SCHOOL OF CHEMICAL ENGINEERING

EKC 451: PROCESS DESIGN AND ANALYSIS

SEM I 2017/2018

PLANT DESIGN FOR THE PRODUCTION OF

SODIUM HYPOCHLORITE

Task 2

GROUP NUMBER :7

GROUP MEMBERS :

1) JOANNA JAYAMALAR A/P JAMES GUNAM 125138

2) NG ZHI HENG 125161

3) ENGKU MOHAMAD HAFZANURUDIN BIN ENGKU YUNUS 127206

4) FAKHIRA HUDA CHE YUSUF 127207

SUPERVISOR : ASSOCIATE PROFESSOR DR. LIM JIT KANG

DATE OF SUBMISSION : 17th NOVEMBER 2017

Chapter 1: Process Analysis ...................................................................................................................................... 4

1.1 Process Description ........................................................................................................................................ 4

1.1.1 Seawater purification ............................................................................................................................... 4

1.1.2 Electrolysis Process ................................................................................................................................. 5

1.1.3 Dechlorination of depleted brine / seawater ............................................................................................ 6

1.1.4 Production of 50wt% of Caustic Soda, NaOH ........................................................................................ 7

1.1.5 Production of Sodium Hypochlorite........................................................................................................ 7

1.2 Process Flow Diagram (PFD) ......................................................................................................................... 8

1.3 Justification of Material of Construction ........................................................................................................ 9

i) Stainless steel .................................................................................................................................................. 9

ii) Carbon Steel .............................................................................................................................................. 10

iii) Titanium .................................................................................................................................................... 10

1.4 Justification of Equipment............................................................................................................................. 11

1.4.1 Reaction Equipments ............................................................................................................................. 11

1.4.2 Mass Transfer Equipments .................................................................................................................... 15

1.4.3 Heat Transfer Equipments ..................................................................................................................... 20

1.4.4 Auxiliary Equipment ............................................................................................................................. 25

1.5 Economic Potential........................................................................................................................................ 31

1.5.1 Economic Potential Without Recycle Stream ................................................................................................ 32

1.6 Separation Operations used in Sodium Hypochlorite Plant ........................................................................... 36

Table 5: Physical Separation ............................................................................................................................... 36

Table 6: Physical Separation ............................................................................................................................... 37

Table 7: Separation by Filtration ......................................................................................................................... 38

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 Table 8: Separation by Filtration ......................................................................................................................... 39

Table 9: Separation by Absorption ...................................................................................................................... 40

Table 10: Separation by Absorption .................................................................................................................... 41

Chapter 2: Mass Balance of the Process Plant ........................................................................................................ 42

2.1 Mass Balance of Each Unit ........................................................................................................................... 43

2.2 Overall Mass Balance .................................................................................................................................... 65

2.3 Stream Table ................................................................................................................................................. 90

2.3.1 Stream 1-10 ........................................................................................................................................... 90

2.3.2 Stream 11-20 ......................................................................................................................................... 91

2.3.3 Stream 21-30 ......................................................................................................................................... 93

2.3.4 Stream 31-40 ......................................................................................................................................... 95

2.3.5 Stream 41-51 ......................................................................................................................................... 97

Chapter 3: Energy Balance of the Process Plant ..................................................................................................... 99

3.1 Energy Balance of Each Unit ..................................................................................................................... 100

3.2 Overall Energy Balance .............................................................................................................................. 122

Chapter 4: Justification on Aspen Plus Simulation .............................................................................................. 127

Chapter 5: Utilities & Other Issues ....................................................................................................................... 142

5.1 Utility Stream Balance ................................................................................................................................ 142

5.1.1 Cooling & Heating Utilities ................................................................................................................ 142

5.1.2 Electricity ............................................................................................................................................ 144

5.2 Waste Generation ............................................................................................................................................ 145

5.2.1 Solid Wastes ............................................................................................................................................. 145

5.2.2 Liquid Wastes ........................................................................................................................................... 146

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Chapter 6: References ............................................................................................................................................... 148

Chapter 7: Appendix ............................................................................................................................................. 150

7.1 Meeting Minute .......................................................................................................................................... 150

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Chapter 1: Process Analysis

1.1 Process Description

1.1.1 Seawater purification

Seawater is used as raw material. Before the sea water is fed into the electrolyser, sea water goes
through to primary and secondary brine purification to remove any wanted impurities such as magnesium
ions, calcium ions and any large solid particle inside the seawater. Firstly, seawater is passed through an
automatic, self-cleaning fine mesh strainer to remove the large solid particle inside the seawater. [2]Then, the
seawater can pass through brine reactor to precipitate calcium and magnesium ions as calcium carbonate
(CaCO3) and magnesium hydroxide (Mg(OH)2).

Assumption: only consider CaCl2 and MgCl2 in the sea

*Precipitation of Calcium ions (in CaCl2 in the sea)

𝐶𝑎𝐶𝑙2 (𝑎𝑞) + 𝑁𝑎2 𝐶𝑂3 (𝑙) → 𝐶𝑎𝐶𝑂3 (𝑠) + 2𝑁𝑎𝐶𝑙(𝑎𝑞)

*Precipitation of Magnesium ions (in MgCl2 in the sea)

𝑀𝑔𝐶𝑙2 (𝑎𝑞) + 2𝑁𝑎𝑂𝐻 (𝑎𝑞) → 𝑀𝑔(𝑂𝐻)2 (𝑠) + 2𝑁𝑎𝐶𝑙(𝑎𝑞)

Seawater with sodium chloride, calcium carbonate (solid), magnesium hydroxide (solid) and some
magnesium and calcium chloride (which didn’t precipitate) then passed through clarifier. Calcium carbonate
and magnesium hydroxide are removed as sludge by sedimentation. Next, the remaining calcium carbonate
and magnesium hydroxide is filtered by allowing seawater to pass through pre-coat type leaf filter. The pre-
coat used in this filter is cellulose and when the filter reaches its maximum operating pressure which is
2.5kg/cm2 , the filter is cleaned and a pre-coating filter (safety filter) is used to stop the cellulose fibers from
being released by pressure leaf filter.[3]

Then a heat exchanger is used to control the temperature of seawater at operating temperature of the
resin (60℃ and 1atm) and electrolyser (normally between 80℃ to 95℃ and 1 atm [4], cannot be more than
120℃).

4
 Chelating resin has high sensitivity towards magnesium and calcium ions and is used to absorb those
metal ions. The calcium and magnesium ions must below 20ppb.

Chelating resin tower equation (absorb remaining calcium and magnesium ion)

1 1
𝑀𝑔𝐶𝑙2 (𝑎𝑞) + 𝑅𝑆𝑂3 − 𝑁𝑎+ (𝑎𝑞) → 2 𝑆𝑂3 − 𝑀𝑔2+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) [5]
2

1 1
𝐶𝑎𝐶𝑙2 (𝑎𝑞) + 𝑅𝑆𝑂3 − 𝑁𝑎+ (𝑎𝑞) → 𝑆𝑂3 − 𝐶𝑎2+ (𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞)
2 2

The remaining compounds from chelating resin tower is sodium chloride and water. To further be filtered,
sodium chloride and water enters electrodialysis membrane before entering electrolyzer for electrolysis of sodium
chloride.
1.1.2 Electrolysis Process
Purified seawater with 26wt% NaCl [4] is fed into the anode compartment of the electrolyser at 60℃ and
direct current (DC) is passed into the electrolyser during electrolysis. The chloride ions are oxidised to chlorine gas
at the anode compartment while demineralized water is reduced to hydrogen gas and hydroxide ions at the cathode
compartment. The ion-conducting membrane (perfluorinated sulfonate) [4] only allows sodium ions to pass through
to the cathode compartment to combine with hydroxide ions to become sodium hydroxide. The concentration of
sodium hydroxide allowed to pass through the membrane is 30wt% until 33wt% of sodium hydroxide, NaOH.

Electrochemical reaction

(Operating Condition: 80℃ to 95℃ and 1atm [4])

Anode reaction

2(𝑁𝑎+ (𝑎𝑞) + +𝐶𝑙 − (𝑎𝑞)) → 2𝑁𝑎 + (𝑎𝑞) + 𝐶𝑙2 (𝑎𝑞) + 2𝑒 −

Cathode reaction

2𝐻2 𝑂 (𝑙) + 2𝑒 − → 2𝑂𝐻 − (𝑎𝑞) + 𝐻2 (𝑔)

Overall reaction

2𝑁𝑎𝐶𝑙(𝑎𝑞) + 2𝐻2 𝑂(𝑙) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2 (𝑔) + 𝐶𝑙2 (𝑔)

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Three products through the electrolysis

1. 30wt% to 33wt% caustic soda at 80℃ to 90℃ [4]

2. Wet chlorine gas at 80℃ to 90℃ [4]
3. Hydrogen gas at 80℃ to 90℃[4]
Side products

1. Depleted seawater at 80℃ to 90℃ [4]

1.1.3 Dechlorination of depleted brine / seawater

Spent seawater is then passed through the dechlorination tower to remove the free chlorine content in
seawater. Chlorine gas is dissolved in the depleted seawater as hypochlorous acid. 25℃ of 98wt% of hydrochloric
acid is fed into the dechlorination tower to separate the chlorine gas from the depleted brine. The operating pressure
of vacuum packed tower is 0.32kg/cm2 to 0.34kg/cm2 with packing material of ceramic saddle [6]. Then, the chlorine
[3]
gas from the dechlorination tower together with the chlorine gas produce from the electrolyser (at 80℃ 𝑡𝑜 90℃ )
passes through the dryer to remove the moisture content. 70℃ of dry chlorine gas is released from the dryer then pass
through the heat exchanger to cool down to 20℃. Then, certain fraction of chlorine gas will be used to produce the
sodium hypochlorite while certain fraction of chlorine gas will go through the chlorine processing plant. Chlorate
decomposer for the brine is only used if necessary

*Assumption: chlorate is not produced hence chlorate decomposer is no need.

