Optimization study of alkyl polyglycoside C12

synthesis using indirect method

Cite as: AIP Conference Proceedings 2349, 020018 (2021); https://doi.org/10.1063/5.0051813
Published Online: 24 June 2021

Febri P. A. Kinanti, Dyah U. C. Rahayu, Agnesya P. Gustianthy, et al.

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AIP Conference Proceedings 2349, 020018 (2021); https://doi.org/10.1063/5.0051813 2349, 020018

© 2021 Author(s).
 Optimization Study of Alkyl Polyglycoside C12 Synthesis
Using Indirect Method
Febri P. A. Kinanti1, Dyah U. C. Rahayu1, a), Agnesya P. Gustianthy2, and Yuni K.
Krisnandi1
1
Department of Chemistry, Faculty of Mathematics and Natural Sciences (FMIPA), Universitas Indonesia, Depok
16424, Indonesia
2
PT Pertamina Research and Technology Center, Jl. Raya Bekasi Km.20, Pulogadung, Jakarta 13920, Indonesia
a)
Corresponding author: dyahutamicr@sci.ui.ac.id

Abstract. Alkyl polyglycosides (APGs) are classified as non-ionic and green surfactants that can be synthesized from
renewable materials such as glucose and fatty alcohol. APGs are commonly applied as surfactants in enhancing oil recovery
(EOR) since APGs exhibit excellent interfacial activities, emulsified abilities, foaming performance, and wettabilities. In
this research, the mixture of APG C12 was synthesized following the indirect method, which was consisted of two stages,
i.e. butanolysis and transacetalization. Butanolysis was carried out by reacting glucose in technical grade with 1-butanol
(1:2.8, m/m) and PTSA catalyst 1 mol% at 106oC for 6h. The mixture of APG C4 from butanolysis then was further applied
in transacetalization without purification by adding 1-dodecanol with some optimizations, i.e. mass ratio of 1-dodecanol,
reaction time, and temperature. The optimum condition to afford the APG C12 mixture was the mass ratio of glucose in
technical grade and 1-dodecanol 1:7.5 m/m with PTSA catalyst 0.5 mol% at 115oC for 4h. All the mixture of APGs were
analyzed for its remaining reducing sugar level using Benedict’s test and further characterized using FTIR, UV-Vis, and
LC-MS/MS. Moreover, physical characteristic tests such as compatibility, emulsion stability, solubility, and interfacial
tension tests were also conducted on all the mixture of APGs. This study reveals that APGs can be synthesized using the
indirect method with moderate to good physical characteristics which can be used for EOR surfactant for further
application.

INTRODUCTION
The consumption number of petroleum in Indonesia has been increasing rapidly [1]. Because there is no alternative
energy to replace petroleum, Indonesia needs to increase oil production by optimizing existing old oil fields by
applying the enhanced oil recovery (EOR) method [2]. EOR is the process of recovery oil by injecting chemicals
which are not existing at the reservoir [3]. EOR consists of several techniques based on the injection of liquids or other
agents to modify physical properties to increase the recovery factor and lifetime of petroleum fields [4]. The most
commonly EOR method used is the chemical injection method with surfactants, polymers, or alkaline compounds as
injected chemicals [5]. One of the chemicals which can be used for EOR is alkyl polyglycosides (APGs) surfactant.
The use of surfactants for EOR applications can reduce the viscosity, stabilize dispersion that affects the petroleum
flow from the reservoir is easier, and act as an emulsifier [6]. APGs are green surfactants having good interfacial
properties. APGs can be synthesized from fatty acid alcohol and carbohydrate with the presence of an acid catalyst.
APGs were commonly synthesized by the Fischer method using the direct method (acetalization) or the indirect
method (butanolysis and transacetalization) [7]. Recent studies have shown that APGs synthesis using the indirect
method is more preferable in the industries due to its effectiveness [1]. In our previous research, the optimum condition
to synthesize APG C4 was successfully obtained from butanolysis in the indirect method [8]. Therefore, in this study,
we continue to synthesize APG C12 using the indirect method with optimization on transacetalization to produce
optimal APG C12 products.

