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Effect of Process Condition in Plasma Electrolysis of Chloralkali Production

Article  in  International Journal of Chemical Engineering and Applications · October 2013

DOI: 10.7763/IJCEA.2013.V4.308

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 International Journal of Chemical Engineering and Applications, Vol. 4, No. 5, October 2013

Effect of Process Condition in Plasma Electrolysis of

Chloralkali Production
Nelson Saksono, Fakhrian Abqari, Setijo Bismo, and Sutrasno Kartohardjono


NaCl, will be decomposed in the solvent and form ions in the
Abstract—Chlor-alkali is one of the most important processes solution. Positive discharge electrode is called anode and the
in chemical industry. This process produces chlorine and negative one is cathode. Each electrode bonds ions which
caustic soda that becomes the main feedstock of daily needs have different discharge, so that ions with negative discharge
products. In this study, the process condition on chlorine gas
production by electrolysis plasma is examined. Plasma
will go to anode and the positive ions will go to cathode.
electrolysis can increase the chlorine gas production up to 24 Nevertheless, electrolysis of NaCl solution (brine electrolysis)
times in single compartment reactor and can reach up to 59 used in chlor-alkali production has significant weaknesses,
times in double compartment reactor compared to electrolysis those are low conversion resulted by the electrolysis process
process. In reactor with single compartment, high voltage and the use of high electric current when the electrolysis
results high current then cause high-energy consumption. The process occur [4]. Hence, it is needed to observe other
highest chlorine gas production is at 0.5 M and 300 V that
results 4.63 mmol within 15 minutes. On the other hand, using
possible technologies that can be applied in the production of
double compartment reactor, current is lower due to its higher chlor-alkali to reduce the energy consumption.
distance between two electrodes that makes the higher One of the technologies that can reduce the energy
resistance. In this case, the highest chlorine gas production is at consumption is plasma electrolysis. The plasma electrolysis
0.5 M NaCl and 700 V that results 11.25 mmol within 15 process is similar with electrolysis process, but it is done with
minutes. The use of ion selective membrane can keep the high enough voltage until the electric spark is formed
movement of charge from one electrode to other. Ion selective
membrane can separate side product of NaOH, but side producing the plasma on the electrolyte solution. The plasma
reaction of chlorine ion still exists. will produce reactive species such as radicals on large
amount which are accelerated by the sharp potential gradient
Index Terms—Plasma electrolysis, voltage, concentration, and have enough kinetic energy to induce unique chemical
depth, distance, ion-selective membrane. changes in aqueous solutions, so it is able to increase the
formation of products in solution several more times than the
Faraday electrolysis process [5], [6]. Using this technology
I. INTRODUCTION
may reduce the energy consumption several times than
Chlor-alkali industry is one of the most important conventional electrolysis so the productivity is more effective
industrial sectors in chemical industry. This sector supports [6].
other sectors because its products can be used as raw
materials in other industry. In Europe, chlor-alkali industry
supported about 55% of chemical and pharmaceutical II. METHOD
industries which gave profits up to 660 billion in 2009 [1].
Chlor-alkali Industry produces chlorine, hydrogen, caustic The design of reactor is shown in Fig. 1. The reactor has
soda (NaOH), hypochlorite, and other derivatives of chlorine two compartments where one compartment is equipped with
from NaCl and water (H2O) as raw materials. Chlorine (Cl2) graphite as anode and stainless steel as cathode in the other
and caustic soda (NaOH) are two of ten chemical substances side. This reactor can also be modified as one compartment
which are the most produced and used as raw materials of reactor by closing the connector between two compartments.
other daily products, such as: medicines, detergents, The reactor is batch system made from acrylic housing filter
deodorants, plastics, herbicides, insecticides, disinfectants, connected with globe valve. The electric source is connected
etc. [2]. Chlor-alkali production needs much electrical energy to 3-kVA-slide regulator with the output is then connected to
to process the electrolysis of alkali solution (NaCl). The cost 4x transformer. Diode Bridge is used to rectify the electric
for electricity in industry can reach until 70% of the selling current. The current is measured and noted from
price of the products [3]. Therefore, the effort to reduce the ampere-meter Yuhua A830L.
consumption of electrical energy in this industrial sector is The reactor design is also fulfilled with chlorine and
needed by doing research to get more efficient method and hydrogen gas measurement. The chlorine gas produced is
technology. passed into KI 2% solution and hydrogen gas is passed into
Chlor-Alkali uses the electrolysis process to produce its hydrogen analyzer. KI bonded the chlorine gas and reacted to
products. Electrolysis is a method of compound’s bonding form iodine that results the orange color in KI solution. Then,
separation by passing the electric current. Ionic compound, the solution was titrated by Na2S2O3 0.01 N. This study
analyzed the formation of plasma by varying NaCl
concentration from 0.05 M to 0.5 M with voltage from 500 V
Manuscript received July 29, 2013; revised September 30, 2013.
The authors are with the Department of Chemical Engineering, – 700 V. Furthermore, it measured the chlorine gas produced
Universitas Indonesia, Depok 16424, Indonesia (e-mail: and calculated the energy consumption of the process.
[email protected]).