Chlorine gas dissolve in sea water to produce hypochlorous acid and hydrochloric acid.

𝐶𝑙2 (𝑔) + 𝐻2 𝑂(𝑙) ⇌ HOCl(aq) + HCl(aq)

Addition of hydrochloric acid to separate the chlorine gas from the depleted brine. (Shifts the equilibrium of the
reaction to the left)

𝐻𝑂𝐶𝑙(𝑎𝑞) + 𝐻𝐶𝑙(𝑎𝑞) 𝑖𝑛 𝑒𝑥𝑐𝑒𝑠𝑠 → 𝐶𝑙2 (𝑔) + 𝐻2 𝑂(𝑙)

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1.1.4 Production of 50wt% of Caustic Soda, NaOH

Certain fraction of 30wt% to 35wt% of caustic soda is used to react with chlorine gas to form sodium
hypochlorite while certain fraction of caustic soda at 80℃ to 90℃ will pass through the evaporator to remove some
of the water moisture from sodium hydroxide to concentrate it up to 50wt%.

1.1.5 Production of Sodium Hypochlorite

Basically, the process to produce the sodium hypochlorite is same as the direct chlorination of sodium
hydroxide, the main difference is in electrolysis (chor-alkali industry), caustic soda and chlorine is generated from
seawater instead of purchasing them. A fraction of 32wt% of caustic soda from the electrolyser is used to react with
chlorine gas to produce the 12.5wt% of sodium hypochlorite. 32wt % of caustic soda must be diluted to 14wt % to
16wt % [3, 7] of caustic soda before it is used to react with the chlorine gas. Initial concentration of caustic soda
cannot be more than 20wt % because it increases the possibility of precipitation of sodium chloride salt. Then ,
14wt % to 16wt % caustic soda is cooled down to 15.56℃ by cooling water. [7] The chlorine gas is then reacted
with 32wt % caustic soda in the packed tower with random packing material. The reaction occurs at 1 atm and
cannot more than 30℃ to avoid the formation of chlorate. [3, 7] After that, liquid bleach is passed through the buffer
tank and then heat exchanger to cool down the liquid below 30℃. The liquid bleach is stored in a hypo tank as
product.

Reaction in the packed tower

Main reaction

𝐶𝑙2 (𝑔 𝑜𝑟 𝑙) + 2𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙) At 27.78℃ and 1atm

Side reaction (Decomposition of sodium hypochlorite)

*Temperature of the reaction is controlled at below 30℃ to avoid the decomposition of sodium hypochlorite.)

3𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) → 𝑁𝑎𝐶𝑙𝑂3 (𝑎𝑞) + 2𝑁𝑎𝐶𝑙(𝑎𝑞)

2𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) → 2𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝑂2 (𝑔)

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1.2 Process Flow Diagram (PFD)

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1.3 Justification of Material of Construction

Based on our proposed plant of production of sodium hypochlorite, we have decided to

utilize 3 different types of material of construction which are stainless steel, carbon steel and
titanium. It is necessary for this plant to use 3 different types of materials due to the presence of
chlorine which will lead to corrosion of materials.

i) Stainless steel
Stainless steel is an alloy of iron with minimum 10.5% of chromium. Chromium is the
one which helps prevent corrosion thus higher chromium content, more difficult for it to corrode.
Below are the justifications to use stainless steel in our production plant:

• Corrosion resistance:
Low alloy grades resist corrosion in atmospheric conditions whereas high alloy grades
can resist corrosion in most acids, alkaline solutions, and chloride bearing environments,
even at elevated temperatures and pressures. [8]

• Easy fabrication:
It can be cut, welded and fabricated easily comparative to other materials. [8]

• Works at high and low temperature resistance:

Some stainless-steel grades can be used at any temperature range due to its strength while
other grades exhibit good toughness at cryogenic temperature. [8]

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 ii) Carbon Steel
Carbon steel is a type of allow which has iron and carbon composition in it. Other elements
are present which are namely, manganese 1.65%, silicon of 0.6% and copper of 0.6% maximum
in it. Common type of carbon steel used in industry is medium carbon steel with carbon content
of 0.30-0.59%. Below are the justifications to use carbon steel in our production plant:

• Low cost
Carbon steel is preferred to be used in most chemical plants as it has low cost according
to current market price. [9]

• Wear resistance
Carbon steel has better wear resistance especially for medium carbon steel. It can last
long for construction purpose in industries. This is will ensure that the equipment
utilizing medium carbon steel doesn’t have to be replaced often. [9]

iii) Titanium
Titanium metal has a composition of 6% aluminium, 4% vanadium, 0.25% iron, 0.20%
oxygen and the remaining are titanium. Titanium is mostly available as titanium oxide, TiO2.
Since our production plant produces chlorine thus it advisable to use titanium metal in our plant.
Below are the justifications on the usage of titanium metal in our production plant:

• Resistant to chemicals
Titanium metal has high resistance towards chemical attack. This is will cause no
corrosion on the equipment or will take longer time to corrode compared to other
materials. [10]

• Light weight
It is tough but light weight compared to other materials. This makes it easier for welding,
fixing and maintenance purpose of equipment in the production plant. [10]

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 1.4 Justification of Equipment
1.4.1 Reaction Equipments

Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure(atm)

Stainless 60 1 Helps to precipitate Continuous Liquid

Steel any ions
R-101 Brine
Reactor

Justification:

Brine reactor is used in this production of sodium hypochlorite to precipitate calcium and magnesium ions before it goes
into the clarifier. It is specifically meant for brine solution only. Sodium hydroxide and sodium carbonate as used as
chemical reagents in this reactor.

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 Operating Conditions
Code Equipment Material of Construction Purpose/Usage Continuous/Batch Pha
Temp (oC) Pressure (atm)

Membrane:
perfluorinated sulfonate

Anode: Titanium coated To generate chlorine

with ruthenium dioxide 90 1 gas and 35wt% Continuous Liquids, Gas
(RuO2) sodium hydroxide
from sea water.
Cathode: Nickel based

Structure: stainless steel

Justification:

Membrane The electrolyser is one of the most important units as it generates the raw materials for the production of sodium hypochlorite
EZ-
electrolyser (chlorine gas and sodium hydroxide).After the seawater has undergo several purification treatment, the purified seawater with
201
26wt% NaCl is fed into the anode compartment of the electrolyser at 60℃ and the DC current is passed into the electrolyser during
the electrolysis. The chloride ions are oxidised to chlorine gas at the anode compartment while demineralized water is added to the
cathode compartment and water is reduced to hydrogen gas and hydroxide ions. The chemical reactions are;
Anode reaction : 2(𝑁𝑎+ (𝑎𝑞) + 𝐶𝑙−(𝑎𝑞))→ 2𝑁𝑎+(𝑎𝑞) + 𝐶𝑙2(𝑎𝑞) +2𝑒−
Cathode reaction : 2𝐻2𝑂 (𝑙)+2𝑒−→2𝑂𝐻−(𝑎𝑞) + 𝐻2(𝑔)
Overall reaction : 2𝑁𝑎𝐶𝑙(𝑎𝑞) + 2𝐻2𝑂(𝑙)→ 2𝑁𝑎𝑂𝐻(𝑎𝑞)+ 𝐻2(𝑔) + 𝐶𝑙2(𝑔)

12
From the overall reactions, chlorine gas and sodium hydroxide solution with the concentration of 30wt% to 33wt%.

The type of electrolyzer chosen is membrane electrolyzer. This is because membrane is a more environmental-friendly alternative
than mercury and diaphragm membrane, besides other advantages such as higher efficiency and less electricity
consumption.Specifically,the ion-conducting membrane used is perfluorinated sulfonate).This type of membrane is chosen because
it is chemically stable with higher selectivity. Electrolysis using perfluorinated ion exchange membrane is the most energy saving
process for chlor-alkali industry.[11]

13
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp (oC)
(atm)

To react the
Plastics /PVC- chlorine gas with
27.78 1 sodium hydroxide Continuous Liquids, Gas
lined FRP
to produce sodium
hypochlorite
Packed bed Justification:
column The packed bed column (reaction vessel) is basically the heart of this plant as this is where the main product,
R-301 (reaction
sodium hypochlorite is produced. The reaction producing the chemical is;
vessel)
Cl2 + 2 NaOH = NaOCl + NaCl + H2O
As such, the reaction happens simply by mixing both reactants together. Packed bed column is used as the
packings inside the reactor can increase the contact area between the raw materials, hence increasing the
production rate of the product. The packings inside the reactor could be of any random packing material.

