Calcium Impregnation in Mesoporous Silica Made using Methyl

Ricinoleate as Template and Its Application as

Transesterification Catalyst

Andriayani

1,2*

, Marpongahtun

1,5

, Yugia Muis

, Dikki Novran

and Justaman Karokaro

Chemistry Department, Universitas Sumatera Utara, Jl. Bioteknologi No 1, Medan, Indonesia

Pusat Kajian IPTEK Minyak Atsiri Euca plytu, Universitas Sumatera Utara, Jl. Bioteknologi No 1, Medan, Indonesia

Degree Program Chemistry Department, Universitas Sumatera Utara, Jl. Bioteknologi No 1, Medan, Indonesia

Laboratorium Pengujian BARISTAM North Sumatera, Medan, Indonesia

Laboratorium Penelitian Terpadu Universitas Sumatera Utara, Medan, Indonesia

Keywords: Mesoporous Silica, Metil Ricinoleic, Impregnation, Calcium Oxide, Transesterification.

Abstract: The impregnation of CaO in mesoporous silica made using methyl ester ricinoleate as a template was

carried out. The impregnated silica mesoporous product was applied as a catalyst in the transesterification

reaction of castor oil. Silica mesoporous products before impregnation and after impregnation were

characterized using FT-IR, XRD, SEM and porosity analysis using BET. Mesoporous silica data before

impregnation has a significant difference compared to mesoporous silica after impregnation. Its application

as a catalyst in the transesterification reaction of castor oil produces 74.44% ricin methyl ester.

1 INTRODUCTION

Porosity greatly influences the physical properties of

a material such as density, heat conductivity,

strength and others (Schubert, Ulrich S. and Husing,

2005). The synthesis technique of mesopore material

(2-50 nm pore diameter) is currently developing

rapidly because mesopore material has unique

properties, such as a more regular pore structure,

large surface area and uniform pore size distribution.

So much applied as catalysts (Li et al., 2011),

adsorbents (Yan et al., 2006), drug delivery

(Slowing et al., 2008), biosensors (Hasanzadeh et

al., 2012), optics (Kumari & Sahare, 2013) and

others.

The synthesis technique of mesoporous material

is carried out by combining inorganic components as

material and organic components such as surfactants

functioning as pore printers (templates). The pore

will be obtained after the organic component has

been removed by calcination.

In the previous study (Andriayani et al., 2013)

have been done synthesized of material silica using

sodium risinoleate as a template by varying the

addition of HCl 0,1N. We have also examined the

effect of variations in HCl concentrations in the

synthesis of mesoporous silica materials using

methyl ester ricinoleate as a template (Andriayani et

al., 2018). In this paper, tetraethylortosilicate

(TEOS) is used as a source of silica, risinolet methyl

ester as a template is made by extracting Ricinus

communis seeds that grow in wild forests in the

North Sumatera Karo region. Also used are 3-

aminopropyltrimethoxysilane (APMS) as a co-

structure directing agent (CSDA). Product

mesoporous silica impregnated by CaO and

analyzed using FT-IR, XRD, SEM and BET. The

mesoporous silica impregnation product was applied

as a catalyst in the reaction of castor oil

eseterification to ricinoleate ester. Given the

increasingly limited fossil fuels, ricinoleic esters can

be an alternative to fuels sourced from plants.

2 RESEARCH AND METHOD

2.1 Synthesis Meterial Mesopori Silika

MS 8.4Me

Methyl esters of ricinoleate (C

) 4.52 g (0.015

mol), 100 ml deionized water and 8.4 grams of

methanol were put into two neck flasks and

Andriayani, ., Marpongahtun, ., Muis, Y., Novran, D. and Karokaro, J.

Calcium Impregnation in Mesoporous Silica Made using Methyl Ricinoleate as Template and Its Application as Transesteriﬁcation Catalyst.

DOI: 10.5220/0010136900002775

In Proceedings of the 1st International MIPAnet Conference on Science and Mathematics (IMC-SciMath 2019), pages 96-101

ISBN: 978-989-758-556-2

sterilized at room temperature for 15 minutes, and

added 30 ml HCl 0.1M (mixture A). A mixture of

1.2 g (0.007 mol) APMS (C

SiO

N) and 6.02 g

(0.029 mol) TEOS (C

SiO

) was made by stirring

for 10 minutes (mixture B). The mixture (B) was

added to the mixture (A) and then stirred for 2 hours.

Then it is cured in an oven at 80C for 3 days (72

hours) until a porous solid is formed. The mixture is

centrifuged and the solids are separated and washed

with deionized water. The solid is dried at 50C and

then calcined at 550C for 6 hours. Silica

mesoporous products were obtained as much as 1.7

g and coded MS 8.4Me. The product were

characterized using FT-IR, XRD, SEM analysis and

isotherm adsorption / desorption.

