Influence of Ions and Temperatures on Water-Ethanol-Gasoline

Liquid-Liquid Equilibrium

Okta Bani

, Lilis Sukeksi

1,2

, Taslim

, Iriany

1,2

and Muhammad Dedi Anggreawan

Department of Chemical Engineering, Universitas Sumatera Utara, Jl Almamater, Medan, Indonesia

Center of Excellence for Natural Resources Based Technology, Universitas Sumatera Utara, Medan, Indonesia

mhddedianggreawan@yahoo.com

Keywords: Water-Ethanol-Gasoline Equilibrium, Ions, KH

, KCl, KOH.

Abstract: Water-ethanol-gasoline liquid-liquid equilibrium (LLE) was investigated. In this study, the LLE data was

obtained gravimetrically and volumetrically by turbidity titration under influence of KH

, KCl, and

KOH. Effect of temperature was also evaluated at 30 and 50℃. Results suggest that presence of ions alter

the LLE and different ions affect the LLE differently. At concentration of 20 mM, temperature had

significant effect on the LLE. Increasing temperature reduced the heterogeneous region and allowed more

water in gasoline phase.

1 INTRODUCTION

World energy demand is predicted to increase with

Asian countries leading the trend (U.S. EIA, 2016).

To meet the energy demand, alternative energy is

currently being developed with lignocellulosic

ethanol as one of the potential candidate. Cellulosic

ethanol has gained popularity these recent years, but

it is yet to be commercialized because it is too

expensive and inefficient (Johnson, 2016; Olofsson

et al., 2017; Klein-Marcuschamer et al., 2011).

While many researches had been conducted

emphasizing on different aspects of the production

such as pretreatments (type and condition),

hydrolysis (enzyme type and load), fermentation

(microbes and condition), process scheme (SSF,

SScF, CBP, and DMC), pre fermentation processing

(hydrolysate detoxification, sugar pre concentration,

additives), cell/enzyme immobilization, and so on

(Li et al., 2017; Singh et al., 2017; Vohra et al.,

2014; Hernawan et al., 2017; Xu and Wang, 2017;

Kumar et al., 2016; Lam et al., 2014; Johnson, 2016;

Ziolkowska, 2014), few focused on alternative

purification step or its integration into the process

scheme. One possible scheme is production of

alcohol gasoline blend, known as gasohol, by

extraction of fermentation broth (Leeper and

Wankat, 1982; Lee and Pahl, 1985). Coupled with

direct broth recycling using non-sterile fermentation

(Chen and Wan, 2017), this method can reduce

operation cost to overcome the economic barrier of

cellulosic ethanol. Previous attempt on integration of

purification step and direct broth recycling using

biodiesel had shed some light on its viability, though

extraction using gasoline might be more

economically feasible (Bani, 2014). However,

integrating extraction using gasoline into process

scheme requires careful consideration due to

possible enzyme and microbe inhibition, formation

of emulsion, water infiltration into gasohol, etc. The

interdependency of these factors also further

complicates the analysis of such system. Therefore,

this study aimed to collect water-ethanol-gasoline

equilibrium data as foundation for the system

analysis.

2 MATERIALS & METHODS

2.1 Materials Collection

Aquabidest, ethanol, KOH, KCl, and KH2PO4 were

purchased from local chemical store (CV. Rudang

Jaya) while gasoline was purchased from local petrol

station. All chemicals used were of technical grade

and gasoline was Pertamax from PT. Pertamina.

Specification of Pertamax gasoline is tabulated in

Table 1.

100

Bani, O., Sukeksi, L., Taslim, ., Iriany, . and Anggreawan, M.

Inﬂuence of Ions and Temperatures on Water-Ethanol-Gasoline Liquid-Liquid Equilibrium.

DOI: 10.5220/0008525601000103

In Proceedings of the International Conference on Natural Resources and Technology (ICONART 2019), pages 100-103

ISBN: 978-989-758-404-6

Table 1: Some Specification of Pertamax Gasoline

(Pertamina 2017).