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 1.4.2 Mass Transfer Equipments

Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure (atm)

Chelating resin is
used to absorb ions
Tower:
such as calcium and
Stainless Steel
PB-101/ Chelating 60 1 magnesium from Continuous Liquid
102 Resin Resin: seawater passing
Tower Sodium through it
Polystyrene
Sulphonate

Justification:

Chelating resin tower is used in this process to further purify the seawater input before it enters the electrolyser. The
input to the electrolyser must solely be sodium chloride. With the help of chelating resin, magnesium and calcium
chloride are removed to ensure that only sodium chloride enters electrolyser.

15
 Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure (atm)

Membrane: To separate
Polymer minerals and
60 1 Continuous Liquid
product water with
Electrodes:
Electrodialysis the aid of direct
Titanium
ED -101 Membrane current (DC)
plated with
applied on the
Platinum
electrodes

Justification:

Water and sodium chloride enters electrodialysis membrane and it separates the ions when it accumulates on the
electrodes. It consists of large number of cation and anion exchange membranes which are separated by dilute flow
spacers. This equipment can reach demineralized water recovery of about 95% or more. Hydroxyl ions and hydrogen
gas are formed at the cathode whereas chlorine gas may be formed at the anode. In order to achieve 28 wt% of sodium
chloride solution, the water must be removed by using membrane electrodialysis technology. Formation of chlorine
gas itself requires high resistant material to be used to design the electrodialysis equipment to prevent corrosion. [1]

16
Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure(atm)

CaCO3 and
Mg(OH)2 is filtered
with the aid of leaf
60 1 filter and its Continuous Liquid

F-101 Pressure Carbon steel maximum operating

Leaf Filter pressure which is

2.42kg/cm2

Justification:

The pressure of leaf filter is functions to filter out remaining unwanted compounds such as calcium carbonate and
magnesium hydroxide. This filter aid starts by forming layer cake which filters out those compounds. Its internal
condition has a maximum pressure of 2.42 atm.

17
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp (oC)
(atm)

To absorb the
moisture from
Titanium 30 1 wet chlorine gas Continuous Liquids, Gas
by using
concentrated
Packed bed sulphuric acid
PC- column/ Justification:
201 dryer The chlorine gas produced from the dechlorination tower will still have some fraction of water vapour
due to the reaction of hypochlorous acid and hydrochloric acid. The moisture needs to be removed so that
the concentration of sodium hypochlorite produced will not be altered(less than 12.5wt%).In the
dryer,98wt% of sulphuric acid will be contacted with the chlorine gas to absorb the water vapour to a
final moisture content of max. 12.5 w/w ppm[12].

18
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp ( C)o
(atm)

To separate
Titanium 90 0.31 to 0.33 chlorine gas from Continuous Liquids, Gas
depleted sea water
Justification:
Dechlorination tower is a separation unit to remove chlorine gas from the depleted brine solution. After the
Dechlorination electrolysis process, some of the brine leaving the electrolyzer will contain some available/free Cl2, which are chlorine
R-201 tower (Packed molecules physically absorbed in brine and in the form of hypochlorous ions. This waste stream cannot simply be
bed column) discharged to the water body as the chlorine content might be harmful to the aquatic organism. Hence, 98wt% of HCl
will be fed into the tower to facilitate the conversion of hypochlorous acid (the solution produced when chlorine gas
dissolved in the water) into moist chlorine gas. The chemical reaction for this process is;
𝐻𝑂𝐶𝑙 + 𝐻𝐶𝑙 → 𝐶𝑙2 + 𝐻2 𝑂

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 1.4.3 Heat Transfer Equipments

Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure (atm)

To control the
temperature of
E-101 Heat Stainless 60 1 Continuous Liquid
seawater
Exchanger steel

Justification:

Heat exchanger at this point helps to control temperature of seawater before it enters the chelating resin tower. Heat
exchanger works with the aid of steam input.

20
 Material of Operating Conditions Continuous/
Code Equipment Purpose/Usage Phase
Construction Temp (oC) Pressure (atm) Batch

To cool down the

Titanium 30 1
sodium hypochlorite
Continuous Liquid
Heat Exchanger solution to below
30˚C
Justification:
E-302
This heat exchanger is used to cool down the sodium hypochlorite solution to below 30˚C as above this
temperature, the chemical will become unstable and will undergo rapid decomposition in the form of chlorate.
Plate heat exchanger is used as the large surface area of the plates will account to higher heat transfer rate.

21
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp (oC)
(atm)

To cool down the

50 to caustic solution
Heat Stainless Steel 1 (14wt% -16wt %) Continuous Liquids
15.56
Exchanger
from 50℃ to
15.56℃.
Justification:
E-301 This heat exchanger is used to cool down the diluted sodium hydroxide solution so that it could be at the
optimum operating condition before being fed into the reaction vessel to react with chlorine gas. If the
temperature is too high, the subsequent reaction will impose a problem in terms of high production of by-
products from decomposition of sodium hypochlorite. Plate heat exchanger is used as the large surface
area of the plates will account to higher heat transfer rate.

22
 Operating Conditions
Material of Continuous
Code Equipment Purpose/Usage Phase
Construction o
Temp ( C) Pressure (atm) /Batch

70 to 20 1
Stainless Steel To cool down the
Heat Exchanger Dry chlorine from Continuous Gas
70℃ to 20℃.

Justification:
E-201 This heat exchanger is used to cool down the dry chlorine gas before being fed into the reaction vessel. This is done
to condensate the remaining amount of water vapour that has not been removed in the dryer besides providing the
optimum operating temperature for the reaction with sodium hydroxide solution inside the reactor. Plate heat
exchanger is used as the large surface area of the plates will account to higher heat transfer rate.

23
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp (oC)
(atm)

To concentrate the
Stainless Steel
caustic soda Continuous
90 1 Liquid
solution from 30-
35wt% to 50wt%
EV-201 Falling Film
Justification:
Evaporator
The evaporator is used to concentrate the caustic soda solution from the concentration produced from the
electrolyzer (30-35wt %) to the commercial concentration of sodium hydroxide (50wt %) before storing it in
storage tank. Falling film evaporator is used as it can handle heat sensitive materials, have shorter residence time
and high heat transfer coefficient, which means the concentration of caustic soda could be done rapidly.

24
 1.4.4 Auxiliary Equipment

Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure(atm)

Pre-coating filter
(safety filter) is used
to stop the cellulose
Filter: 60 4 to 5 fibers from being Continuous Liquid
Stainless released by pressure
F-102 Pre- (max)
Steel leaf filter and saves
coating
Filter Pre-coat: it from corrosion

Cellulose

Justification:

Pre-coat used is cellulose. It forms a slurry to pass through with seawater in pressure leaf filter until it helps remove the
unwanted ions. It forms like a filter cake in the pressure leaf filter. This filter stops the cellulose from being released by
leaf filter. Cellulose acts as filter aid inside pressure leaf filter which replace the torn part of leaf during filtration.

25
 Operating Conditions
Material of
Code Equipment Temp Pressure Purpose/Usage Continuous/Batch Phase
Construction
(oC) (atm)

Stainless steel
(high
temperature) To dilute the
25 1 caustic soda Continuous Liquids
Carbon steel
solution
(low
Dilution temperature)
T-301 tank
Justification:
The caustic soda produced by the membrane electrolyzer from the electrolysis process has a concentration
of 30wt% to 33wt%. The solution needs to be diluted as the concentration of caustic soda cannot be more
than 20wt % as it increases the possibility of precipitation of sodium chloride salt. Hence, the dilution tank
will dilute the caustic soda solution to 14wt% to 16wt% before reacting it with chlorine gas in the sodium
hypochlorite reactor.

26
 Operating Conditions
Material of
Code Equipment Pressure Purpose/Usage Continuous/Batch Phase
Construction Temp (oC)
(atm)

To receive the
hypochlorite
solution from
packed bed column
PVC-lined FRP 26.67 1 atm and recycle certain Continuous Liquids
fraction of solution
Buffer tank into the column
T-302
while certain
fraction of solution
become product.
Justification:
The buffer tank is used to produce a recycle stream back to the inlet of reaction vessel. The recycle stream is
important to increase the purity of sodium hypochlorite produced.

27
 Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Code Temperature(⸰C) Pressure(atm)

Self-cleaning fine
mesh strainer needed
25 1
to remove large solid
ST- Strainer Stainless particle inside the Continuous Liquid
101 steel seawater

Justification:

Strainer works as fine cleaning of large particles before seawater enters brine reactor. It aids to remove sands and
unwanted large particles to prevent them from damaging the following equipment in the chemical plant. Since it is the
first equipment for seawater to be pumped into, it needs to withstand pressure difference and be corrosion resistant.

28
Code Equipment Material of Operating Condition Purpose/ Usage Continuous/ Batch Phase
Construction
Temperature(⸰C) Pressure(atm)

Calcium carbonate
and magnesium
hydroxide substance
Stainless 60 1 are settled as sludge Continuous Liquid
Steel by sedimentation
C-101 Clarifier
since it wasn’t
removed in the
beginning

Justification:

Clarifier works to settle down excessive sludge such as calcium carbonate and magnesium hydroxide that couldn’t be
removed by the strainer at the beginning of the process. It works on the principle of gravity settling which leads to
heavier suspended solids settle below. The settled solids are swept to the centre of the tank.

