Carbon-based solid acid catalyst from de-oiled canola meal for biodiesel
production

B.V.S.K. Rao, K. Chandra Mouli, N. Rambabu, A.K. Dalai, R.B.N.

Prasad

PII: S1566-7367(11)00270-6
DOI: doi: 10.1016/j.catcom.2011.07.011
Reference: CATCOM 2800

To appear in: Catalysis Communications

Received date: 14 April 2011

Revised date: 6 July 2011
Accepted date: 8 July 2011

Please cite this article as: B.V.S.K. Rao, K. Chandra Mouli, N. Rambabu, A.K. Dalai,
R.B.N. Prasad, Carbon-based solid acid catalyst from de-oiled canola meal for biodiesel
production, Catalysis Communications (2011), doi: 10.1016/j.catcom.2011.07.011

This is a PDF file of an unedited manuscript that has been accepted for publication.
As a service to our customers we are providing this early version of the manuscript.
The manuscript will undergo copyediting, typesetting, and review of the resulting proof
before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that
apply to the journal pertain.
 ACCEPTED MANUSCRIPT

Carbon-based solid acid catalyst from de-oiled canola meal

for biodiesel production

P T
B.V.S.K. Raoa,b, K. Chandra Moulia, N. Rambabua, A.K. Dalaia1 and R.B.N. Prasadb

RI
SC
a
Catalysis and Chemical Engineering Laboratories, Department of Chemical and Biological

Engineering, College of Engineering, University of Saskatchewan,

NU
Saskatoon, SK S7N 5A9, Canada
b
MA
Centre for Lipid Research, Indian Institute of Chemical Technology,

Hyderabad – 500 007, A.P. India

ED
PT
CE
AC

1
Corresponding author, E-mail address: ajay.dalai@usask.ca; Tel. +1-306-966-4771; Fax: +1-306-966-4777

1
 ACCEPTED MANUSCRIPT

Abstract

A carbon-based acid catalyst was prepared by the sulfonation of partially carbonized de-

oiled canola meal (DOCM), a by-product of canola seed processing. Partial carbonization of

T
DOCM was carried out at 300 and 400°C and the partially carbonized material prepared at

P
RI
400°C was steam activated to improve its surface properties. Four types of carbon catalysts were

prepared using the partially carbonized material and DOCM by concentrated sulphuric acid

SC
treatment. The spectral and elemental analysis clearly indicated that the catalyst had enough

NU
acidic sites in the form of sulfonate groups having the ability to promote esterification reaction.

The catalyst partially carbonized at 300°C established various functional groups such as aromatic
MA
carbon atoms, phenolic -OH, COOH, and carbonyl groups on the surface as evidenced by the
13
MAS C NMR and FTIR spectra. The catalyst produced by partial carbonization at 300°C
ED

followed by sulphuric acid treatment showed better performance towards esterification of oleic
PT

acid and high FFA canola oil. The maximum conversion reached 93.8% after 24 h at 65°C using

1:60 mol:mol of FFA to methanol and 7.5 wt % of catalyst to FFA. The performance of the
CE

catalyst was reduced gradually during its recycling and reached to 40.5% at the end of 4th cycle.
AC

Keywords: Partial carbonization; de-oiled canola meal; Solid acid catalyst; Free Fatty Acid;

Biodiesel; Esterification.

2
 ACCEPTED MANUSCRIPT

1. Introduction

Due to environmental concerns and the depletion of conventional materials, the utilization

of renewable materials has gained worldwide attention. Biodiesel (short-chain alkyl esters of

T
long-chain fatty acids) is usually produced from vegetable oils and animal fats, and is well

P
RI
recognised as an alternative fuel to depleting fossil fuels. However, due to its high production

cost and the non-availability of proper raw materials, it has not yet attained the anticipated

SC
worldwide momentum. The main challenge in the development of a commercially viable

NU
technology lies in handling low quality feed stocks such as high free fatty acid (FFA) oils, waste

cooking oils, soap stock [1-2], etc. and added value to major by-products of oilseed and biodiesel
MA
processing, such as de-oiled meal and glycerol.

The concept of environmentally friendly approaches to chemical processes has motivated

ED

the use of heterogeneous solid acids in place of homogeneous liquid acid catalysts [3-5]. Several
PT

reports on the preparation of biodiesel use heterogeneous acid catalysts, such as Amberlist-15

[6], Nafion [7], zeolites [8-9], La/zeolite beta [10], MCM-41 [11], sulfonated polystyrene
CE

compounds (SPS) [12], poly (vinyl alcohol) cross-linked with sulfosuccinic acid (SSA) [13], and
AC

hierarchical macroporous-mesoporous SBA-15 sulfonic acid [14]. Many of these heterogeneous

acid catalysts exhibit superior performance compared to sulphuric acid catalysts, but many have

drawbacks such as water sensitivity, tedious preparation methods, less activity at lower

temperatures, and the use of expensive metals.