4th International Seminar on Chemistry

AIP Conf. Proc. 2349, 020018-1–020018-6; https://doi.org/10.1063/5.0051813
Published by AIP Publishing. 978-0-7354-4100-2/$30.00

020018-1
 MATERIALS AND METHOD

Materials
The materials used were 1-butanol, glucose in technical grade, 1-dodecanol, p-toluene sulfonic acid (PTSA),
sodium hydroxide (NaOH), Benedict’s solution, brine water, n-octane, NaCl, methanol, and ethyl acetate. Structure
elucidation was carried out using FTIR Shimadzu IR Prestige-21, UV-Vis Shimadzu UV-2450, and LC-MS/MS
Waters Xevo G2-S QTOF using C18-column with a temperature of 50°C (column) and 25°C (room), flow rate 0.2
ml/min, and positive mode. Interfacial tension (IFT) values were measured using spinning drop tensiometer M6500.

Synthesis of APG C4 Mixture via Butanolysis

Butanolysis was carried out according to Rachman et al. 2020 with some modifications [8]. In this study, a mixture
of glucose in technical grade with 1-butanol 1:2.8 (m/m) and PTSA catalyst 1 mol% were reacted in a three-neck
round-bottom flask at 106oC for 6h. After completing the reaction, the mixture was evaluated for its reducing sugar
level using Benedict’s test. Neutralization of the reaction mixture then was carried out with NaOH 50% (m/v) for 30
min accompanied by stirring at 90°C. The reaction mixture was further evaporated to remove the remaining amount
of 1-butanol and afford the mixture of APG C4.

Synthesis of APG C12 Mixture via Transacetalization

The mixture of APG C-4 then was continued to the transacetalization without prior purification. The
transacetalization was carried out by varying reaction conditions as summarized in Table 1. The qualitative reducing
sugar test was carried out using Benedict’s test. The reaction mixture then was neutralized with NaOH NaOH 50%
(m/v) until pH 7-9 at 90°C accompanied by stirring for 30 min. After completing the neutralization, the reaction
mixture then was evaporated to remove the remaining amount of 1-dodecanol and yield the mixture of APG C12.

TABLE 1. Variation of reaction conditions at the transacetalization

Glucose (tech. grade):
Variations Temperature (°C) Time (h) Catalyst (mol%)
1-dodecanol (w/w)
1 1:7.5 110 4 0.5
2 1:7.5 115 4 0.5
3 1:7.5 120 4 0.5
4 1:7.5 115 2 0.75
5 1:2.8 115 2 0.75

Analysis and Characterization of APG C4 and C12 Mixtures

Each of the APG mixture (APG C4 and C12) then was characterized using FTIR, UV-Vis, and LC-MS/MS. Several
analyses for physical characterization of each mixture were also conducted such as IFT values, compatibility, emulsion
stability, and solubility tests.

RESULTS AND DISCUSSION

In this study, a mixture of APG C4 was successfully synthesized using the indirect method. The synthesis was
carried out using the technical grade of glucose, 1-butanol, and PTSA catalyst at 106°C for 6h by reflux (Figure 1).
Neutralization with NaOH then was carried out to stop the reaction [9]. NaOH was chosen to neutralize the reaction
mixture because it has non-corrosive properties and will not react with the products formed. After neutralizing the
reaction mixture, the remaining alcohol then was evaporated. The mixture of APG C4 afforded in brown-gummy
liquid and showed no color changes in Benedict's test which indicates the absence of residual reducing sugar in the
mixture of APG C4.