29
Table 1: No of Equipment used

Type of Equipment No of Units

Strainer 1

Brine Reactor 1

Clarifier 1

Pressure Leaf Filter 1

Pre-coat Filter 1

Chelating Resin Tower 2

Electrodialysis Membrane 1

Electrolyzer 1

Chlorination tower 1

Packed column (includes de-chlorination 2

tower)

Dryer 1

Heat Exchangers 5

Falling Film Evaporator 1

Dilution Tank 1

Buffer Tank 1
Pumps are used in chemical industries to change the parameter of variable. It is also
utilized to recover back the head-loss from one equipment to another. For the production of
sodium hypochlorite through electrolysis of seawater, pumps aren’t considered for mass and
energy balance as it is only used to maintain the flow of the production process not to change the
parameter of the variable in the process. Therefore, usage of pumps isn’t shown in this report.

30
1.5 Economic Potential

Economic potential of a project can be used as an indicator to predict the possible revenue and
profit either in short or long-term period. Plant design and economic evaluations can be useful
especially in the research and development stages of a new chemical engineering plant. This is
because it can be used as a useful guidance as to the economic potential of a project. Besides that,
these studies can identify those parts of the process where major cost savings can be expected
(such as recycle streams), and thus where research and development efforts might be focused.
Moreover, economic potential evaluation study also determines whether the project proposed
is suitable to be carried out without excessive loss of revenue. There are two major determinants
of the potential rate at which an economy can grow in a long run. One of it is the rate of decrease
in key inputs such as capital, while the another is the rise in the productivity such as production of
sodium hypochlorite.
In our proposed production plant, an increase in the conversion of reaction can help to
minimize the raw material capital cost thus increase the economic potential of the whole
production for the fixed production capacity of sodium hypochlorite production of 40000
tonnes/year.

31
1.5.1 Economic Potential Without Recycle Stream

Calculation of economic potential (EP) is important for a first draft to observe how well
our chemical plant can make profit based on feed, product and by-product capacity and price. EP
can be calculated as follows:

Economic Potential (EP) = Product value + By-product value – Raw material value

Our plant production runs for a total of 300 days per year whereby 65 days is given aside
for repair, maintenance and shutdown purposes. [13] One day covers around 24 hours in a usual
production plant.

The table below shows the price of our raw materials and product:

Table 2: Price of raw material, product and by-products

Material Price (USD) per ton Price (RM) per ton

Seawater 0.00 0.00

Sodium hypochlorite 189.13 800

Chlorine gas 331 1400

Sodium hydroxide 284 1200

Sodium chloride 71.20 301.18

Hydrogen 2700 11421

** 1 USD= RM 4.23 (2nd November 2017)

32
Table 3: Cost of product and reactant per annum

Mass Flow Rate Cost (RM/hr plant

Component Price (RM/ton) Cost of Production per Annum (RM/yr)
(kg/hr) operation)
Seawater 0 90000 0 0
Sodium
800 583.761 467.18 3363696
hypochlorite
Chlorine gas 1400 10.3633 14.51 104472
Sodium hydroxide 1200 41.004 49.2 354240
Sodium chloride 301.18 677.295 203.99 1468728
Hydrogen 11421 16.1042 183.93 1324296

The following equation is used to calculate economic potential of the production plant:

Economic Potential (EP) = (Product value + By-product value) – Raw material value

Economic Potential (EP)= (3363696+104472+354240+1468728+1324296) – 0.00

= RM 6,615,432/ year

33
 Table 4: Economic potential of Sodium Hypochlorite production

Conversion Mass Flow Rate (ton/hr) Economic Potential

(%)
Seawater Sodium Hypochlorite RM/hr RM/Year
10 97.32841719 9.732841719 7786.27 56061168.30
20 97.32841719 19.46568344 15572.55 112122336.60
30 97.32841719 29.19852516 23358.82 168183504.90
40 97.32841719 38.93136688 31145.09 224244673.20
50 97.32841719 48.66420859 38931.37 280305841.50
60 97.32841719 58.39705031 46717.64 336367009.80
70 97.32841719 68.12989203 54503.91 392428178.11
80 97.32841719 77.86273375 62290.19 448489346.41
90 97.32841719 87.59557547 70076.46 504550514.71
100 97.32841719 97.32841719 77862.73 560611683.01

34
 Economic potential RM/year
605000000.00

Economic potential, RM/year

505000000.00

405000000.00

305000000.00

205000000.00

105000000.00

5000000.00
0 20 40 60 80 100 120
Conversion, %

Figure 1: Graph of seawater conversion against Economic Potential

The figure above shows that the relationship between the conversion of seawater and the economic potential (RM/Year) that is
is directly proportional to each other. The economic potential increases as the conversion increases. As it is directly proportional, the
amount of seawater reacted to produce sodium hypochlorite is directly proportional to the per annum profitability. Note that our
production plant operation has no recycle unit. This is because in the second reaction in packed column reactor (de-chlorination tower),
100% of sodium hydroxide and chlorine are converted into our desired product.

35
1.6 Separation Operations used in Sodium Hypochlorite Plant

Table 5: Physical Separation

Type of Separation Operation Physical separation

Equipment Self-cleaning mesh strainer

Operating Conditions Temperature(˚C) 25

Pressure(atm) 1

Purpose:

To remove the large solid particle inside the seawater.

Justification:

Before the sea water is fed into the electrolyzer, sea water must go through to primary

and secondary brine purification to remove any unwanted impurities such as magnesium

ions, calcium ions and any large solid particle inside the seawater. Hence, strainer is the

first separation unit for the seawater to pass through for removal of large solid particles,

as the presence of those particles will result in damages on the consequent unit operations.

36
Table 6: Physical Separation
Type of Separation Operation Physical separation
Equipment Clarifier
Operating Conditions Temperature(˚C) 60
Pressure(atm) 1
Purpose:
To remove calcium carbonate and magnesium hydroxide in the form of sludge by

means of gravity settling. The inlet is seawater with sodium chloride, calcium

carbonate (solid), magnesium hydroxide (solid) and some magnesium and some

trace amount of calcium chloride.

Justification:

This is a physical treatment process which is used to remove calcium carbonate and

magnesium hydroxide which is being precipitated in the brine reactor (continuous

stirred tank reactor).

37
Table 7: Separation by Filtration
Type of Separation Operation Filtration
Equipment Pressure Leaf Filter
Operating Conditions Temperature(˚C) 60
Pressure(atm) 2.4 (max)
Purpose:
To remove the remaining calcium carbonate and magnesium hydroxide that have not been

completely removed yet during sedimentation process in the clarifier.

Justification:

Filtration is the separation of solids from liquids by forcing the liquid to flow through a

porous medium and depositing the solids on the medium. The pre-coat type leaf filter is used

to filter out the remaining calcium carbonate and magnesium hydroxide to ensure complete

removal of them in the brine solution. The pre-coat used in this filter is cellulose to improve

filtration rate and product clarity. Pressure leaf filter is commonly used in chlor-alkali

industries.

38
Table 8: Separation by Filtration
Type of Separation Operation Filtration
Equipment Safety Filter
Temperature(˚C) 60
Operating Conditions Pressure(atm) 1
Purpose:
To stop the cellulose fibers released by pressure leaf filter by using a pre-coating

filter. This is done when the filter reaches its maximum operating pressure which is

2.4 atm and needs to be cleaned.

Justification:

When the filter reaches its maximum operating pressure (2.4 atm), the filter is cleaned

and a pre-coating filter (safety filter) is used to stop the cellulose fibers released by

pressure leaf filter. Filter cleaning is important as during pre-coat, the pre-coat itself

(diatomaceous earth or perlite) becomes the major resistance to flow. Hence, as cycle

after cycle is run on a filter, the solid contaminants being removed, and/or the filter

aid may begin to accumulate in and on the leaf, restricting the filter cloth or the nozzle

resulting in reduced flow rate and shorter filter cycles.

39
Table 9: Separation by Absorption
Type of Separation Operation Absorption Process
Equipment Chelating Resin Tower
Operating Conditions Temperature(˚C) 60
Pressure(atm) 1
Purpose:
To absorb magnesium and calcium ions by using resin (sodium polystyrene sulfonate). The

concentration of those ions should be below 20ppb.

Justification:

The main advantage of membrane cell process is the production of high purity caustic soda.

But the disadvantage is the requirement of high quality brine. The creation of purified brine

to feed into the electrolytic cell is a multi-step process. After several filtration processes, the

NaCl will still contain trace amounts of Mg2+ and Ca2+. If these contaminants were to make

it to the electrolytic cell, then the membrane and related anode / cathode could have fouled

thus reducing their lifespan and driving up electrical costs. The ion-exchange resin towers

which are placed in series will be used to absorb the remaining ions contained in the brine.

The utilized resin (sodium polystyrene sulfonate) has a very high selectivity for metal ions

so that the content of calcium and magnesium ions can be reduced to below 20ppb.