Recent studies using sulfonated carbon-based acid catalysts prepared from aromatic

hydrocarbons, carbohydrates, glycerol, revealed that these are promising materials for the

production of biodiesel [15-24]. Shu et al. [25] reported the use of inexpensive vegetable oil

asphalt for the preparation of a sulfonated carbon-based catalyst useful for biodiesel synthesis.

3
 ACCEPTED MANUSCRIPT

Bio-oil, produced from biomass via fast pyrolysis, can be further processed for fuels and

chemicals. Bio-char, a by-product from this process has proven to be a promising raw material

for the production of activated carbons because of its availability at a low price [26]. This is

T
presently being considered for soil amendment [27-28] and can become a low-priced carbon

P
RI
catalyst support. Dehkhoda et al. [29] utilized bio-char obtained from hardwood for the

production of a solid acid catalyst and demonstrated its usefulness in producing biodiesel using

SC
high FFA feed stock.

NU
Canada is the single largest canola producer in the world, producing 20% of the world’s

canola/rapeseed and is the largest exporter worldwide. Canola oil is mainly used in food
MA
industries. The sustainable production of canola to meet demand is key to meeting the 2015 goals

of 15M tonnes of canola grown in Canada [30]. Canadian canola and soybean farmers strongly
ED

support the development of a domestic biodiesel industry that utilizes Canadian-grown feed
PT

stocks [31]. Canola meal is a major by-product of the canola seed processing industry and its

production in Canada is expected to increase from 2 million to 4 million tonnes over the next
CE

four to eight years as domestic crush capacity increases. This will put increasing pressure on the
AC

value of canola meal in its primary market. Although oil cakes are primarily used for animal feed

and agricultural applications, they are also widely used for the production of industrial enzymes,

antibiotics, biopesticides, vitamins, and other biochemicals [32]. Hence, alternate applications to

canola meal will boost the economy of canola producers. De-oiled canola meal (DOCM), which

contains proteins, carbohydrates, and crude fibre as major constituents, is a good low-cost raw

material for producing carbonaceous catalyst supports. The cost of commercial catalyst

Amberlist-15 (Sciencelab) is much higher than the relatively cheap carbon acid catalyst prepared

from Canola meal [33]. DOCM can be converted into activated carbon with high surface area

4
 ACCEPTED MANUSCRIPT

and can be used as an adsorbent. The carbonaceous carbon support prepared through partial

carbonation can also be utilized as a catalyst support for FTS and higher alcohol synthesis, due to

the presence of various functional groups present on the surface. In the present paper, a

T
carbonaceous catalyst support that was produced from DOCM is converted into a heterogeneous

P
RI
acid catalyst for the production of biodiesel using oleic acid and high FFA canola oil.

SC
2.0 Experimental

2.1 Methods and Materials

NU
Canola meal was procured from Bungi Oil Industries, Saskatoon, SK, Canada. Other
MA
chemicals and solvents were of analytical grade and purchased from M/s. VWR and used

without any further purification.

ED

2.1.1 De-oiling of canola meal

PT

Canola meal (100 g) was de-oiled by the soxhlet extraction method [34] using hexane (500

ml) as the solvent. The de-oiled meal (97 g) was made without solvent and used to prepare the
CE

carbon catalyst.
AC

2.1.2 Catalyst preparation

Method A: DOCM (20 g) was taken in a 500 ml glass beaker and concentrated sulphuric

acid (100 ml, 98%) was added in three portions over a period of 30 min. The contents were

heated from ambient temperature to ~190°C on a hot plate with occasional mixing using a glass

rod. As the temperature increased, considerable foaming was observed and the reaction was

continued by controlling the foam with the help of proper mixing, with the overall reaction

performed over a period of 5 h. At the end of the reaction, the contents were cooled to ambient

temperature and the reaction mixture slurry was placed in cooled distilled water. The carbon

5
 ACCEPTED MANUSCRIPT

catalyst was filtered and washed with hot distilled water (80°C) until the wash water was neutral

to pH and free of sulphate ions (BaCl2 precipitation test). The sulphated carbon catalyst was

dried in a 110°C oven overnight. The yield of the catalyst prepared by Method A was 53%.

T
Method B: DOCM (20 g) was taken in an Inconel tubular reactor (25.4 mm OD, 22 mm

P
RI
ID, length of 870 mm) and pyrolyzed at 300 and 400°C at a heating rate of 4°C/min under a

stream of nitrogen (100 ml/min) for 4 h to get partially carbonized material (10 g at 300°C and

SC
8.0 g at 400°C). The carbonized material was ground to powder and sulfonated using

NU
concentrated sulfuric acid (0.2 g/ml, 98%) at 80-85°C over a period of 10 h in a round-bottom

flask with a refluxing condenser and magnetic stirring system. The carbon-based catalyst was
MA
washed repeatedly with hot distilled water (80°C) until the wash water was neutral to pH and

free of sulfate ions (BaCl2 precipitation test). The catalyst was dried in a 110°C oven for 12 h.
ED

The yield of the catalyst prepared by Method B after sulfuric acid treatment was 90%.
PT

Method C: DOCM (20 g) was taken in an Inconel tubular reactor as described earlier and

pyrolyzed at 400°C at a heating rate of 4°C/min under a stream of nitrogen (100 ml/min) for 4 h
CE

to get partially carbonized material (8.0 g). This material was subjected to steam activation [35]
AC

at 400°C (4°C /min flow rate) with a water flow rate of 15 g/h over a period of 2 h. A continuous

nitrogen flow of 100 ml/min was maintained during the experiment. The steam activated carbon

material was ground to powder and treated with sulphuric acid, as described in Method B. The

yield of the catalyst prepared by Method C after sulfuric acid treatment was 90%.