2.2 Impregnation Mesoporous Silica

with CaO

Silica mesoporous material (MS 8.4Me-CaO) (0.36

gram) and Ca (NO3) 2 (1.18 g) were added to glass

beaker and 16 grams of dried methanol were added.

The mixture is stirred for 8 hours at room

temperature. The mixture is vacuumed in a

desiccator until the solid dries and then the solid is

calcined at 650C for 8 hours. The mesoporous silica

product that has been impregnated by CaO (MS

8,4Me-CaO) is characterization using FT-IR, XRD,

AAS, BET and SEM.

2.3 Application of Mesoporous

silica-CaO (MS 8.4Me-CaO) as a

Catalyst in Transesterification of

Castor Oil

Mesoporous silica-CaO (MS 8.4Me-CaO) (0.2

gram), methanol (p.a) (6.14 gram) and castor oil (15

gram) were put into a two neck flask. The mixture is

stirred with a magnetic stirrer for 4 hours at a

temperature of 80C by the reflux method. After the

reaction is complete the silica-CaO mesoporous

solid is separated by filtration. The filtrate was

extracted using n-hexane and distilled water. The n-

hexane phase was vacuum and a pale yellow methyl

ester product was obtained 9.21 grams (61.4%). The

methyl ester product was characterized using FT-IR

and GC-MS.

3 RESULT AND DISCUSSION

3.1 Characteristics of Mesoporous

Silica (MS 8.4Me) before and after

CaO Impregnation

Synthesis of mesoporous silica was carried out using

methyl ester ricinoleate as a template,

tetraethylortosilicate as a source of silica, the

addition of 8.4 grams of methanol and the

maturation process in an oven at 80 C for 72 hours.

The solids were separated by centrifugation, washed,

dried and calcined at 550C for 6 hours and obtained

1.6 grams of mesoporous silica (MS 8.4Me) white

solids (figure 1A) Then the silica mesoporous

product was pregnated with CaO and calcined at 650

padaC for 8 hours and white silica-CaO mesoporous

solids (MS 8.4Me-CaO) were obtained 0.47 grams

(Figure 1B).

Figure 1: Product of mesopori silica (MS 8.4Me): (A)

before and (B) after CaO impregnation.

Changes that occur in the silica mesoporous function

groups before impregnation and after CaO

impregnation can be proven using FT-IR spectrum

based on wave number data. Spectrum Ft-IR of

mesoporous silica prior to impregnation (MS 8.4Me)

(Figure 2 black) showed an absorption peak at

3421.72 cm

-1

widening due to the presence of OH

(Si-OH) strain on the surface of silica material. This

is also supported by the absorption peak at 952.84

-1

due to strain (–SiO-H). The absorption peak at

1103.28 cm

-1

is sharp due to the asymmetric

streaching of Si-O-Si (as Si-O-Si) and the wave

number at 806.25 cm

-1

due to symmetric streaching

of Si-O-Si (s Si-O- Si). Spectrum data adjusted for

literature: (AlOthman & Apblett, 2010; Khalil,

2007; Liu et al., 2010; Zhao et al., 2011). FT-IR

spectra of mesoporous silica after impregnation of

CaO (MS 8,4Me-CaO) (Figure 2 in red). The peak

absorption at 3425.58 cm

-1

is widened due to the OH

Calcium Impregnation in Mesoporous Silica Made using Methyl Ricinoleate as Template and Its Application as Transesteriﬁcation Catalyst

group strain (Si-OH). Another absorption peak is

seen at 1099.43 cm

-1

which is strong due to the

asymmetric strain of Si-O-Si (as Si-O-Si) and

supported symmetric streching of Si-O-Si (s Si-O-

Si) at 513.07 cm

-1

. Changes in the function of

mesoporous silica impregnation of CaO (MS 8,4Me-

CaO) (Figure 2 in red) show the absorption peak at

956.69 cm

-1

which is widening and appears to

overlap with Si-O-Si asymmetrical absorption at

1099.43 cm

-1

. This is due to the existence of the Si-

O-Ca- group. This is due to the mesoporous that has

been impregnated by the formation of Si-O-M bonds

(M = metal) which is in the wave number 1000-900

with a strong band (Smith, 1960). This proves that

the surface of mesoporous silica has been

impregnated by CaO and is supported by the low

intensity of absorption of the -Si-OH group in MS

8.4Me-CaO (68.67 a.u) compared to MS 8.4Me

before impregnation (78.78 au).

Figure 2: Spectrum FT-IR mesopori silica before

impregnation (MS 8.4Me) and after CaO impregnation

(MS 8.4Me-CaO).