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 FIGURE 1. Reaction scheme of synthesis APG C4 mixture

Figure 2 showed the UV-Vis and FTIR spectra of the APG C4 mixture. According to Figure 2(a), the APG C4
mixture exhibited a maximum absorption at a wavelength of 222.5 nm from acetal chromophore. FTIR spectrum
(Figure 2(b)) showed stretching vibration of C-O-C bonds at the wavenumber of 1100-1200 cm-1 indicating the
formation of APG C4 mixture [10]. Besides, a broad peak at the wavenumber 3000-3300 cm-1 revealed that the mixture
still consisted of O-H bond from hydrophilic groups in APGs.

FIGURE 2. (a) UV-Vis and (b) FTIR spectra of APG C4 mixture

(a)

(b)

FIGURE 3. Proposed fragmentation scheme of APG C4 from glucose (a) tetramer and (b) trimer

LC-MS/MS was carried out to prove the characterization of the APG C4 mixture. LC chromatogram of APG C4
mixture showed several peaks indicating that the compound was still in a mixture. However, two peaks at the retention

020018-3
times of 1.39 and 2.75 min showed the mass number close to APG C4. A peak at 1.39 min was identified as APG C4
from glucose tetramer with [M+H]+ of 741.29 m/z while a peak at 2.75 min belongs to APG C4 from glucose trimer
with [M+H]+ of 579.24 m/z. The proposed fragmentation scheme of these APG C4 compounds was shown in Figure
3.
The mixture of APG C4 was subjected as a reactant in transacetalization without further purification to form the
mixture of APG C12 (Figure 4). The synthesis of APG C12 was studied for its optimal condition by varying the ratio
mass of glucose in technical grade and 1-dodecanol, temperature, time, and the amount of catalyst. After working up
in similar steps with butanolysis, the APG C12 mixture afforded as yellow to brown liquid depending on the reaction
temperature. The higher the reaction temperature, the darker the APG C12 mixture appearance. The Benedict’s test
was performed on all variations of the APG C12 mixture to determine qualitatively remaining glucose in the mixture.
The mixture of APG C-2 from variations 2 and 4 exhibited no color changes indicating the absence of remaining
glucose.

FIGURE 4. Reaction scheme of synthesis APG C12 mixture

Figure 5 displayed the UV-Vis and FTIR spectra of all variations APG C12 mixture. Based on Figure 5(a), all the
APG C12 mixture exhibited a maximum absorption at a wavelength of 222-225 nm from acetal chromophore. FTIR
spectra (Figure 5(b)) showed stretching vibration of C-O-C bonds at the wavenumber 1100-1200 cm-1 and O-H bonds
at the wavenumber of 3000-3300 cm-1. The UV-Vis and FTIR spectra were quietly similar to APGs and the previous
APG C4 mixture.

FIGURE 5. (a) UV-Vis and (b) FTIR spectra of all variations APG C12 mixture

LC-MS/MS was conducted to characterize the structure of the APG C12 mixture. LC chromatogram of APG C12
mixture showed several peaks indicating the impurities of the synthesized compound since the APG C4 mixture as
reactant without purification before use. However, two peaks at the retention time of 2.38 and 3.08 min indicated the
mass number close to APG C12. A peak at 2.38 min was identified as APG C12 from glucose tetramer with [M+H]+
of 855.46 m/z while a peak at 3.08 min belongs to APG C12 from glucose trimer with [M+H]+ of 691.31 m/z. The
proposed fragmentation scheme of these APG C4 compounds was shown in Figure 6.
The synthesized APGs mixtures were tested for compatibility, emulsion stability, and solubility test to evaluate
their physical properties. The compatibility test was carried out by dissolving APGs solution into formation water and
observed for 2 weeks. Surfactants compatible with formation water will give a dissolved finish. The APG C4 mixture
solution that had completely dissolved in the formation water gave clearly-finish, while all variations APG C12
mixture solutions showed a cloudy-finish which indicated that the mixtures were not compatible with formation water
(Table 2, column 2).