2.2 Catalyst characterization

To study their physical and chemical characteristics, the prepared catalysts were
13
characterized using different techniques such as N2 adsorption, NH3-TPD, FTIR, C NMR,

SEM, elemental analysis, and TG-DTA. BET surface area and pore volume of the supports and

6
 ACCEPTED MANUSCRIPT

catalysts were measured by the adsorption of N2 at 77 K. Prior to analysis, the catalyst was

degassed in vacuum at 200°C until the static pressure remained less than 6.6 x 10-4 Pa. The

temperature programmed desorption (TPD) of NH3 was performed using Quantachrome

T
equipment (Model ChemBET 3000, Quantachrome Corporation, FL, USA) for the measurement

P
RI
of the total acidity of catalysts. 0.1 g sample was placed in an adsorption vessel (U-shaped) and

activated at 400 °C in H2 flow for 2 h (heating rate 10 °C/min). Then the sample was cooled to

SC
100 °C in He flow. At this temperature, 0.1% NH3 in N2 was passed through the sample for 1 h

NU
followed by cooling to room temperature in He flow. TPD was carried out from room

temperature to 500 °C at a heating rate of 10 °C/min with He flow rate of 35 ml/min. After each
MA
TPD, the amount of ammonia adsorbed was determined form the calibration curve obtained from

varying volumes of ammonia in He.

ED

The framework vibration of the catalysts was examined by FTIR spectroscopy. The KBr pellet
PT

technique was employed to obtain infrared spectra of the samples at room temperature, using a
CE

JASCO FTIR 4100 infrared spectrometer. The spectra retrieved were in the wave number range

of 400-4000 cm-1, with a resolution of 4 cm-1.. A Bruker DRX-360 NMR console was used to
AC

13
run the C magnetic angle spinning (MAS) NMR spectra of the catalyst, using an Oxford

360MHz Widebore (89 mm bore diameter) magnet, 8.45 T and a Bruker BL7 MAS probe (7 mm

O.D. rotor) at a rotation speed of 5000 Hz. The morphological features of the catalysts were

studied from electron micrographs obtained with a JEOL 2011 SEM. Before taking the SEM

images, each catalyst was ground to 100 mesh size and the ground powder samples dispersed in

heptane in an ultrasonic bath for several minutes. A few drops were then deposited on 200 mesh

copper grids covered with a holey carbon film. The electron micrographs were recorded in

electron negative films and in a digital PC system attached to the electron microscope. Analyses

7
 ACCEPTED MANUSCRIPT

of the carbon, hydrogen, nitrogen, and sulfur content of the catalysts were carried out using a

CHNSO analyzer (Elementar Americas, Inc.). A PerkinElmer thermo gravimetric differential

thermal analyzer (TG/DTA) was used to measure weight changes of the sample when heated

T
under a flow of argon (flow rate of 40 ml/min) at a constant heating rate of 10°C/min.

P
RI
The number of acid sites was estimated using a method described in literature [36], which

involves an aqueous ion-exchange step of the catalyst H+ ions with base of NaHCO3 (sulfonic

SC
acid groups, carboxyl groups), followed by titration of the resulting solution with HCl. In a

NU
typical experiment, about 30 mg of activated carbon was placed in 50 ml of the 0.005 N solution

of sodium bicarbonate. The vial was shaken for 24 h, filtered, and 5 ml of each filtrate was
MA
titrated with HCl.
ED

2.3 Reaction study

Oleic acid and high FFA canola oil (prepared by mixing 25% of oleic acid in refined
PT

canola oil) were used as substrates for the catalyst evaluation in esterification reaction. A 250 ml
CE

two-necked round-bottom flask with a refluxing condenser, an oil bath maintained at 65°C, and a

magnetic stirrer were used to conduct the reactions at atmospheric pressure. In a typical
AC

experiment, 5.64 g of oleic acid was mixed in 50 ml of anhydrous methanol in the round-bottom

flask and the required quantity of solid acid catalyst was added. The flask was placed in the oil

bath and the contents stirred using a magnetic stirring bar at 600 rpm. In the experimental setup

used, intimate mixing was observed at 600 rpm; hence, all experiments were carried at the same

stirring speed. Samples were drawn at defined time intervals to check the progress of

esterification reaction. The samples drawn from the reaction mixture were centrifuged to

separate the catalyst traces, the methanol evaporated, and the product analysed for acid value

(A.V.) [34]. The conversion was calculated using the following formula

8
 ACCEPTED MANUSCRIPT

Conversion (%) = (Initial A.V. – Final A.V.) / Initial A.V x 100

Similarly, the FFA present in the high FFA canola oil was converted into methyl esters

under identical experimental conditions as used for oleic acid.

