Performance Evaluation of Electrolyzer Report

Date : 25-04-2023
Plant : CAP
Prepared by Aiman M I
1. Introduction
As an energy-intensive industry, the chlor-alkali process has caused issues due to heavy electricity
consumption. Chlor-alkali electrolysis takes a key role in this process. The performance of the
electrolyzer should be evaluated.
2. Evaluation Standard
The first step is for the evaluator to determine the appropriate calculation that applies to the equipment
to be evaluated. Calculations are made based on the calculation formula provided by the licensor. The
data were taken from two sources like control room and the laboratory. The performance of the
electrolyzer is approached by current efficiency. The formula of current efficiency is shown below.
Qi ∗Ci −Qo ∗Co 2∗ O2
CE=1 − ∗ 100 − − LC
I ∗ N ∗ 0.0373 Cl 2
3. Result
The electrolyzer monitoring on Friday, April 25 2023 is shown below.
Table 1. The recapitulation of data on April 25 2023

Catholyte Temp. Acidity inlet Acidity outlet Current Membrane Anode/Cathode Suggested
Load Voltage pH
R-230 (TI 220) anolyte anolyte Efficiency Lifetime Lifetime HCl Injected

kA V degree C Max. 0.15 N 0.001N-0.005N % Months Months L/h

A 11,21 465,50 86,77 0,07193 0,00505 96,03 6 111 166,14 1,89
B 11,08 465,50 86,50 0,05278 0,00452 96,79 6 111 119,32 2,03
C 11,89 466,20 87,78 0,06171 0,00426 96,51 4 108 167,82 2,10
D 11,19 466,20 86,28 0,05363 0,00521 96,79 4 115 127,53 1,87
E 11,13 465,10 87,51 0,08150 0,00458 95,55 25 100 199,39 2,02
F 11,20 465,10 85,92 0,10002 0,00399 94,68 25 100 227,40 2,20
G 11,23 445,00 83,62 0,07916 0,00564 95,86 24 25 177,99 1,83
H 11,03 445,00 82,80 0,05682 0,00202 96,20 30 31 145,66 2,72
I 16,16 273,40 86,89 0,05831 0,00085 95,54 16 18 139,39 3,23
J 11,40 288,00 86,52 0,05277 0,00388 96,57 22 91 83,87 2,22
K 11,67 288,00 88,33 0,06958 0,00308 95,67 21 86 133,97 2,39
L 12,34 288,00 87,16 0,05597 0,00367 96,35 21 84 86,43 2,27
M 11,63 288,00 85,43 0,06405 0,00319 96,00 22 90 87,53 2,38
N 16,12 262,90 84,31 0,07576 0,00053 94,75 15 17 175,54 3,56
O 15,87 271,80 80,54 0,04639 0,00330 96,86 27 29 90,45 2,35
P 15,60 271,80 81,82 0,05044 0,00335 96,73 27 29 126,14 2,34
Q 15,86 270,30 81,04 0,05235 0,00324 96,62 12 15 123,49 2,37
R 15,73 270,30 81,74 0,04639 0,00543 97,27 10 13 120,11 1,84
S 16,03 429,10 85,20 0,05277 0,00750 96,26 19 39 200,57 3,30
T 15,99 437,70 87,21 0,10214 0,00229 94,29 39 39 411,43 2,64
Note:
Based on table 1, the acidity of outlet anolyte at electrolyzers A, D, G, I, N, R, and S are lower or
higher than the maximum or minimum range. The value of pH still need to be adjusted to the normal
range for those electrolyzers.

The data are provided in table 1, then the data illustrated in graphical form so that it is easy to
understand. Overall, the graph shows the current efficiency of all electrolyzers.

98.50
97.50
96.50
95.50
94.50
93.50
92.50
91.50
90.50
89.50
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

A B C D
Figure 1. Rectifier 1 electrolyzer

Note:
a. R-230-A : Current efficiency showed an upward trend and the voltage was stable compare with
the previous date. The value of pH still need to be controlled to the normal range.
b. R-230-B : Current efficiency showed downward trend of performance and the voltage was stable.
c. R-230-C : Current efficiency showed an upward trend of performance and the voltage was stable.
d. R-230-D : Current efficiency slightly declined of performance and the voltage was stable. The
value of pH still need to be controlled to the normal range.

98.00
97.50
97.00
96.50
96.00
95.50
95.00
94.50
94.00
93.50
93.00
92.50
92.00
91.50
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

E F G H
Figure 2. Rectifier 2 electrolyzer
Note:
a. R-230-E : Current efficiency showed an upward trend and the voltage was stable compare to
previous voltage.
b. R-230-F : Current efficiency slightly elevated and the voltage was stable compare to previous
voltage.
c. R-230-G : Current efficiency slightly declined and the voltage was stable compare to previous
voltage. The value of pH still need to be controlled to the normal range.
d. R-230-H : Current efficiency slightly declined compare to previous date and the voltage
was stable compare with the previous date.

97.80
97.20
96.60
96.00
95.40
94.80
94.20
93.60
93.00
92.40
91.80
91.20
90.60
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

J K L M
Figure 3. Rectifier 3 electrolyzer
Note:
a. R-230-J : Current efficiency showed an upward trend and the voltage was stable.
b. R-230-K : Current efficiency elevated significantly and the voltage was stable.
c. R-230-L : Current efficiency showed an upward trend to previous date and the voltage was stable.
d. R-230-M : Current efficiency showed downward trend and the voltage was stable.

