumption was successfully achieved on N-BEA in a continuous
flow operation. The presence of mesopores originated from inter-
crystalline voids in N-BEA improved the oxygenate production
with stability in activity performance of the catalyst.
Acknowledgements
We acknowledge the CSIR for the research funding of the pro-
ject under 11th FYP. Our sincere thanks to the Director, IIP for help-
ful suggestions and GC, GC-MASS and SEM groups at IIP for
analysis.
References
[1] Voirol AJ, Durand I, Hillion G, Delfort B. Glycerin for new biodiesel formulation.
Oil gas Sci Tech Rev IFP 2008;63:395–404.
[2] Soares RR, Simonetti DA, Dumesic JA. Glycerol as a source for fuels and
chemicals by low-temperature catalytic processing. Angew Chem Int Ed
2006;45:3982–95.
[3] Dufour J, Iribarren D. Life cycle assessment of biodiesel production from free
acid-rich wastes. Renew Energy 2012;38:155–62.
[4] Atadashi IM, Aroua MK, Aziz ARA, Sulaiman NMN. Refining technologies for the
purification of crude biodiesel. Appl Energy 2011;88:4239–51.
[5] Hoekman SK, Broch A, Robbins C, Ceniceros E, Natarajan M. Renew of biodiesel
composition, properties and specifications. Susta Energy Rev 2012;16:143–69.
[6] Fernando S, Adhikari S, Kota K, Bandi R. Glycerol based automotive fuels from
future bio-refineries. Fuel 2007;86:2806–9.
[7] Bher A, Eilting J, Irawadi K, Leschinski J, Lindner F. Improved utilization of
renewable resources: new important derivatives. Green Chem 2008;10:13–30.
[8] Klepacova A, Mravec D, Hajekova E, Bajus M. Etherification of glycerol. Petrol
Coal 2003;45:54–7.
[9] Al-Lal AM, Garcia-Gonzalez JE, Llamas A, Monjas A, Canoira L. A new route to
synthesize tert-butyl ethers from glycerol. Fuel 2012;93:632–7.
[10] Stratiev DS, Shishkova IK, Dobrev DS. Fluid catalytic cracking feed
hydrotreatment and its severity impact on product yields and quality. Fuel
Process Tech 2012;94:16–25.
[11] Jimenez G, Aguilar-Lopez G. The fluidized-bed catalytic cracking unit building
its future environment. Fuel 2011;90:3531–41.
[12] Lee HJ, Seung D, Kim H. Etherification of glycerol by isobutylene: effects of the
density of acidic sites in ion exchange resin on the distribution of products.
Korean J Chem Eng 2011;28:756–62.
[13] Tonetto G, Atias J, De-Lasa H. FCC catalysts with different zeolite crystallite
sizes: acidity, structural properties and reactivity. Appl Catal A
2004;270:9–25.
[14] Klepacova A, Mravec D, Hajekova E, Bajus M. Etherification of glycerol with
tert-buty alcohal catalysed by ion exchanged resins. Chem Pap
2006;60:224–9.
[15] Frusteri F, Arena F, Cannilla C, Spadaro L, Blasi OD. Catalytic etherification of
glycerol by tert-butyl alcohol to produce oxygenated additives for diesel fuel.
Appl Catal A 2009;367:77–83.
[16] Yuan Z, Xia S, Chen P, Hou H, Zheng X. Etherification of biodiesel-based
glycerol with bioethanol over tungstophosphoric acid to synthesize glycerol
ethers. Energy Fuel 2011;2011(25):3186–91.
[17] Pariente S, Tanchoux N, Fajula F. Etherification of glycerol with ethanol over
solid acid catalysts. Green Chem 2009;11:1256–61.
[18] Klepacova A, Mravec D, Hajekova E, Bajus M. Tert-butylation of glycerol
catalysed by ion-exchange resins. Appl Catal A 2005;294:141–7.
[19] Kiatkittipong W, Suwanmanee S, Laosiripojana N, Praserthdam P,
Assabumrungrat S. Cleaner gasoline production by using glycerol as fuel
extender. Fuel Process Tech 2010;91:456–60.
[20] Melero JA, Vicente G, Paniagua M. Etherification of biodiesel-derived glycerol
with ethanol for fuel formulation over sulfonic modified catalysts. Bioresource
Tech 2012;103:142–51.
[21] Yadav GD, Chandan PA, Gopalaswami N. Green etherification of bioglycerol
with 1-phenyl ethanol over supported heteropolyacid. Clean Tech Envi Policy
2012;14:85–95.
[22] Srinivas D, Ratnasamy P, Saikia L. A process for the preparation of primary
glycerol ethers useful as biofuel additive from glycerol. WO patent 113079;
2009.
[23] Edward AB, Steinmetz MB. Process for glycerol tert butyl ethers WO patent
2009;117044.
[24] Zhao W, Yang B, Yi C, Lei Z, Jie X. Etherification of glycerol with isobutylene to
produce oxygenate additive using sulphonated peanut shell catalyst. Ind Eng
Chem Res 2011;49:12399–404.
[25] Ding L, Zheng Y. Effect of template concentration and gel dilution on
crystallization and particle size of zeolite beta in the absence of alkali
cations. Micro Meso Mater 2007;103:94–101.
[26] Nandan D, Sreenivasulu P, Saxena SK, Viswanadham N. Facile synthesis of a
sulfonated carbon–silica-meso-composite and mesoporous silica. Chem
Comm 2011;47:11537–9.