P T
3.0 Results and discussion

RI
3.1 Screening of catalyst activity

SC
The procured canola meal contained 3.2% of oil; hence it was subjected to soxhlet

NU
extraction to recover any residual oil present. The characteristics of canola meal and de-oiled

DOCM are shown in Table 1. The TGA spectrum of DOCM shown in Fig. 1 clearly indicates
MA
that it has two distinguished dissociation zones at around 300 and 500°C; hence two temperature

points of 300 and 400°C were selected for the partial carbonization of DOCM. The partially
ED

carbonized material produced at 400°C was further activated by steam treatment to improve
PT

surface characteristics. To retain the functionalities formed during partial carbonization, the

steam activation temperature was restricted to 400°C (at which the carbon material was
CE

produced). The carbon materials produced were subjected to sulphuric acid treatment for the
AC

production of a carbon-based acid catalyst. In addition, DOCM was subjected to concentrated

sulphuric acid treatment, also producing a carbon-based acid catalyst. Henceforth, the carbon

catalyst prepared by (i) direct sulphuric acid treatment to DOCM will be referred as CAT 1; (ii)

the catalyst partially carbonized at 400°C and treated with sulphuric acid as CAT 2; (iii) the

catalysts partially carbonized at 400°C, steam activated, and treated with sulphuric acid will be

referred as CAT 3; and, (iv) the catalyst partially carbonized at 300°C and treated with sulphuric

acid as CAT 4.

Table 2 shows the physical properties of the prepared catalysts (BET area; C, H, N, SO

analyses, and total acidity). The surface (BET) area of eacg catalyst was less than 10 m2/g, and in

9
 ACCEPTED MANUSCRIPT

the range for similar catalysts prepared from biomaterials [29]. Steam treatment improves the

surface area by opening the pores of the material. Steam treatment of the partially carbonized

material improved the surface area from 9 to 59 m2/g, and this was further decreased by acid

T
treatment, due to the occupation of the pores by surface functional groups. All catalysts showed

P
RI
the same range of surface properties after acid treatment. Therefore, steam activation did not

improve the surface properties of CAT 3 compared to CAT 2. The acid site densities estimated

SC
by titration method [36] of all the prepared catalysts were in the range of 1.81 to 2.16 mmol/g.

NU
As shown in Table 1, de-oiled meals are good sources of carbohydrates and proteins. During

partial carbonization, these compounds undergo structural degradation/rearrangement and

MA
produce phenolic and polyaromatic rings, a fact well established in the literature [16, 20]. Some

of these new functional groups such as hydroxyl (-OH) and aromatic rings undergo sulfonation
ED

reaction with sulphuric acid and produce sulphonic groups that, along with other acidic
PT

functional groups, make the carbonized material acidic in nature.

The NH3-TPD plots of all the catalysts are shown in Fig. 2 and the total acid density values are
CE

presented in table 2. There are two distinctive peaks, corresponding to weak and strong acid sites
AC

at 220 and 350°C, respectively. The strong acid sites are present due to the presence of –SO3H

groups whereas weak acid sites presents due to other –OH groups on the surface of catalysts. The

density of both weak and strong acid sites increased from CAT 1 to CAT4. The FTIR spectra of

all the catalysts are shown in Fig. 3. The figure clearly shows the presence of -SO2 stretching

peaks at 1028, 1162 and 1702 cm-1. The intensity of these peaks increased from CAT 1 to CAT

4. The peak corresponding to C=O stretching vibration at 1704 and polyaromatics at 1606 and

1376 are observed on CAT 2, 3 and 4 but not on CAT 1.

10
 ACCEPTED MANUSCRIPT

In the case of CAT 1, the DOCM was directly treated with concentrated sulphuric acid at a

temperature around 190°C. Instead of creating new functional groups, this treatment destroyed

the major components of DOCM, such as carbohydrates and proteins, hence forming carbonized

T
material with low acidity. In all other cases (CAT 2, CAT 3, and CAT 4), the DOCM was

P
RI
partially carbonized, creating new functionalities such as hydroxyl and aromatic structures,

which in turn react with sulphuric acid at 85°C and undergo sulfonation, creating -SO3H

SC
functionalities on the surface of the catalysts. This is confirmed from TPD as well as FTIR

NU
analysis. The less acidity of the catalyst 2 and 3 compared to CAT 1is due to greater amount of

material loss noticed under treatment at 400°C compared to that at 300°C. This is clear evidence
MA
that functionality is destroyed at higher temperatures and that less reactive functionalities are

available for the sulfonation reaction.