DOI: 10.7763/IJCEA.2013.V4.308 266

 International Journal of Chemical Engineering and Applications, Vol. 4, No. 5, October 2013

10
12 13
conductivity in solution. Higher conductivity may cause the
11
electrons move easily so that the chance of collisions between
500 V 220V species in the solution increases [6], [7]. This collision makes
the scattered energy becomes larger so that the radicals
formed by the excitation of electrons in the ions are more [8].
9

1
B. The Effect of Voltage in Chlorine Gas Production
3 2
Fig. 3 shows the production of chlorine for 15 minutes of
testing at a voltage of 500 V, 600 V and 700 V. At a
concentration of 0.1 M NaCl, the production of chlorine gas
is relatively low at 0.05 mmol, 0.09 mmol, and 0.16 mmol.
4
5 6
7
This is due to the unstable formation of plasma and more
8
dominant electrolysis process. At a concentration of 0.2 M
NaCl, the production of chlorine gas is higher than 0.1 M that
1. Reactor 8. Hydrogen Analyzer
is 0.11 mmol, 0.48 mmol, and 0.86 mmol. At this
2. Anode (Graphite) 9. Thermometer concentration, the plasma formed was not stable. However,
3. Cathode (Stainless Steel) 10. Ampere-meter the signs are formed plasma looks more stable than at a
4. Connector 11. Diode “Bridge”
5. NaCl Solution (Catholyte) 12. Transformer
concentration of 0.1 M NaCl. At a concentration of 0.3 M
6. NaCl Solution (Anolite) 13. Slide Regulator NaCl, the production of chlorine is 1.96 mmol, 2.34 mmol,
7. Bubbler of KI Solution and 3.54 mmol. At a concentration of 0.4 M NaCl, the
Fig. 1. Equipment configuration production of chlorine is 2.16 mmol, 5.66 mmol, and 6.24
mmol. Whereas at a concentration of 0.5 M NaCl, the highest
chlorine production reach 5.78 mmol, 10.13 mmol, and 11.25
III. RESULTS AND DISCUSSIONS mmol
From the results obtained, the higher the voltage, the
A. The Effect of NaCl Concentration in Chlorine Gas
higher the chlorine produced. It is because of the plasma
Production
formed more stable and able to trigger more radicals that
The effect of concentration in chlorine gas production is accelerate the rate of reaction in chlorine formation. Joule
shown in Fig. 2. Using 500 V as cell-voltage, the highest heating effect that will get bigger with the higher voltage
chlorine production is 5.78 mmol for15 minutes at 0.5 M affects plasma stability. This is due to the conversion of
NaCl. The lower concentration will also produce lower electrical energy into heat energy that makes the solution
chlorine gas such as 0.05 mmol, 0.11 mmol, 1.96 mmol, and around the electrode evaporate (local vaporization solvent) to
2.16 mmol for 0.1 M, 0.2 M, 0.3 M, and 0.4 M NaCl form gas sheath [9]. The formation of gas bubbles will trigger
respectively. For 600 V, chlorine produced is 0.09 mmol, the collision between the gas bubbles with an electrical
0.48 mmol, 2.34 mmol, 5.66 mmol, and 10.13 mmol for each charge so that scattering of energy occurs and let the
concentration from 0.1 to 0.5 M NaCl respectively. formation of plasma [10].
Furthermore, for 700 V, chlorine produced is 0.16 mmol,
0.86 mmol, 3.54 mmol, 6.24 mmol, and 11.25 mmol 12
0.1 M
respectively. 0.2 M
10 0.3 M
Chlorine Gas (mmol)

12.0 0.4 M
500 V 8 0.5 M
600 V
10.0
700 V 6
Chlorine Gas (mmol)

8.0
4
6.0
2
4.0
0

2.0 450 500 550 600 650 700 750

Voltage (V)

0.0 Fig. 3. Variation of voltage in chlorine gas production for 15 minutes at 70 –

80oC
0 0.1 0.2 0.3 0.4 0.5 0.6
NaCl Concentration (M)
From the results of voltage and concentration variation, it
Fig. 2. The production of chlorine as a function of NaCl concentration within can be seen that the role of concentration over a major effect
15 minutes at 70 – 80oC on the amount of chlorine gas product results. Both variables
contributed each in the process of production of chlorine gas
Higher concentrations make the number of available with the plasma electrolysis method. However, both have
chlorine in solution more. This can lead to the formation of different influences. The voltage affects the plasma formation
chlorine radicals so that increased the production of chlorine. that in turn influences the formation of radical species in
In addition to the amount of chlorine content in the solution, solution. However, the quantity of chlorine gas generated is
the higher the concentration will result to the higher more influenced by how much of the available chlorine in