Characteristics

Unit

Value

Octane number

RON

>92

Oxidation stability

min

>480

Sulfur content

% m/m

0.05

Lead content

g/L

0.013

Oxygen content

% m/m

<2.7

Aromatic content

% v/v

<50

Benzene content

% v/v

Sediment

mg/L

Colour

Blue

Die content

g/100 L

<0.13

2.2 Liquid Liquid Equilibrium Data

Collection

Water-ethanol-gasoline equilibrium data was

obtained by turbidity titration. The procedure began

by preparing a water-ethanol mixture in a 100-ml

flask. The mixture was titrated with gasoline using a

5-ml burette until it became turbid, then added again

with gasoline. Afterwards, it was titrated with

ethanol to clarity, then added again with ethanol.

Each phase change and liquid addition was recorded.

The titration was repeated until the flask was full.

Initial mixture composition was adjusted with each

procedure iteration to obtain enough data for

construction of ternary phase diagram. The

experiment was repeated under influence of

potassium ions (KOH, KCl, and KH

) and

temperature of 30 and 50°C. Ion influence was

investigated by replacing aquabidest with ionic

solution at concentration of 20 mM. Temperature

variation was maintained within ±2°C by immersing

the flask in water bath during titration.

2.3 Ternary Phase Diagram

Construction

LLE Data was plotted in R using ggtern library

using gg_smooth_tern plotting (Hamilton, 2017).

LLE composition was calculated as mass fraction by

adding up each component during each phase

change. For gravimetric data, the mass change

during each addition of liquid was treated as added

mass of said liquid. For volumetric data, the titer

volume was converted to mass using the liquid

density at the room temperature during experiment.

3 RESULTS AND DISCUSSIONS

3.1 Effect of Potassium Ions

Ternary phase diagrams for water-ethanol-gasoline

system without presence of ions and under influence

of KOH, KCl, and KH

are shown in Figure 1-4.

Figure 1: Water-Ethanol-Gasoline LLE System.

Figure 2: Effect of KOH on Water-Ethanol-Gasoline LLE

System.

Addition of KH

increased the heterogeneous

region of the diagram, indicating that the system had

more separation. However, it is worth noting that

was emulsified in this system and as such,

require a more thorough investigation to reach better

conclusion. For KOH, the shape of heterogeneous

region became rounder. This resulted in less water in

the gasoline phase at low ethanol concentration

region but more water in gasoline phase at high

ethanol concentration region, which means that

KOH promote both separation and homogeneity. A

more sophisticated method is required to ascertain

this result. For KCl, its addition seemed to promote

100

Ethanol

Gasoline Aquaeous

Water

100

Ethanol

Gasoline Aquaeous

KOH

Inﬂuence of Ions and Temperatures on Water-Ethanol-Gasoline Liquid-Liquid Equilibrium

101

homogeneity as evidenced from the shrinking

heterogeneous region.

Figure 3: Effect of KCl on Water-Ethanol-Gasoline LLE

System.

Figure 4: Effect of KH

on Water-Ethanol-Gasoline

LLE System.

3.2 Effect of Temperature

Ternary phase diagrams for water-ethanol-gasoline

system at 30°C and at 50°C are shown in Figure 5. It

is apparent that temperature has significant effects

on the LLE as the heterogeneous region shrank

significantly, which suggests that more water will

present in gasoline and more gasoline will present in

water. Similar finding at different temperature range

was also reported (Cerempei, 2011)

Figure 5: Effect of Temperature on Water-Ethanol-

Gasoline LLE System. : 30℃, : 50℃

4 CONCLUSIONS

Water-ethanol-gasoline LLE is influenced by

presence of ions and temperature. The most

pronounced of these two is temperature. Different

ions bode different effects on the system, although

more data are required to ascertain these results.

ACKNOWLEDGEMENTS

The authors would like to thank the Ministry of

Higher Education of Indonesia for the funding

through TALENTA USU 2017.

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