40
Table 10: Separation by Absorption
Type of Separation Operation Absorption Process
Equipment De-chlorination Tower
Operating Conditions Temperature(˚C) 80-90
Pressure(atm) 1
Purpose:
To remove the free chlorine content in the seawater by contact with 98wt% hydrochloric
acid.
Justification:

Any plant which uses gaseous or liquid chlorine must comply with strict environmental

regulations. The waste gas de-chlorination unit is an essential feature to ensure that chlorine

cannot escape into the environment under any circumstances and can be reuse back for the

production of desired end product. The brine leaving the electrolyzer will contain some

available/free Cl2, which are chlorine molecules physically absorbed in brine and in the form

of hypochlorous ions. In the brine tower, 98wt% of hydrochloric acid is being fed so that the

hypochlorous ions are converted to Cl2.The chemical reaction is:

𝐻𝑂𝐶𝑙 + 𝐻𝐶𝑙 → 𝐶𝑙2 + 𝐻2 𝑂

The excess amount of HCl will shift the reaction to the right, producing more Cl2.The Cl2

gas will join the rest produced from the electrolyzer to be dried before reacting with sodium

hydroxide for production of sodium hypochlorite.

41
Chapter 2: Mass Balance of the Process Plant

The law of conservation of mass stated that the matter can be changed from one form to
another, mixtures can be made, or separated, and pure substances can be decomposed, but the total
amount of mass remain constant. To be put into simpler terms, law of conservation states that mass
can neither be created nor destroyed. The mass balance for any system can be calculated using the
following equation:

𝐼𝑛𝑝𝑢𝑡 + 𝐺𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 − 𝑂𝑢𝑡𝑝𝑢𝑡 − 𝐶𝑜𝑛𝑠𝑢𝑚𝑝𝑡𝑖𝑜𝑛 = 𝐴𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

However, for this system accumulation term is accumulated as the system operates at continuous
mode. It is assumed that the system operates at steady state, so there is no accumulation in the
reactor, no generation of reactants and no consumption for the products. Thus, the mass balance
will be simplified into the equation:

𝐼𝑛𝑝𝑢𝑡 = 𝑂𝑢𝑡𝑝𝑢𝑡

42
2.1 Mass Balance of Each Unit

ST-101 Strainer

43
E-101 Heat Exchanger 1

44
R-101 Brine Reactor

45
C-101 Clarifier

46
F-101 Pressure Leaf Filter

47
F-102 Pre-coating Filter

F-102 Pre-coating Filter

48
PB-101/102 Chelating Resin Tower

49
ED-101 Electrodialysis Membrane

50
EZ-102 Electrolyzer

51
R-201 Dechlorination Tower

52
53
PC-201 Packed column for drying

54
E-201 Heat Exchanger 2

55
56
EV-201 Falling Film Evaporator

57
E-301 Heat Exchanger 3

58
59
T-301 Dilution Tank

60
E-302 Heat Exchanger 4

61
R-301 Chlorination Tower

62
T-302 Buffer Tank

63
E-303 Heat Exchanger 5

64
2.2 Overall Mass Balance

65
Justification for the output from mass balance

A) R-101 Brine reactor reaction (Precipitation process)

First reaction: precipitation of calcium carbonate (sodium carbonate as precipitant)
𝐶𝑎𝐶𝑙2 (𝑎𝑞) + 𝑁𝑎2 𝐶𝑂3 (𝑎𝑞) → 𝐶𝑎𝐶𝑂3 (𝑠) + 2𝑁𝑎𝐶𝑙(𝑎𝑞)
The conversion of the reaction is assumed to be 70%.
By doing the weight basis and mole basis,
Chemical compounds Stoichiometry (mole Molecular weight Weight basis
basis) (g/mol) (Calcium chloride as
basis)
𝐶𝑎𝐶𝑙2 (𝑎𝑞) 1 110.98 1
𝑁𝑎2 𝐶𝑂3 (𝑎𝑞) 1 105.9888 0.955
𝐶𝑎𝐶𝑂3 (𝑠) 1 100.0869 0.902
𝑁𝑎𝐶𝑙(𝑎𝑞) 2 58.44 1.053

Based on the weight basis, 1 kg of calcium chloride react with 0.955kg of sodium carbonate to produce 0.902kg of calcium carbonate and
1.053kg of sodium chloride.

Based on the mole basis, 1 mole of calcium chloride react with 1 mole of sodium carbonate to produce 1 mole of calcium carbonate (solid) and 2
mole of sodium chloride.

Composition of 𝐶𝑎𝐶𝑙2 in the feed brine

Molar flow rate of CaCl2 is 16.6324kmol/hr in the feed brine.

66
Calcium chloride has to be precipitated inside the brine reactor hence it can be removed easily.

In order to remove 16.6324kmol/hr of calcium chloride from the brine reactor, the molar flow rate of sodium carbonate supplied to the
reactor is

0.3243𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙2 1 𝑚𝑜𝑙𝑒 𝑁𝑎2 𝐶𝑂3 0.3243𝑘𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3

𝑥 =
ℎ𝑟 𝑚𝑜𝑙𝑒 𝐶𝑎𝐶𝑙2 ℎ𝑟

Due to the reaction is 70% conversion of the reaction, the output brine from the brine reactor will have 30% of sodium carbonate remaining.

0.3243𝑘𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3 0.09729𝑘𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3

𝑥(1 − 0.7 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛) =
ℎ𝑟 ℎ𝑟

Molar flow rate of calcium carbonate in the output brine is

0.3243𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙2 1 𝑚𝑜𝑙𝑒 𝐶𝑎𝐶𝑂3

𝑥 𝑥0.7 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
ℎ𝑟 𝑚𝑜𝑙𝑒 𝐶𝑎𝐶𝑙2

0.22701𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3
=
ℎ𝑟

Molar flow rate of the sodium chloride

0.3243𝑘𝑚𝑜𝑙 𝐶𝑎𝐶𝑙2 2 𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙
𝑥 𝑥 0.7 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
ℎ𝑟 𝑚𝑜𝑙𝑒 𝐶𝑎𝐶𝑙2
0.45402 𝑘𝑚𝑜𝑙𝑁𝑎𝐶𝑙
=
ℎ𝑟
67
Second reaction: precipitation of magnesium chloride (sodium hydroxide as precipitant)
𝑀𝑔𝐶𝑙2 (𝑎𝑞) + 2𝑁𝑎𝑂𝐻 (𝑎𝑞) → 𝑀𝑔(𝑂𝐻)2 (𝑠) + 2𝑁𝑎𝐶𝑙(𝑎𝑞)
In this process 32wt% of sodium hydroxide (precipitatant) is used to precipitate the magnesium chloride.
Assumption: 70% of conversion rate of the reaction
Chemical compounds Stoichiometry Molecular weight Ratio of molecular
(g/mol) weight
(Magnesium chloride as
basis)
𝑀𝑔𝐶𝑙2 (𝑎𝑞) 1 95.211 1
𝑁𝑎𝑂𝐻(𝑎𝑞) 2 39.997 0.8402
𝑀𝑔(𝑂𝐻)2 (𝑠) 1 58.3197 0.6125
𝑁𝑎𝐶𝑙(𝑎𝑞) 2 58.44 1.2276

Based on the weight basis, 1 kg of magnesium chloride react with 0.8402kg of sodium hydroxide to produce 0.6125kg of magnesium hydroxide
and 1.2276kg of sodium chloride.
Based on the mole basis, 1 mole of magnesium chloride react with 1mole of sodium hydroxide to produce 1 mole of magnesium hydroxide
(solid) and 2 mole of sodium chloride.
Molar flow rate of 𝑀𝑔𝐶𝑙2 in the feed brine is 1.2214kmole/hr
To remove 1.2214kmole/hr of magnesium chloride from the brine reactor, the amount of sodium hydroxide required is
1.2214𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2 2𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻 2.4428𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻
𝑥 =
ℎ𝑟 𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2 ℎ𝑟

68
Molar flow rate of sodium hydroxide remaining in the output brine after precipitation
2.4428𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻 0.7328𝑘𝑚𝑜𝑙𝑒 NaOH
𝑥(1 − 0.7 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛) =
ℎ𝑟 ℎ𝑟

Molar flow rate of solid magnesium hydroxide in the output brine.

1.2214𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2 1 𝑚𝑜𝑙𝑒𝑀𝑔(𝑂𝐻)2
𝑥 𝑥(0.7 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
ℎ𝑟 𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2
0.85498𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝑂𝐻
=
ℎ𝑟
Molar flow rate of solid magnesium chloride in the output brine.
1.2214𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2
𝑥 (1 − 0.7 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
ℎ𝑟
0.36642𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2
=
ℎ𝑟

Molar flow rate of sodium chloride is

1.2214𝑘𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2 2 𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙
𝑥 𝑥(0.7 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑐𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛)
ℎ𝑟 𝑚𝑜𝑙𝑒 𝑀𝑔𝐶𝑙2
1.70996 𝑁𝑎𝐶𝑙
=
ℎ𝑟
Total molar flow rate of sodium chloride in the output brine is
1.70996 𝑘𝑚𝑜𝑙 𝑁𝑎𝐶𝑙 0.45402 𝑘𝑚𝑜𝑙𝑁𝑎𝐶𝑙 16.6324 𝑘𝑚𝑜𝑙𝑁𝑎𝐶𝑙 18.79638𝑘𝑚𝑜𝑙𝑁𝑎𝐶𝑙
+ + =
ℎ𝑟 ℎ𝑟 ℎ𝑟 ℎ𝑟
69
B) Separation efficiency of C-101 clarifier by sedimentation
The separation efficiency is assumed as 70%, 70% of solid magnesium hydroxide and calcium carbonate with be removed together as sludge.
C) Separation efficiency of F-101 pressure leaf filter.
The solid magnesium hydroxide and calcium carbonate will be completely removed by pressure leaf filter. Cellulose is used as precoat of the
filter to increase the separation efficiency of pressure leaf filter.
C) F-102 Precoating filter
Precoating filter is used to remove the cellulose (precoat on the pressure leaf filter).