ED

To compare the catalytic activity of CAT 1, CAT 2, CAT 3, and CAT 4, the esterification
PT

of oleic acid with methanol for the production of biodiesel was conducted under similar

experimental conditions. Since oleic acid is most abundant as fatty acid and a commonly used
CE

model compound, these studies were carried out using oleic acid as the model fatty acid. The
AC

canola oil is being studied using these catalysts and the results will be reported in another paper.

Since a reaction temperature of 65°C (boiling point of methanol) was found to be optimum for

the esterification reaction of fatty acids, all reactions were carried out at 65°C, and a catalyst

concentration of 7.5% ,with a higher molar ratio of methanol to fatty acid (60:1 mol/mol). Excess

methanol was used to nullify the effect of water formed during the esterification reaction. The

prepared catalysts were physically stable up to 250°C, as evidenced from the thermo gravimetric

analysis (Fig. 1). As the reaction was carried out at 65°C, there is no significant weight loss of

the catalysts observed in the reaction itself. Strong acid groups such as –SO3H mainly catalyze

11
 ACCEPTED MANUSCRIPT

the esterification reaction. Compared to the other three catalysts, CAT 1 showed inferior

esterification activity (Fig. 4) and, although the amount of oxygen in CAT 1 is higher (Table 2)

giving it more oxygen functionalities, its activity is lower than that of the other three catalysts

T
because the percentage of S is less in CAT 1

P
RI
Between CAT 2 and CAT 4, which were prepared using partially carbonized DOCM at

400 and 300°C, respectively, CAT 4 showed higher conversions than CAT 2. The partial

SC
carbonization at 300°C retained more functional groups, which upon sulphuric acid treatment

NU
produced more acidic functionalities on the surface of CAT 4. This observation also coincides

with the difference in their total acidity values and elemental analysis data with respect to
MA
sulphur content (Table 2). CAT 3, which was modified by steam activation, showed better

performance than CAT 2, but its esterification activity was less than that of CAT 4. Fig. 5 shows
ED

two distinctive endothermic peaks at 350 and 550°C in the case of CAT 4 and only one peak at
PT

550°C in the case of CAT 1. This clearly indicates that more functional groups were present on

the surface of CAT 4 that decomposed when the DOCM was subjected to direct sulphuric acid
CE

treatment. This appears to be the main reason for the low activity of CAT 1 compared to CAT 4.
AC

Hence, CAT 4 was chosen as the best performing catalyst in the catalyst characterization and

biodiesel preparation optimization studies.

3.2 Characterization of catalyst (CAT 4)

A detailed and thorough characterization of CAT 4 was carried out to understand the

physical and chemical properties of the material. As shown in Table 2, the catalyst showed less

than 10 m2/g BET surface area, indicating the catalyst is nonporous. The amorphous nature of

the catalyst was also confirmed by XRD analysis (figure not shown). CHNS and acidity of the

catalysts are shown in Table 2. As expected, the carbon content of the catalysts increased by

12
 ACCEPTED MANUSCRIPT

approximately 10% after partial carbonation. Sulphuric acid treatment also improved the

percentage of sulfonated groups present in the catalysts after acid treatment. The FTIR spectra of

the carbon catalyst before and after H2SO4 treatment is shown in Fig. 6. The characteristic peaks

T
that correspond to the stretching modes of –SO3H groups appeared at 1028 (-SO2 symmetrical

P
stretching mode), 1162 (-SO2 asymmetric stretching mode), and 1702 cm-1 in the H2SO4 treated

RI
carbon catalyst spectra [22, 37]. These peaks are not present in the catalyst before acid treatment,

SC
which indicates the presence of strong acidity in the catalysts after acid treatment. The band at

NU
1704 cm-1 is due to C=O stretching vibration of the –COOH group. The bands at 1606 and 1376

cm-1 also confirm the presence of poly aromatic hydrocarbons in the CAT 4. The broad band at
MA
>3000 cm-1 is due to the presence of –OH and –NH of carboxylic, phenolic and amide groups,
13
respectively. The MAS C NMR spectra (Fig. 7) of CAT 4 exhibited resonance peaks at 130,
ED

154, 167, and 180 ppm attributable to aromatic carbon atoms, phenolic -OH, COOH, and
PT

carbonyl group respectively [38]. The thermo gravimetric analysis (Fig. 1) showed that the CAT

4 was stable until 250°C. The SEM images (Fig. 8) of all the catalysts show that the catalyst
CE

particles have irregular shapes.

AC

3.3 Optimization study (CAT 4)

During the optimization studies, the temperature and molar ratio of feed to methanol were

kept constant at 65°C and 1:60 mol/mol, respectively. The effect of catalyst dosing and reaction

time on the esterification reaction were studied. As shown in Fig. 9, an increase in catalyst

dosing from 2.5 to 7.5% increased the conversion of oleic acid from 79.8 to 93.8%. A further rise

in concentration to 10% showed no significant increase in the oleic acid conversion to biodiesel.