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 (a)

(b)

FIGURE 6. Proposed fragmentation scheme of APG C12 from glucose (a) tetramer and (b) trimer

TABLE 2. Compatibility, emulsion stability, and solubility results of the APGs mixtures
Emulsion Solubility
Sample Compatibility
Stability (s) Methanol NaOH Ethyl acetate n-Hexane NaCl
APG C4 Clear 40 Soluble Soluble Soluble Emulsion Soluble
APG C12; 1 Cloudy 40 Soluble Insoluble Soluble Emulsion Insoluble
APG C12; 2 Cloudy 43 Soluble Insoluble Soluble Emulsion Insoluble
APG C12; 3 Cloudy 30 Soluble Insoluble Soluble Emulsion Insoluble
APG C12; 4 Cloudy 40 Soluble Insoluble Soluble Emulsion Insoluble
APG C12; 5 Cloudy 41 Soluble Insoluble Soluble Emulsion Insoluble

Table 2 (column 3) showed emulsion stability results for APGs mixtures. The APG C12 mixture from variation 2
displayed the best emulsion stabilities. The higher the reaction temperature, the better emulsion stability. However, at
120°C the emulsion stability was found to be the smallest compared to others. Solubility results for APGs mixtures
were exhibited in Table 2, columns 4-8. According to Table 2, the APG C12 mixture cannot work in high salinity,
high pH, and the presence of certain ions because the solubility test results still showed the insolubility of the APG
C12 mixture when dissolved in several solvents.

TABLE 3. IFT values of the APGs mixtures

Temperature Rotation Sample Density Density Drop D vertikal IFT Value
Sample Trial
(°C) (rpm) (g/cm3) (g/cm3) (mm) (mN/m)
APG C4 1 50 3000 0.9843 0.8471 1.1459 0.2676
2 50 6000 0.9843 0.8472 0.9920 0.6945
APG C12; 1 1 50 3000 0.9768 0.8473 1.1700 0.2690
2 50 6000 0.9768 0.8474 1.049 0.7760
APG C12; 2 1 50 3000 0.9667 0.8475 1.1700 0.2480
2 50 6000 0.9667 0.8476 0.9440 0.5210
APG C12; 3 1 50 3000 0.9802 0.8477 1.2200 0.3133
2 50 6000 0.9802 0.8478 1.0700 0.8450
APG C12; 4 1 50 3000 0.9844 0.8479 1.1800 0.2920
2 50 6000 0.9844 0.8480 0.934 0.5790
APG C12; 5 1 50 3000 0.9792 0.8481 1.2100 0.3033
2 50 6000 0.9792 0.8482 0.9500 0.5871

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 Table 3 showed the IFT values of the APGs mixtures The higher the temperature reaction, the lower the IFT value.
However, at 120°C the IFT value increased. According to Table 3, a reaction at 115°C is an effective temperature for
synthesizing the APG C12 mixture. The smallest IFT value was obtained from the APG C12 mixture in variation 2.
The low IFT value indicated that the compound had a good ability to reduce the interface tension of oil and water and
increase the percentage of oil recovery [10].
Overall, APGs can be synthesized using an indirect method by reacting fatty acid alcohol and carbohydrate with
the presence of an acid catalyst. Further research needs to be conducted to apply APGs as EOR surfactants. APGs can
be further used as EOR application since APGs fit the criteria for EOR surfactants, i.e. had a fairly good ability to
recover heavy oil with high salinity and high temperature [11].

CONCLUSION
In this study, the APG C12 mixture was successfully synthesized using the indirect method with the optimum
condition of transacetalization achieved from the mass ratio of glucose in technical grade and 1-dodecanol 1:7.5 m/m
with PTSA catalyst 0.5 mol% at 115oC for 4h. The physical properties from compatibility, emulsion stability,
solubility, and IFT value test revealed that the APG C12 mixture in this work still had fair properties to be applied in
EOR application. However, APGs can be further developed as promising EOR surfactants with several modifications
on APGs synthesis.

ACKNOWLEDGMENTS
This work was supported by Hibah Publikasi Terindeks Internasional (PUTI) Prosiding 2020 NKB-
1003/UN2.RST/HKP.05.00/2020 from DRPM Universitas Indonesia.

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