D) PB-101/ 102 Chelating resin tower

Sodium polystyrene sulphonate (resin) will be used to remove unwanted ions-Mg2+ and Ca2+ ions in the brine.
At this stage all the unwanted magnesium and calcium ions are assumed to be removed completely from the brine.

70
E) ED-101 Membrane electrodialysis

Figure 2:Structure of membrane electrodialysis [14]

Membrane electrodialysis is used to concentrate the sodium chloride salt content inside the brine to achieve operating feed condition of salt solution
of electrolyser [15] (about 28wt% of sodium chloride). Based on the calculation, 2667kg/hr of water will be supplied to the membrane and we
assume only sodium chloride salt can pass through the membrane to the water while remaining desalted solution will be removed.

71
F) EZ-102 Membrane electrolyzer

Figure 3:Membrane Electrolyser[16]

The efficiency of membrane is assumed to be 90% based on the reference [17], 90% efficiency of membrane indicates only 90% of sodium ions
is able to pass through the membrane from the anode to the cathode to combine with the hydroxide ions at cathode to form 32wt% sodium
hydroxide.
2𝑁𝑎𝐶𝑙(𝑎𝑞) + 2𝐻2 𝑂(𝑙) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻2 (𝑔) + 𝐶𝑙2 (𝑔)

72
Weight basis
Chemical compound Molecular weight Stoichiometry Ratio (weight basis)
𝑁𝑎𝐶𝑙(𝑎𝑞) 58.44 2/2=1 1
𝐻2 𝑂(𝑙) 18.01528 2/2=1 0.3083
𝑁𝑎𝑂𝐻(𝑎𝑞) 39.997 2/2=1 0.6844
𝐻2 (𝑔) 2.016 ½=0.5 0.0172
𝐶𝑙2 (𝑔) 70.9 ½=0.5 0.6066

Based on the mole basis, 1 mole of sodium chloride with 1 mole of water will able to produce 1 mole of sodium hydroxide, 0.5 mole of
hydrogen gas and 0.5 mole of chlorine gas.
Based on the weight basis, 1 kg of sodium chloride with 0.3083kg of water to produce 1.3686kg of magnesium hydroxide, 0.0172kg of hydrogen
gas and 1.2276kg of 0.6066kg of chlorine gas.
Flow rate of 𝑁𝑎𝐶𝑙2 in the feed brine before entering the electrolyzer
Mole flow rate=17.75155kmole/hr
Only 90% of sodium ions can pass through the membrane

Amount of sodium hydroxide produced

17.75155𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙 1 𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻 15.976395𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝑂𝐻
𝑥 𝑥90% 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 =
ℎ𝑟 1𝑚𝑜𝑙𝑒𝑁𝑎𝐶𝑙 ℎ𝑟

Amount of demineralized water required to supply hydroxide ions to combine with sodium ions to form sodium hydroxide.
17.75155𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙 1 𝑚𝑜𝑙𝑒𝐻2 𝑂 17.75155𝑘𝑚𝑜𝑙𝑒 𝐻2 𝑂
𝑥 =
ℎ𝑟 𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙2 ℎ𝑟

73
Since the membrane electrolyser produces 32wt% of sodium hydroxide[16] , the amount of deminerized water required to supply to cathode to
maintain the concentration of caustic soda is
639.024𝑘𝑔 𝑁𝑎𝑂𝐻
= 0.32
𝑥𝑘𝑔 𝐻2 𝑂 + 639.024𝑘𝑔 𝑁𝑎𝑂𝐻

639.024 − 0.32𝑥639.024
𝑥𝑘𝑔 𝐻2 𝑂 =
0.32

𝑥𝑘𝑔 𝐻2 𝑂 = 1357.926𝑘𝑔𝐻2 𝑂
Since only 90% of kg H2O will combine with sodium ions to produce sodium hydroxide,
The remaining amount of H2O,
17.75155kmole 𝐻2 𝑂 1.775144𝑘𝑚𝑜𝑙𝑒𝐻2 𝑂
𝑥 (1 − 0.9 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦) =
ℎ𝑟 ℎ𝑟

1.775144𝑘𝑚𝑜𝑙𝑒𝐻2 𝑂 18𝑘𝑔 31.952592𝑘𝑔𝐻2 0

𝑥 =
ℎ𝑟 𝑘𝑚𝑜𝑙𝑒 ℎ𝑟
The extra water need to add into the electrolyzer,
1357.926𝑘𝑔𝐻2 𝑂 31.952592𝑘𝑔𝐻2 0 1325.973408𝑘𝑔𝐻2 0
− =
ℎ𝑟 ℎ𝑟 ℎ𝑟
Total deminerized water needed to feed into electrolyzer
1325.973408𝑘𝑔 𝐻2 𝑂 319.52592𝑘𝑔 𝐻2 𝑂 1645.499328𝑘𝑔 𝐻2 𝑂
+ =
ℎ𝑟 ℎ𝑟 ℎ𝑟

74
Total hydrogen can be produced from membrane electrolyzer
17.75155𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙 0.5 𝑚𝑜𝑙𝑒𝐻2 7.988 𝐻2
𝑥 𝑥0.9 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 =
ℎ𝑟 𝑘𝑔𝑁𝑎𝐶𝑙 ℎ𝑟

Total chlorine can be produced from membrane electrolyzer

17.75155𝑘𝑚𝑜𝑙𝑒 𝑁𝑎𝐶𝑙 0.5 𝑚𝑜𝑙𝑒𝐶𝑙 7.9881975𝑘𝑚𝑜𝑙𝑒 𝐶𝑙2
𝑥 𝑥90% 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 =
ℎ𝑟 1𝑚𝑜𝑙𝑒𝑁𝑎𝐶𝑙 ℎ𝑟

Amount of chlorine gas will dissolve in the brine water is determined from solubility curve of chlorine gas into the water at 80℃. (The depleted
brine released from the electrolyser is at 80℃.

75
 Figure 4: solubility of chlorine gas into the water[18]

About 2.2g of chlorine will dissolve into 1 kg of water at 80℃.

Before the chlorine gas dissolve into the water, the volume of brine is 2667.6022kg/hr.
Amount of chlorine gas dissolve into the water is
2.2x10−3 𝑘𝑔 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒 2667.6022𝑘𝑔 𝑤𝑎𝑡𝑒𝑟
𝑥
𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 ℎ𝑟
= 5.8687𝑘𝑔 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑔𝑎𝑠 𝑤𝑖𝑙𝑙 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒 𝑖𝑛𝑡𝑜 𝑡ℎ𝑒 𝑤𝑎𝑡𝑒𝑟.

76
The amount of chlorine gas released from the electrolyser is
7.98819kmoleC𝑙2 kg 560.49kgC𝑙2
x70.9 − 5.8687kg =
hr 𝑘𝑚𝑜𝑙 ℎ𝑟

Formation of hypochlorous acid (Reversible reaction)

*5.8687kg of Cl2 will dissolve in the water in the form of hypochlorous acid and hydrochloric acid.

𝐶𝑙2 (𝑔) + 𝐻2 𝑂(𝑙) ⇌ HOCl(aq) + HCl(aq)

Chemical compound Molecular weight Stoichiometry Ratio

𝐶𝑙2 (𝑔) 70.9 1 1
𝐻2 𝑂(𝑙) 18.01528 1 0.2541
𝐻𝑂𝐶𝑙(𝑎𝑞) 52.46 1 0.7399
𝐻𝐶𝑙(𝑎𝑞) 36.46094 1 0.5143

Amount of water react with chlorine gas to produce hypochlorous acid and hydrochloric acid
5.8687𝑘𝑔𝐶𝑙2 0.2541𝑘𝑔𝐻2 𝑂 1.4912𝑘𝑔𝐻2 𝑂
𝑥 =
ℎ𝑟 𝑘𝑔𝐶𝑙2 ℎ𝑟
Amount of hypochlorous acid produced
5.8687𝑘𝑔𝐶𝑙2 0.7399𝑘𝑔𝐻𝑂𝐶𝑙 4.34225𝑘𝑔𝐻𝑂𝐶𝑙
𝑥 =
ℎ𝑟 𝑘𝑔𝐶𝑙2 ℎ𝑟
Amount of hydrochloric acid produced
5.8687𝑘𝑔𝐶𝑙2 0.5134𝑘𝑔𝐻𝐶𝑙 3.013𝑘𝑔𝐻𝐶𝑙
𝑥 =
ℎ𝑟 𝑘𝑔𝐶𝑙2 ℎ𝑟

77
Composition of brine released from the electrolyser
Mass flow rate of the water
2642.76kg/hr
Amount of hypochlorous acid
4.34225kgHOCl/hr
Amount of hydrochloric acid
3.031kgHCl/hr
In real case, there must be some sodium ions, chloride ions and other heavy metal ions in the brine released from electrolyser due to the efficiency
of membrane and resin tower are not 100%, and seawater has other ions but not only sodium ions, chloride ions, magnesium ions and calcium
ions.