Therefore, 7.5% of catalyst loading was found to be optimum for the esterification of oleic acid

on CAT 4. The effect of time-on-stream on esterification activity was studied up to 48 h, with

13
 ACCEPTED MANUSCRIPT

conversion reaching to 93% at 24 h. The esterification activity of Cat 4 was compared with

Amberlist-15 (wet), a commercial solid-acid catalyst, under optimum experimental conditions.

The activity profile (Fig. 10) clearly demonstrates that Cat 4 exhibits an almost similar

T
esterification trend to Amberlist-15 (wet). Since Cat 4 is produced from a low-cost raw material,

P
RI
it can probably compete with commercial catalysts for the esterification of fatty acids into

biodiesel. The esterification study was extended for high FFA canola oil using CAT 4, under

SC
similar experimental conditions used for the oleic acid-methanol system. The fatty acid

NU
conversion reached 93% in 24 h, similar to the methanol-oleic acid system.

Attempts were also made to use CAT 4 for the transesterification reaction of refined canola
MA
oil as a substrate using temperature and a feed/methanol ratio of 65°C and 1:12 mol/mol,

respectively at 10% catalyst loading. The transesterification did not proceed over prolonged
ED

reaction times (48 h), which was confirmed by TLC.

PT
CE
AC

14
 ACCEPTED MANUSCRIPT

3.4 Catalyst reuse studies

Catalyst efficiency is defined based on its reusability. In the catalyst reuse studies, oleic

acid esterification was performed over a 24-h reaction time using Cat 4. At the end of each

T
experiment, the catalyst was filtered from the reaction mixture, washed with fresh methanol,

P
RI
dried at 100°C for 2 h, and then reused in the next cycle of experiments. Fig. 11 clearly shows

that the catalyst’s esterification activity was reduced to 40.5% at the end of 4th cycle. Even

SC
though deactivation of catalytic activity is noticed in the case of carbon-based solid acid catalysts

NU
[18, 36], the DOCM-based carbon acid catalyst showed significant deactivation when compared

to the previously reported similar catalysts. This clearly demonstrates that the sulfonate groups
MA
attached to the carbon functionalities are leaching during the course of esterification. However,

the acidic characteristics can be regenerated by sulphuric acid treatment, as suggested in the
ED

literature [37].
PT

4. Conclusions
CE

A DOCM-derived carbon acid catalyst was prepared by partial carbonation at 300°C

followed by sulphuric acid treatment. The presence of functionalities such as carboxylic,

AC

phenolic, and sulfonic groups were identified by FTIR analysis. BET, elemental and back

titration methods confirmed the catalyst was nonporous and acidic in nature. The catalyst was

successfully employed in the esterification of oleic acid and high FFA canola oil and achieved a

conversion of 93.8% at a temperature, reaction time, molar ratio of substrate to methanol, and

catalyst concentration of 65°C, 24 h, 1:60 mol/mol and 7.5%, respectively. The performance of

the catalyst was comparable with commercial catalyst Amberlite-15 (wet). The catalyst

deactivated gradually over four recycles, and the activity could be regenerated by sulphuric acid

treatment.

15
 ACCEPTED MANUSCRIPT

Acknowledgements

The authors are thankful to Bungi Canada Ltd. for supplying raw material for this

research. The financial assistance provided by the Canada Research Chair Program, Agricultural

T
Biorefinery Innovation Network (ABIN), and Natural Sciences and Engineering Research

P
RI
Council of Canada (NSERC) are greatly acknowledged.

SC
5. References

[1] I. Mohamad, and O. Ali, Bioresource Technol. 85(2002) 253–256.

NU
[2] S. Sivaprakasam, C. G. Saravanan, Energ. Fuel. 21 (2007) 2998–3003.
MA
[3] B. Harton, Nature, 400 (1999) 797-799.

[4] J. M. DeSimone, Science, 297 (2002) 781-799.

ED

[5] T. Okuhara, Chem. Rev. 102 (2002) 3641-3666.

[6] M. M. R. Talukder, J. C. Wu, S. K. Lau, L. C. Cui, G. Shimin, A. Lim, Energ. Fuel. 23

PT

(2009) 1–4.
CE

[7] K. Ngaosuwan, E. Lotero, K. Suwannakarn, J. G. Goodwin, P. Praserthdam, Ind. Eng. Chem.

Res. 48 (2009) 4757–4567.

AC

[8] M. J. Ramos, A. Casas, L. Rodriguez, R. Romero, A. Perez, Appl. Catal. A: Gen. 346 (2008)

79–85.

[9] A. Corma, H. Garcia, S. J. Iborra, Catal. 120 (1989) 78-87.

[10] Q. Shu, B. L. Yang, H. Yuan, S. Qing, G. L. Zhu, Catal. Commun. 8 (2007) 2159–2165.

[11] P. P. Joaquín, D. Isabel, M. Federico, S. Enrique, Appl. Catal. A: Gen. 254 (2003) 173–88.