Analysis of the structure of mesoporous silica

material before impregnation and after impregnation

of CaO (Figure 3) shows diffraction of X-ray

diffraction (XRD). The mesoporous silica

diffractogram before impregnation (MS 8.4Me)

(Figure 3 in black) at an angle of 2 theses shows the

diffractogram shape broad (broad) with the peak of

the diffractogram at 24.0, this shows that the silica

mesopore material is nanoparticles and is

amorphous. This is consistent with data reported by

previous researchers (Li et al. 2011; Zhao et al.

2011; Shah, Li, and Ali Abdalla 2009; Khalil 2007;

and Park et al. 2006). XRD diffractogram

mesoporous silica impregnation of CaO (MS 8.4

Me-CaO) (Figure 3 in red) shows the change in the

shape of the diffractogram. XRD diffractogram

mesoporous silica impregnation of CaO (MS 8.4

Me-CaO) (Figure 3 in red) shows a change in the

shape of the diffractogram. Si atom diffractogram

shifts at 24, whereas the diffractogram peaks at 32,

41, 46 indicate the presence of impregnated Ca

metal on the silica surface. This is in accordance

with the references of Albuquerque et al. (2008).

Figure 3: Diffractogram XRD of mesoporous silica before

and after CaO impregnation.

Analysis of silica material porosity before

impregnation and after impregnation of CaO (Figure

4) shows that there are differences in the

adsorption/desorption isotherm graphs. Graph

adsorption/desoprtion isotherm of mesoporous silica

before impregnation (Figure 4 in black) based on the

shape of the lop hysteresis is approaching Type IV

according to the specific IUPAC classification for

silica mesoporous material. The shape of lop

hysteresis is Type H3 and Type H4, where the shape

of lop hysteresis is a bit more complex because the

reversible micropore filling area is followed by

multilayer physisorption and capillary condensation,

so that Lop H4 is the same as Lop H3 for non-

micropore material. This is adjusted by reference

(Sing & Williams, 2004). While the adsorption

graph desorption of isotherm of silica mesoporous

material after impregnation Figure 4 in red) lop

hysteresis form is Type H3 according to Sing and

Williams (2004) reference, this is due to aggregate

and plate particle shape, characteristic desorption

indentation and lower approaching end point (Lop).

closure point). Lop H3 does not have a plateau at

high P/P0 values (mesoporous volume is not well

formulated), so interpretation of high P/P0 values is

more difficult. Branch adsorption graphs on type H3

show that gas adsorption only occurs on surfaces or

IMC-SciMath 2019 - The International MIPAnet Conference on Science and Mathematics (IMC-SciMath)

manolayers so that this shows that the obtained silica

material can be grouped also on Type II isotherm

charts for non-porous solids (Gregg S. J., and Sing,

1982). This is due to the silica impregnated surface

of CaO in the pores that are already covered by CaO

so that the shape of the hysteresis lop resembles non-

pore solids.

Figure 4: Graph adsorption/desorption isotherm of

mesopore silica before and after CaO impregnation.

The graph of pore size distribution mesoporous

silica before and after the pre-impregnation of CaO

calculated using the Barret-Joyner-Halenda (BJH)

method can be seen in (Figure 5). The mesopore

pore size distribution before impregnation (Figure 5

in black) shows the pore size distribution in the

range 1.59 nm - 9.4 nm. While the pore size

distribution of silica mesoporous material after CaO

impregnation (Figure 5 in red) shows the pore size

distribution in the range of 1.63 nm - 6.63 nm. The

pore size distribution graph of the two materials has

a difference in the value of dV/dD, which is because

the calcination treatment again after the

impregnation of CaO causes the dV/dD value to be

lower, because the pore is already covered by the

metal Ca. While silica mesoporous material before

impregnation the dV/dD value is greater in the same

pore size distribution range because the pores are not

covered by metal.

Figure 5: Graph adsorption/desorption isotherm of

mesopore silica before and after CaO impregnation.

3.2 Catalytic Activity of Mesoporous

Silica (MS 8,4Me-CaO)

The mesoporous silica impregnation CaO (MS

8.4Me CaO) was tested for its catalytic activity in

the transesterification reaction of castor oil. The

catalytic system of esterification reactions takes

place under heterogeneous conditions where the

silica-CaO mesoporous is insoluble (remains in a

solid state). This reaction condition is advantageous

because it is easily separated between the product

and the catalyst. The reaction was carried out at

80C for 4 hours. After the reaction was stopped, the

catalyst solids were separated and the filtrate was

extracted with n-hexane and washed with distilled

water, after which it was obtained a pale yellow

methyl ester product of 9.21 grams (70.6%) (Figure

6). The ricinoleate methyl ester product was

characterized using FT-IR and GC-MS.