Additional of hydrochloric acid to the R-201 dechlorination tower

Certain amount of HCl has to be added into the depleted brine to shift the equilibrium of reaction to regenerate chlorine gas. The pH of depleted
brine is maintained at around pH 2 to pH 4.[19]
In the absence of better information of density hydrochloric acid, hypochlorous acid in 80℃, the method used to determine the density of
aqueous solution by assuming volume additivity of the solution cannot be applied. Since the brine solution is mostly made up from water (about
99wt%), we will assume the density of brine is equal to density of pure water at 80℃.
By doing the interpolation from the data in Properties of water (saturated liquid) from “heat transfer tenth edition” written by J.P.Holman[20],
the density of brine solution at 80℃ is

78
 80 − 76.67 𝑥 − 973.7
=
82.22 − 76.67 970.2 − 973.7
= 971.6𝑘𝑔/𝑚3
Mole of HCL in the solution = 0.083kmole
Mole of HOCL in the solution=0.083kmole
The volume of the brine,
𝑀𝑎𝑠𝑠
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑟𝑖𝑛𝑒 = 𝐷𝑒𝑛𝑠𝑖𝑡𝑦

𝑚3
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑟𝑖𝑛𝑒 = 2753.86𝑘𝑔𝑥
971.6𝑘𝑔
= 2.834356𝑚3
= 2834.356𝑙𝑖𝑡𝑟𝑒

Molarity of HCL in the solution

83𝑚𝑜𝑙𝑒
= 0.029𝑀
2834.356𝑙

Molarity of HOCL in the solution

83𝑚𝑜𝑙𝑒
= 0.029𝑀
2834.356𝑙
In a 0.029 M solution of HCl, the H3O+ concentration will be 0.0292 M, so pH = -log(0.029) = 1.5376

79
Calculation of pH of HOCL
[𝐻 + ][𝐶𝑙𝑂− ]
𝐾𝑎 =
[𝐻𝐶𝑙𝑂]
Ka of hypochlorous acid is 3.58x10-8 [21]
𝑥2
3.58x10-8 = (0.029−𝑥)

[H+] =3.231x10-5
pH= -log[H+]
=-log[0.029+3.231x10-5]
=1.5341
The solution is very acidic and no additional of HCl is required based on the calculation.
This may due to we consider only several type of compound inside the seawater and the efficiency of resin tower is 100% to remove all unwanted
metallic ions from the seawater. We do not consider the presence of bicarbonates inside the seawater and this is the reasons why the brine is
alkaline.[14]
Hence, now we assume 10kg/hr of hydrochloric acid is enough to shift the balance of the reaction to the left to regenerate back the water and
chlorine gas.

Determination the amount of sodium hydroxide and chlorine gas required to produce 40000 tonnes of sodium hypochlorite.

𝐶𝑙2 (𝑔) + 2𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙)

80
Table 11: Molecular weight of the compounds
Chemical compounds Molecular weight Ratio of molecular weight (weight basis)
Chlorine 70.91 1.00
2 Caustic soda (sodium hydroxide) 80.00 1.13
Sodium hypochlorite 74.45 1.05

Based on the ratio of the molecular weight, 1 kg of chlorine will react with 1.13 kg of sodium hydroxide to produce 1.05 kg of sodium
hypochlorite.
Since the reaction is spontaneous, the conversion is assumed to be 100%.
Table 12: Mole basis (Assume if 1kg of chlorine is used)
Chemical compounds Mole Ratio of mole
Chlorine 1/70.91=0.014102kmole 1.000000
Caustic Soda (sodium hydroxide) 1.13/80.00=0.014125kmole 1.001631
Sodium hypochlorite 1.05/74.45=0.014103kmole 1.000071

wt% of available Cl2,

Available chlorine is the amount of chlorine equivalent in the oxidizing power
We want to produce 12.5 wt% of sodium hypochlorite,
12.5 𝑤𝑡% 𝑠𝑜𝑑𝑖𝑢𝑚 ℎ𝑦𝑝𝑜𝑐ℎ𝑙𝑜𝑟𝑖𝑡𝑒
= 11.904762 𝑤𝑡% 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒
1.05

81
For 1 ton of bleach solution production,
Pure chlorine gas required,
11.904762𝑤𝑡% 𝑎𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝐶𝑙2
𝑥1000𝑘𝑔 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
100
= 119.047620𝑘𝑔 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑔𝑎𝑠

Pure caustic soda required,

1.13𝑘𝑔 𝑁𝑎𝑂𝐻
119.047629𝑘𝑔 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑔𝑎𝑠𝑥 = 134.523821𝑘𝑔 𝑜𝑓 𝑐𝑎𝑢𝑠𝑡𝑖𝑐 𝑠𝑜𝑑𝑎
1.00𝑘𝑔 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑔𝑎𝑠
By referring Oxychem, table at page 8 and do the interpolation,

12.50 − 11.55 𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝐶𝑙2 𝑖𝑛 𝑔𝑝𝑙 𝑓𝑜𝑟 12.5% 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 129.6
=
12.60 − 11.55 143.4 − 129.6
Figure
Figure4.2:
5:Available
Availablechlorine
chlorineatatdifferent
differentpurity
purityofofbleach
bleach[1]
[1]
82
 142.085714𝑔 𝐶𝑙2
𝐴𝑣𝑎𝑖𝑙𝑎𝑏𝑙𝑒 𝐶𝑙2 𝑖𝑛 𝑔𝑝𝑙 𝑓𝑜𝑟 12.5% 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 =
𝑙
Since the bleach solution is stable at pH 12 until pH 13 (The NaOCl will not easily to decompose), the excess of NaOH is required to increase the
pH value of the solution. By referring the table in Oxychem handbook in page 16, 0.4g/l until 4g/l of excess NaOH is required to maintain the pH
of sodium hypochlorite at pH 12 until pH 13.

Figure 6:Sodium hypochlorite pH calculated from excess NaOH [1]

Based on the Oxychem book, table in page 5,

Specify gravity of bleach solution with 2g/l excess NaOH is calculated by doing the interpolation.

83
 Figure 7:Specific gravity of bleach solution[1]

142.085714 − 140 𝑆𝐺 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 − 1.183

=
150 − 140 1.195 − 1.183
2𝑔
𝑆𝐺 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑤𝑖𝑡ℎ 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻 = 1.185503Error! Bookmark not defined.
𝑙
Density of bleach solution with 2g/l of excess NaOH,
1𝑘𝑔
= 𝑆𝐺 𝑋 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑤𝑎𝑡𝑒𝑟 = 1.185503 𝑥 = 1.185503𝑘𝑔/𝑙
𝑙
Volume of 1000kg bleach solution

84
 𝑘𝑔
= 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ( ) 𝑥 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ (𝑙) = 1000𝑘𝑔 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑙
1.185503𝑘𝑔
= 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ (𝑙) = 1000𝑘𝑔
𝑙
= 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 1000𝑘𝑔 𝑏𝑙𝑒𝑎𝑐ℎ = 843.523804 𝑙
Weight of the 2g/l of excess NaOH in 1000kg of bleach solution
𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻 ( ) 𝑥 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑙)
𝑙
2𝑔 𝑘𝑔
= 𝑥 843.523804𝑙 𝑥 = 1.687048𝑘𝑔 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻
𝑙 1000𝑔

Weight of 50% caustic soda required,

100
(134.523821𝑘𝑔𝑁𝑎𝑂𝐻 + 1.687048𝑘𝑔 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻) 𝑥 = 272.421738 𝑘𝑔 𝑜𝑓 50% 𝑁𝑎𝑂𝐻
50
From oxychem handbook (pg17), SG of 50% membrane NaOH is 1.5298,

85
 Figure 8:specify gravity of caustic soda solution[1]

Hence density of 50% membrane caustic soda is

𝑘𝑔
𝑆𝐺 𝑜𝑓 50% 𝑁𝑎𝑂𝐻 𝑥 𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 ( )
𝑙
1𝑘𝑔
= 1.5298 𝑥
𝑙
= 1.5298𝑘𝑔/𝑙
Volume of the water required to dilute 50% caustic soda,
𝑀𝑎𝑠𝑠 𝑏𝑎𝑙𝑎𝑛𝑐𝑒 = 𝑖𝑛𝑝𝑢𝑡 = 𝑜𝑢𝑡𝑝𝑢𝑡
= 𝐵𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑘𝑔) − 𝐶𝑙2 (𝑘𝑔) − 50% 𝑐𝑎𝑢𝑠𝑡𝑖𝑐 𝑠𝑜𝑑𝑎 (𝑘𝑔) = 𝑤𝑎𝑡𝑒𝑟 (𝑘𝑔)

86
𝑤𝑎𝑡𝑒𝑟(𝑘𝑔) = 1000𝑘𝑔 𝑜𝑓 𝑏𝑙𝑒𝑎𝑐ℎ 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 – 119.047620𝑘𝑔 𝑜𝑓 𝑐ℎ𝑙𝑜𝑟𝑖𝑛𝑒 𝑔𝑎𝑠 − 272.421738 𝑘𝑔 𝑜𝑓 50% 𝑁𝑎𝑂𝐻
= 608.530642𝑘𝑔 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟