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 International Journal of Chemical Engineering and Applications, Vol. 4, No. 5, October 2013

solution. Radical formation in solution has an influence on 800

the reaction mechanism. Radicals have the ability to react 677
faster than the other species. However, when the content of 700

Electric Power (W)

chlorine in the solution is limited, formed radical (OH 600
radicals or other radical species) cannot encourage the
500
production of chlorine gas.
400 357
C. The Effect of Electrode Distance in Chlorine Gas
Production 300
One of parameters influence the activity of plasma is the
200 137
distance between electrodes. Two compartments reactor has
about 15 cm in distance between anode and cathode. It will 100
cause the lower current flow due to higher resistance in the
0
solution [11]. Energy consumption will be lower, however
0 1 2
Joule heating effect to the solution will also lower. It makes
the formation of gas sheath due to local solvent vaporization Anode Depth (cm)
around the electrodes need longer time and cause plasma will Fig. 5. Effect of anode depth to electric power in electrolysis process
be more difficult to form. In this study, condition is set in
high voltage to make the electric current higher. It will cause The greater the electric current is caused by the wider of
to the higher Joule heating, so plasma can be easily formed. anode surface area to flow the current. Furthermore, the
Chlorine gas product yield is different between the two wider the surface area will make several zones in anode,
type of reactor (one and two compartment) caused by electrolysis zone and plasma electrolysis zone. Because of
differences in both the operating voltage. For one the existence of electrolysis zone, the electric current
compartment reactor with closer distance of electrode, the becomes high. This zone can be minimalized by narrowing
voltage is set to 200V - 300V. As for the two compartments the surface area where the plasma formed (anode). In the
reactor, the voltage is set to 500V - 700V. By seeing the research conducted by Sengupta (1994), it was stated that in
difference voltage, the voltage on the reactor with a two lower and smaller electrode, the current density would be
compartments reactor is two times larger than the one greater. It will increase the amount of heat energy (Joule
compartment reactor. The results of chlorine gas products Heating Effect) and will produce more vapor sheath in
also have the same ratio that is 2 times. This explains the electrode surface area. The vapor formed will cover the
higher voltage can increase the production of chlorine gas in anode and the electron excitation due to the potential
a linear fashion. Increase the voltage 2 times, can increase the difference will cause the formation of plasma. The existence
production of 2 times anyway as shown in Fig. 4. of plasma will cause the electric current become lower and
12 fluctuating [12].
10 0.2
0.185
0.18
Chlorine Gas Production (mmol)
Chlorine Gas (mmol)

8
0.16
6
0.14
4 0.12
2 0.1
0 0.08
0.10 0.20 0.30 0.40 0.50
0.06 0.041
"Electrolysis" 0.03 0.04 0.06 0.14 0.19
"Plasma Electrolysis in One
0.04 0.023
Compartment" 0.67 1.02 1.69 2.50 4.62
0.02
"Plasma Electrolysis in Two
Compartments" 0.16 0.86 3.54 6.24 11.25 0
0 1 2
o Anode Depth (cm)
Fig. 4. Comparison of chlorine gas production for 15 minutes at 70-80 C
Fig. 6. Effect of anode depth to chlorine production in electrolysis process

D. The Effect of Electrode Depth in Chlorine Gas

Besides influencing the electric current, anode depth in the
Production
solution also affects the chlorine gas produced shown in Fig.
One of the variables in this study is the depth of anode. The 6. The test is conducted by measuring the chlorine dissolved
depth is set into three variations: on the surface of the into KI solution for 5 minutes. From the test is resulted that
solution, 1 cm, and 2 cm below the surface of the solution. the deeper the anode, the amount of chlorine gas produced is
From the results of research conducted, the deeper the anode increase to. For anode on the surface of the solution, chlorine
in the solution, then the electric current used is greater. The production is 0.023 mmol. Furthermore, for 1 cm and 2 cm
amount of current flow for anode at the surface of the solution depth, chlorine productions are 0.041 mmol and 0.185 mmol
is about 0.46 A. Furthermore, the 1 cm depth is about 1.19 A respectively as shown in Fig. 5. The depth will influence in
and at 2 cm depth is 2.26 A. If the currents are multiplied by vapor sheath production in anode surface. The wider the
the applied voltage (i.e. 300 V), then it will obtain electric anode covered by vapor sheath, so the plasma formed will be
power consumed as shown in Fig. 5.