Figure 6: Product methyl esters of transesterification

castor oil catalized by mesoporous silica CaO

impregnation (MS 8.4Me CaO).

Proving the formation of ricinoleic methyl esters

from transesterification of castor oil catalysts

catalyzed by silica mesreori impregnation of CaO

(MS 8.4Me-CaO), the functional group changes

were analyzed using FT-IR instruments and

compared with the FT-IR spectrum of castor oil

Calcium Impregnation in Mesoporous Silica Made using Methyl Ricinoleate as Template and Its Application as Transesteriﬁcation Catalyst

before transesterification (Figure 7). The FT-IR

spectrum of methyl ester (Figure 7 in red) shows a

widening peak at 3417.86 cm

-1

due to the stretching

vibrations of the OH group, while sharp peaks at

2924.09 cm

-1

and 2854.65 cm

-1

due to vibrational

frequencies stretching -CH- (sp

) alkane from the

hydrocarbon chain. The sharp peak at 1743.65 cm

-1

is due to the stretching vibration of C = O carbonyl

methyl ester ricinoleate and is supported by the peak

vibration buckling C-O at 1242.16 and 1165 cm

-1

The peak at 3417.86 cm

-1

is due to the presence of

OH groups from methyl ricinoleate on the C-12

atom. Compared to the FT-IR spectrum of castor oil

before transesterification (Figure 7 in black) shows

the low absorption intensity of C-O and C = O

stretching vibrations, this shows the formation of

methyl esters from castor oil.

Figure 7: Spectrum FT-IR of castor oil and methyl esters

from transesterification castor oil by mesoporous silica

impregnation CaO (MS 8.4Me-CaO).

Transeterification of castor oil using MS 8.4 Me-

CaO mesoporous silica catalysts produced a mixture

of methyl esters of fatty acids. This is due to the

extracted castor oil from castor bean seeds (Ricinus

communis) containing several fatty acids such as:

ricinoleic acid (87.7-90.4%), linoleic acid (4.1-

4.7%), oleic acid ( 2.2-3.3%), stearic acid (0.7-

1.1%), linolenic acid (0.5-0.7%) (Setiadji et al.,

2017). So that if esterified other fatty acids might

also be esterified. To find out the composition of

methyl esters formed from castor oil, GC-MS

analysis was performed. GC-MS data results showed

that the percentage of methyl ester ricinoleate was

74.44%. While the remaining 25.56% is esters of

other fatty acids. According to the literature, the

composition of ricinoleic acid is around 87.7-90.4%

so it can be assumed that the total methyl ester

formed reaches 84.88%. The results showed that

only a small portion of ricinoleic acid was not

converted to its methyl ester. This is because the

reaction is reversible and is influenced by several

factors such as: ratio (methanol: oil: catalyst),

reaction time and temperature.

Table 1 shows the results of the MS 8.4Me-CaO-

catalyzed transesterification reaction, the highest

yield was methyl ester ricinoleate. The

transesterification reaction of castor oil using

different catalysts results in different components

and the amount of methyl ester formed.

Table 1: GC-MS analysis of the composition methyl esters

of castor oil esterification with mesoporous silica 8.4Me-

CaO catalyst.

Methyl

ester

Molecular

Formula

Molecular

Weight

/mol

)

Area

1 Methyl

stearate

298 1.19

2 9,12-

Octadecad

ienoic

acid,

metyl

ester

294 2.95

3 Methyil

11-

octadecen

oate

296 3.30

4 Methyil

caprate

186 1.13

5 Methyl

ricinoleate

312 74.4

6 13-

Heptadecy

n-1-ol

O 252 16.9

4 CONCLUSIONS

The impregnation of CaO in mesoporous silica

prepared using methyl ester ricinoleic as a template

was carried out and the product obtained was

applied as a catalyst in the castor oil

transesterification reaction. Mesoporous silica

impregnation product (MS 8.4Me-CaO) was

characterized using FT-IR, XRD, SEM and porosity

analysis using BET. The data obtained have a

significant difference compared to mesoporous silica

(MS 8.4Me) before being impregnated. Its

application as a catalyst in the transesterification

reaction of castor oil produces 74.44% methyl ester

ricinoleic acid.

IMC-SciMath 2019 - The International MIPAnet Conference on Science and Mathematics (IMC-SciMath)

100

ACKNOWLEDGEMENTS

The authors are grateful for the main financial

support from Ministry of Research, Technology and

Higher Education, Republic of Indonesia through the

Decentalization- Penelitian Unggulan Perguruan

Tinggi (PTUPT) Research Grant 2019, coordinated

by Directorate of Research and Community

Services, Universitas Sumatera Utara (DRPM-USU)

with Contract No: 138/UN5.2.3.1/PPM/KP-

DRPM/2019.

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