[12] R. A. Soldi, A. R. S. Oliveira, Appl. Catal. A: Gen. 361(2009) 42–48.

[13] C. S. Caetano, L. Guerreiro, Appl. Catal. A: Gen. 359 (2009) 41–46.

[14] J. Dhainaut, J. P. Dacquin, Green Chem. 12 (2010) 296–303.

16
 ACCEPTED MANUSCRIPT

[15] M. Hara, T. Yoshida, A. Takagaki, Angew. Chem. Int. Ed. 43 (2004) 2955–2958.

[16] M. Toda, A. Takagaki, M. Okamura, J. N. Kondo, S. Hayashi, K. Domen, and M. Hara,

Nature. 438 (2005)178–179.

T
[17] M. H. Zong, Z. Q. Duan, W. Y. Lou, T. J. Smith, H. Wu, Green Chem. 9 (2007) 434–437.

P
RI
[18] X. H. Mo, D. E. Lopez, K. Suwannakarn, Y. Liu, E. Lotero, J. G. Goodwin, J. Catal. 254

(2008) 332–338.

SC
[19] X. H. Mo, E. Lotero, C. Q. Lu, Catal. Lett. 123 (2008) 1–6.

NU
[20] A. Takagaki, M. Toda, M. Okamura, J. N. Kondo, S. Hayashi, K. Domen, Catal Today 116

(2006) 157–167.
MA
[21] J. A. Maciá-Agulló, M. Sevilla, M. A. Diez, and A. B. Fuertes, ChemSusChem 3 (2010)

1352-1354.
ED

[22] B. L. A. P. Devi, K. N. Gangadhar, P. S. S. Prasad, B. Jagannadh, and R. B. N. Prasad,

PT

ChemSusChem. 2 (2009) 617-620.

[23] R. Liu, X. Q. Wang, X. Zhao, P. Y. Feng, Carbon 46 (2008)1664–1669.

CE

[24] W. Y. Lou, M. H. Zong, Bioresour. Technol. 99 (2008) 8752–8758.

AC

[25] Q. Shu, Q. Zhang, G. X. Xu, Z. Nawaz, D. Z. Wang, and J. F. Wang, Fuel Process Technol.

90 (2009)1002-1008.

[26] O. Ioannidou, A. Zabaniotou, Renew. Sust. Energy Rev. 11 (2007) 1966–2005.

[27] S. Steinbeiss, G. Gleixner, M. Antonietti, Soil Biol. Biochem. 41 (2009) 1301-1310.

[28] S. P. Sohi, E. Krull, E. Lopez-Capel, R. Bol, Advances in Agronomy105 (2010) 47–82.

[29] A. M. Dehkhoda, A. H. West, N. Ellis, Appl. Catal. A: Gen. 382 (2010) 197–204.

[30] http://www.saskcanola.com/media/pdfs/scdc-report-2009-2010.pdf.

[31] www.ccga.ca/ news February 28, 2011.

17
 ACCEPTED MANUSCRIPT

[32] S. Ramachandran, S. K. Singh, C. Larroche, C. R. Soccol, A. Pandey, Bioresource

Technol. 98 (2007) 2000–2009.

[33] http://www.canolacouncil.org/canolaprices.aspx

T
[34] AOCS, Official methods and recommended practices of the American Oil Chemists society,

P
4th Edition (Ed.:D. Firestone), AOCS Press, Champaigne, USA (2001).

RI
[35] R. Azargohar, A. K. Dalai, Micro. Meso. Mat. 110 (2008) 413-421.

SC
[36] G. Chen, B. fang, Bioresource technol. 102 (2011) 2635-2640.

NU
[37] R. M. Silverstien, G. C. Bassler, T. C. Morrill, 5th ed., John Wiley and Sons, Indianapolis,

(1991) 218.
MA
ED
PT
CE
AC

18
 ACCEPTED MANUSCRIPT

List of Figures

Figure 1: Thermo gravimetric analysis of the raw DOCM and catalysts.

T
Figure 2: NH3-TPD plots of all the catalysts.

P
RI
Figure 3: FTIR spectra of all the catalysts.

SC
Figure 4: Catalytic activity of DOCM-based carbon acid catalysts for the esterification of oleic

acid with methanol. (Reaction conditions: 5.64 g oleic acid, 50 ml methanol, 0.42 g catalyst,

NU
65°C, 800 rpm, and 6 h)
MA
Figure 5: Differential thermal analysis of the DOCM-based carbon acid catalysts.

Figure 6: FTIR spectra of CAT 4 and CAT 4 before H2SO4 treatment.

ED

Figure 7: MAS 13C NMR spectrum of CAT 4.

PT

Figure 8: SEM photograph of (a) CAT 1; (b) Cat 2; (c) CAT 3; (4) CAT 4.