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 International Journal of Chemical Engineering and Applications, Vol. 4, No. 5, October 2013

bigger [13]. It will increase the amount of compound ion-selective membrane (Nafion ®) is low [14]. This causes
decomposed to form radical species that then produced the the current to be small as shown in Fig. 8.
chlorine gas. Nevertheless, the wider area of anode surface The use of ion-selective membrane may inhibit the transfer
will let the zone of electrolysis exists and the electric current of charge from one electrode to the other electrode. This
will be higher although more products formed. phenomenon resists the plasma to be formed. Based on Fig. 8,
the current characteristic does not seem similar to that in
E. The Effect of Membrane Selective Ion Usage in Plasma
plasma electrolysis where there is a point of critical currents
Electrolysis Process
and fluctuations thereafter.
In-situ separation technology using ion selective
0.4
membranes in chlor-alkali production process is commonly
used in the industry. In this study, the use of ion-selective 0.4
membranes is tested to see its effect on plasma formation and 0.3

Current (Ampere)
productivity of the process. The purpose of the use of
0.3
ion-selective membrane is to reduce the potential for adverse
reactions that cause the production of chlorine gas is not 0.2
optimal. 0.2
In this study, ion selective membrane is installed between
0.1
the anode and cathode compartments. At the anode
compartment contains 0.5 M NaCl solution and the cathode 0.1
compartment contains distilled water. Different design 0.0
solutions in both compartments following the existing design
0 5 10 15 20 25 30
in the chlor-alkali industry. This system will make the anode Time (Minutes)
compartment containing NaCl will produce chlorine gas and
Fig. 8. Current change in process with ion-selective membrane system
cathode compartments were filled with water to produce
hydrogen gas and a solution of NaOH as shown in Fig. 7.
In the Fig. 8, the longer the flow is increasing. On the
Displacement of the charge on the ion selective membrane
observations made, the higher the current due to the increase
is affected by the conductivity of the membrane that is
of temperature in the system. Initial temperature was 29oC
expressed as proton conductivity in the membrane. Charge
and gradually increased up to 35-40oC. Along with increasing
transfer mechanism (proton) can be explained by the areas
temperature, conductivity of ion-selective membrane (proton
contained within the membrane. The first area is the area that
conductivity) increases [8]. This causes the current to
is formed from the hydrophobic polymers of fluorocarbons
increase. However, current and voltage are regulated is not
and hydrophilic regions containing sulfonate groups, protons,
strong enough to create the effect of Joule heating at the
and hydration water. Between the two regions, there is a
anode so that the plasma is not formed and the process is
central region (intermediate) that has the character of both
dominated by the electrolysis.
areas. Hydrophobic fluorocarbon chain and hydrophilic
sulfonate group is set to maximize the interaction between the
membrane fragments. This led to the formation of the
IV. CONCLUSION
grouping ion hydration in aqueous phase at fluorocarbons
area. Research that has been done indicates that proton The application of plasma electrolysis can be implemented
transfer occurs between groups’ ions (protons) due to proton in the production of chlor-alkali. At the time of the plasma
transfer in the sulfonate group [14]. formed, the current will fluctuate and gradually decline. It
can reduce the amount of energy consumption because it can
run with lower current with the same voltage condition. The
H2O NaCl + H2O higher the concentration and voltage will lead to the increase
of production of chlorine gas. Radicalization process will
H+ Na+ produce active species that can make the reaction mechanism
H+
becomes unusual. It will lead to the faster gas product
OH-
Cl- formation process for about 11.25 mmol compared to
OH- electrolysis process which is only 0.19 mmol. Furthermore,
the anode depth also affects the production of chlorine. The
wider the surface area of anode in the solution, the production
Kompartemen Katoda Kompartemen Anoda
of chlorine is increase, but the power consumption is also
increase. The use of ion-selective membrane can inhibit the
Fig. 7. Ion movement in ion-selective membrane system
transfer of charge from one electrode to the other electrode.
This makes the plasma cannot be established.
In this study, the measured of current flow on
ampere-meter are very small. At a concentration of 0.5 M ACKNOWLEDGEMENT
NaCl using reactor without membranes, currents may reach
Directorate General of Higher Education, Ministry of
1-2 A. However, when the membrane is installed, the flow is
Education Republik Indonesia and Directorate of Research
only in the range of 0,1 - 0,3 A. Resistance of the membrane
and Community Service Universitas Indonesia supported this
quite high causes this phenomenon. Research conducted by
work as funding scheme of BOPTN 2013.
Slade et al (2002) showed that the conductivity of the

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 International Journal of Chemical Engineering and Applications, Vol. 4, No. 5, October 2013

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