97.60
97.20
96.80
96.40
96.00
95.60
95.20
94.80
94.40
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

O P Q R
Figure 4. Rectifier 4 electrolyzer
Note:
a. R-230-O : Current efficiency showed an upward trend and the voltage was stable.
b. R-230-P : Current efficiency elevated and the voltage was stable.
c. R-230-Q : Current efficiency showed an upward trend and the voltage was stable.
d. R-230-R : Current efficiency showed an upward trend and the voltage was stable. The value of pH
still need to be controlled to the normal range.

98.00
97.00
96.00
95.00
94.00
93.00
92.00
91.00
90.00
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

I N
Figure 5. Rectifier 5 electrolyzer

Note:
a. R-230-I : Current efficiency slightly declined and the voltage was stable. The value of pH still
need to be controlled to the normal range.
b. R-230-N : Current efficiency showed downward trend and the voltage was stable. The value of
pH still need to be controlled to the normal range.

98.00
97.00
96.00
95.00
94.00
93.00
92.00
91.00
90.00
19-May-22 8-Jul-22 27-Aug-22 16-Oct-22 5-Dec-22 24-Jan-23 15-Mar-23 4-May-23 23-Jun-23

S T
Figure 6. Rectifier 6 electrolyzer

Note:
a. R-230-S : Current efficiency showed an upward trend and the voltage was stable. The value of
pH still need to be controlled to the normal range.
b. R-230-T : Current efficiency showed downward trend and the voltage was stable.
Recomendations:

1. Related to the Asehi Kasei rules that the efficiency of the current calculation will be correct if the
anolyte outlet is sufficient to neutralize the OH-. The calculation of current efficiency is not correct
for electrolyzer A, D, G, I, R, N and S due to the higher or lower acidity outlet.

2. Currently, Electrolyzer F displayed an upward trend and the current efficiency slightly elevated.
The current efficiency of electrolyzer F is by about 94.68%. According to the Roa on April 25 2023,
the value of acidity inlet was around 0.10002 N, this value was more lower than previous date. The
low value of acidity inlet will affect to the high value of current efficiency. The acidity inlet and
outlet plays an important role to measure current efficiency in each electrolyzer. It is necessary to
see the trend increase or decrease.

4. The suggested injection HCl of electrolizer A is 166.14 L/h because the existing condition has a
high value of acidity outlet.

5. The suggested injection HCl of electrolizer D is 127.53 L/h because the existing condition has a
high value of acidity outlet.

6. The suggested injection HCl of electrolizer G is 177.99 L/h because the existing condition has a
high value of acidity outlet.

7. The suggested injection HCl of electrolizer I is 139.39 L/h because the existing condition has a low
value of acidity outlet.

8. The suggested injection HCl of electrolizer R is 120.11 L/h because the existing condition has a
high value of acidity outlet.

9. The suggested injection HCl of electrolizer N is 175.54 L/h because the existing condition has a
low value of acidity outlet.

10. The suggested injection HCl of electrolizer S is 200.57 L/h because the existing condition has a
high value of acidity outlet.

According to the ROA (April 25 2023), the value of Ni was 20.03 ppb at D-170 and the value of Si was
1274 ppb. The maximum value of Ni is 20 ppb meanwhile the maximum value of Si is 5000 ppb. The
source of Ni can arise from salt, cathode, piping, and equipment. Ni can affect to precipitates in
membranes and deposits on cathodes and the consequences are increased voltage and reduced of
current efficiency. On the other hand, Si can arise from salt, water, filter aid, and the atmosphere. The
Si has synergistic effects. Based on the calculation, The current efficiency of several electrolyzers
elevated at this time. In the next few weeks, it is necessary to see the trend constantly increase or
decrease.
Explanation about the transport phenomena of membrane, overvoltage and kinetic.

Membrane Asahi Casei is perfluoro-carboxylic acid type. This membrane showed the excellent
performance when the membrane has formed -COONa +. When the carboxylic group exchanged with
-COOOH, the performance of membrane will decrease. When the start up or shutdown, the acidity
should adjust above the normal condition because the quantity of hydroxyl ion that transported through
membrane is low.

When current passes through membrane, the cell voltage based on thermodynamic and butler former
(kinetic equation) is the sum of the individual components:
E = Eo,a- Eo,c- ƞa- ƞc+IRsolution+IRmembrane

Overvoltage is defined as the difference between the actual potential and the theoritical value due to the
several polarizations. Overvoltage consist of overvoltage of anodic, overvoltage of cathodic, and
overvoltage of ohmic. Overvoltage of anodic (ƞa) is caused by overcoming the energy barrier of the
slowest step of the electrochemical reaction. On the other hand, overvoltage ohmic is the potential drop
across electrolyte ( IRsolution) or across membrane (IRmembrane). This overvoltage can be calculated using
Ohm Law. Overvoltage of concentration (ƞc) occurs when the concentration of a component increases
or decreases at the boundary layer close to the membrane surface due to the selective transport through
the membrane.

The reaction at the anode is a competition reaction between Cl- ions and OH- ions to produce Cl2 and O2
simultaneously. If the acidity is lower, the oxygen content in the chlorine will increase. Inlet acidity is
limited to 0.15 N. If it is greater, it will cause the inlet nozzle to be damaged and dissolve and will
cause a membrane blister. On the other hand, the amount of HCl added shows the number of OH - ions
that migrate from the cathode to the anode . The movement of OH- ions from the cathode to the anode
will have implications for a higher ohmic drop. The ohmic drop in the electrolyte solution will enhance
too. The discharge of the ions from the bulk of the solution to the layer on the electrode
surface and diffusion across the layers. The Na+ at boundary layer close to the membrane surface can
decrease due to the migration of OH -. These phenomena will have an impact on lower current
efficiency.