Figure 9: Esterification of oleic acid and high FFA canola oil by CAT 4 and esterification of
CE

oleic acid by Amberlist-15 (wet). (Reaction conditions: FFA: MeOH (1:60 mol/mol), catalyst
AC

7.5% of free fatty acid, Temperature 65°C)

Figure 10: Effect of catalyst concentration on esterification of oleic acid using CAT 4 (Reaction

condition: 1.13 g oleic acid, 10 ml MeOH, 65°C temperature, and 24 h reaction time)

Figure 11: Reusability of the catalyst. (Reaction conditions: 2.26 g oleic acid, 7.5% CAT 4, 20

ml MeOH, 24 h reaction time, 65°C temperature)

19
 ACCEPTED MANUSCRIPT

Table 1 Composition of raw material.

Sample Raw Material Properties (wt %)

T
Oil Protein Carbohydrate* Fibre Moisture Ash

P
RI
Canola meal 3.2 36.7 34 11.8 7 7.3

SC
De-oiled canola meal 0.3 38.8 35.2 12 6.5 7.2

NU
* by difference
MA
ED
PT
CE
AC

20
 ACCEPTED MANUSCRIPT

Table 2 Physical properties of the catalysts.

BET
Acid Strength
Catalyst area, %C %H %N %S

T
m2/g mmol/g1 µmol NH3/g2

P
CAT 1 4.7 48.2 2.6 2 2.7 1.81 1942
CAT 2 4.3 61.8 2.9 7.3 3.3 2.1 2038

RI
CAT 3* 59 62.4 3.1 7.2 0.2 0.13 -
CAT 3 3.3 62.9 3.1 7.3 3.8 2.05 3162

SC
CAT 4* 13 63.2 3.04 7.2 0.3 0.15 -
CAT 4 4 58 3.6 7.6 4.4 2.16 3287

NU
1
Acidity calculated using the titration method [36]
2
Acidity calculated using the NH3 TPD method
MA
* Before acid treatment
ED
PT
CE
AC

21
 ACCEPTED MANUSCRIPT

TP
RI
TG (µg)

SC
NU
MA
ED

30 130 230 330 430 530

Temperature(°C)
PT
CE

Fig. 1.
AC

22
 ACCEPTED MANUSCRIPT

P T
CAT 4

RI
signal (a.u.)

SC
CAT 3

CAT 2

NU
MA CAT 1

50 150 250 350 450 550

ED

Temperature (°C)

Fig. 2.
PT
CE
AC

23
 ACCEPTED MANUSCRIPT

P T
RI
SC
Transmittence (a.u.)

NU
MA CAT 4

CAT 3
ED
PT
CE

CAT 2
AC

CAT 1

400 900 1400 1900 2400 2900 3400 3900

Wave number (cm-1)

Fig. 3.

24
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA
ED
PT
CE

Fig. 4.
AC

25
 ACCEPTED MANUSCRIPT

CAT 4

TP
RI
DTA (a.u.)

SC
CAT 1

NU
MA
50 150 250 350 450 550 650
ED

Temperature (°C)
PT

Fig. 5.
CE
AC

26
 ACCEPTED MANUSCRIPT

P T
RI
Cat 4

SC
626.56

NU
1704.41 1436.09
1376.28
%T 3098.26 1606.39 1028.98
2925.93 1162.83
MA
Cat 4 before H2SO4 treatment
ED

741.76 559.04
PT
CE

2925.39 2361.31
1637.00 1437.87 1115.48

4000.0 3000 2000 1500 1000 400.0

AC

Wave number (cm-1)

Fig. 6.

27
 ACCEPTED MANUSCRIPT

PT
RI
SC
NU
MA
ED

Fig. 7.
PT
CE
AC

28
 ACCEPTED MANUSCRIPT

(a) (b)

PT
RI
SC
(c) (d)

NU
MA
ED
PT
CE

Fig. 8.
AC

29
 ACCEPTED MANUSCRIPT

120

100

P T
80
Conversion (wt%)

RI
CAT 4 (Oleic acid)
Amberlist-15 (wet) (Oleic acid)

SC
60
CAT 4 (High FFA Canola Oil)

NU
40
MA
20
ED

0
0 10 20 30 40 50 60
Time (h)
PT
CE

Fig. 9.
AC

30
 ACCEPTED MANUSCRIPT

95

90

P T
RI
%Conversion

85

SC
80

NU
75
MA
70
ED

2.5 5 7.5 10
Catalyst conc. (wt%)
PT
CE

Fig. 10.
AC

31
 ACCEPTED MANUSCRIPT

100

80

T
Conversion (wt%)

P
60

RI
SC
40

NU
20
MA
0
1 2 3 4
ED

Cycle no.
PT

Fig. 11.
CE
AC

32
 ACCEPTED MANUSCRIPT

P T
RI
SC
NU
MA
Graphical Abstract
ED

Highlights
PT

De-oiled canola meal derived carbon acid catalyst was prepared successfully
Carboxylic, phenolic, aromatic and sulfonic groups were present in the catalyst
CE

The catalyst was nonporous and acidic in nature

Esterification activity was comparable with commercial catalyst, Amberlite-15 (wet)
AC

33