𝑃𝑢𝑟𝑖𝑡𝑦 𝑜𝑓 𝑐𝑎𝑢𝑠𝑡𝑖𝑐 𝑠𝑜𝑑𝑎 𝑎𝑓𝑡𝑒𝑟 𝑡ℎ𝑒 𝑑𝑖𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑤𝑡%,

(134.523821𝑘𝑔 𝑁𝑎𝑂𝐻 + 1.687048 𝑘𝑔 𝑜𝑓 𝑒𝑥𝑐𝑒𝑠𝑠 𝑁𝑎𝑂𝐻)
𝑥 100%
272.421738 𝑘𝑔 𝑜𝑓 50% 𝑁𝑎𝑂𝐻 + 608.530642 𝑘𝑔 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟
= 15.461774 𝑤𝑡% 𝑜𝑓 𝑑𝑖𝑙𝑢𝑡𝑒 𝑐𝑎𝑢𝑠𝑡𝑖𝑐 𝑠𝑜𝑑𝑎
Production capacity = 40000 tonnes per year
1 month will produce 3333.33 tonnes of 12.5wt% sodium hypochlorite
Raw material required for 1 month production
Chlorine gas
119.904762 Kg Cl2 / 1 ton of 12.5wt% sodium hypochlorite x 3333.33 tonnes of 12.5wt% sodium hypochlorite = 399682.1403 Kg Cl2
Chorine gas required per hour
399682.1403kg of Cl2/month x 1 month/ (30x24) hours =555.114kg of Cl2/hr
50% of sodium hydroxide required for 1 month production
272.421738 kg of 50% sodium hydroxide / ton of 12.5wt % sodium hypochlorite x 3333.33 tonnes =908071.5519kg of 50% sodium hydroxide
908071.5519kg of 50% sodium hydroxide/month x 1month/ (30x24) hours
=1261.21kg 50wt%NaOH/hr
Amount of water required for 1 month production
608.530642 kg of water/ ton of 12.5wt% sodium hypochlorite x 3333.33 tonnes= 2028433.445 kg of water.

87
2028433.445kg water/month x 1month/ (30 x 24) hours =2817.26874kg water/hours
Slightly adjust of the amount of raw material calculated on above is done to get the more accurate composition of product and production capacity
of our plant.
Main Product of our plant

Kg/hr tonnes/yr
Total products from the whole process
12.5wt% sodium hypochlorite 4629.665985 40000.31411
50wt% caustic soda 16.04802947 138.6549746

Chlorine gas 10.36335123 89.5393546

Figure 9:Main product of the plant

Composition of bleach solution product from the plant.

Composition Mass fraction (%)
Sodium hypochlorite 12.60913404
Sodium chloride 9.898949403
Sodium hydroxide 0.07924731
water 77.41266924
Figure 10: Composition of sodium hypochlorite produced from the plant

*The purity of sodium hypochlorite is usually produced at higher purity than labelled purity since sodium hypochlorite decomposes over time.

EV-201 Falling film evaporator

To concentrate the sodium hydroxide content in the solution from 32wt% to 50wt%.

88
Composition of the stream before entering the evaporator.
Mass flow rate of the water: 1357.9260kg/hr
Mass flow rate of sodium hydroxide: 639.024kg/hr
Amount of water that must be removed in the solution as steam
1357.9260𝑘𝑔 𝑤𝑎𝑡𝑒𝑟 639.024𝑘𝑔 𝑜𝑓 50𝑤𝑡% 𝑁𝑎𝑂𝐻
−
ℎ𝑟 ℎ𝑟
718.902𝑘𝑔𝐻2 𝑂
= (steam)
ℎ𝑟

Mass balance on the packed column (Drying of wet chlorine)

Wet Chlorine gas + 98wt% of H2SO4 =Dry chlorine gas + 70wt% of H2SO4
Water content inside the chlorine gas=kg/hr
After 98wt% sulphuric acid absorbs water, 98wt% sulphuric acid is diluted to 70wt% H2SO4
Initial concentration of sulphuric acid
𝑥𝑘𝑔𝐻2 𝑆𝑂4
= 0.98
𝑥𝑘𝑔𝐻2 𝑆𝑂4 + 𝑦𝑘𝑔𝐻2 𝑂
After sulphuric acid absorbs water
𝑥𝑘𝑔𝐻2 𝑆𝑂4
= 0.70
𝑦𝑘𝑔𝐻2 𝑂+23.5985

𝑥𝑘𝑔𝐻2 𝑆𝑂4 = 57.816𝑘𝑔 𝐻2 𝑆𝑂4

𝑦𝑘𝑔𝐻2 𝑂 = 1.1799𝑘𝑔𝐻2 𝑂

89
2.3 Stream Table

2.3.1 Stream 1-10

90
2.3.2 Stream 11-20

91
92
2.3.3 Stream 21-30

93
94
2.3.4 Stream 31-40

95
96
2.3.5 Stream 41-51

97
98
Chapter 3: Energy Balance of the Process Plant

Energy balance is referred to First Law of Thermodynamics which is based on law of

conservation of energy. According to First Law of Thermodynamics, the total energy of a
system is constant. Energy can be transformed from one form to another, but cannot be created
or destroyed.

The accumulation term is eliminated since the system is continuous and the equation becomes:

∆𝐇 + ∆𝐄𝐏 + ∆𝐄𝐤 = 𝐐 + 𝐖

In a chemical plant, ∆EP and ∆Ek is usually negligible compared to heat released or absorbed
by an unit and also the power of the equipment. Thus, the energy balance equation is further
simplified to:

∆𝐇 = 𝐐 + 𝐖

99
3.1 Energy Balance of Each Unit

ST-101 Strainer

100
E-101 Heat Exchanger 1

101
R-101 Brine Reactor

102
C-101 Clarifier

103
F-101 Pressure Leaf Filter

104
F-102 Pre-coating Filter

105
PB-101/102 Chelating Resin Tower

106
ED-101 Electrodialysis Membrane

107
EZ-102 Electrolyzer

108
R-201 Dechlorination Tower

109
110
PC-201 Packed column for drying

111
E-201 Heat Exchanger 2

112
113
EV-201 Falling Film Evaporator

114
E-301 Heat Exchanger 3

115
116
T-301 Dilution Tank

117
E-302 Heat Exchanger 4

118
R-301 Chlorination Tower

119
T-302 Buffer Tank

120
E-303 Heat Exchanger 5

121
3.2 Overall Energy Balance

122
Justification for Energy Balance
Heat capacity at constant pressure Range of (T = K; 0 °C = 273.1 K), unit (cal/(mol.k)
Heat capacity (All only applicable at low pressure)
Calcium chloride Solid phase 16.9+0.00386T (cal/(mol.K) 273-
[22] 1055K

Magnesium chloride Solid phase 17.3 + 273–991K

0.00377T(cal/(mol.K)[22]

Sodium chloride Solid phase 10.79 +0.00420T(cal/(mol.K) 273–

[22] 1074K
Magnesium hydroxide Solid phase 18.2(cal/(mol.K) [22] 292-323K

Calcium carbonate Solid phase 19.68 + 0.01189T − 273–

307600/T2(cal/(mol.K) [22] 1033K

Hydrogen Gas phase 28.84x10-3+0.00765x10- 0-1500℃

5
T+0.3288x10-8T2-0.8698x10-
12 3
T (kJ/(mol.K)[23]

Chlorine Gas phase 33.60x10-3+1.367x10-5T- 0-1200℃

1.607x10-8T2+6.473x10-
12 3
T (kJ/(mol.K)[23]
Hydrochloric acid Gas phase 29.13x10-3+0.1341x10-5T- 0-1200℃
0.9715x10-8T2-4.335x10-
12 3
T (kJ/(mol.K)[23]
Sodium hypochlorite Liquid phase 3.5kJ/kgK -
Sulphuric acid Liquid phase 139.1x10-3+15.59x10- 0-1500℃
5 3
T (kJ/(mol K)[23]
Hypochlorous acid Gas phase 30.54353 + 33.68965T 298-
−20.94787T2+5.421961T3 - 1400K
0.143287/T2(J/(mol.K)[8]

Cellulose Solid phase 1.4[13] -

Sodium hydroxide Liquid 88.34725 -2.495103T 596-
−3.013028T2+0.862607T3 2500K
+0.042216/T2(J/(mol.K)[24]

123
Standard heat of formation of the chemical compounds
Calcium chloride Solid phase -794.96kJ/mol[22]

Magnesium chloride Solid phase -641.8kJ/mol[22]

Sodium chloride Solid phase -411kJ/mol[22]

Magnesium hydroxide Solid phase -924.66kJ/mol[22]

Calcium carbonate Solid phase -1206.9kJ/mol[22]

Hydrogen Gas phase 0
Chlorine Gas phase 0
Hydrochloric acid Gas phase -92.31kJ/mol[23]
Sodium hypochlorite Aqueous phase -347.3kJ/mol
Sulphuric acid Liquid phase -811.32kJ/mol[23]
Hypochlorous acid Gas phase -74.48kJ/mol[1]
Cellulose Solid phase unavailable
Sodium hydroxide Liquid -416.88kJ/mol[24]

Due to the absence of information, the heat of solution and heat of mixing are neglected for
the calculation of energy balance.
Based on the calculation, the strainer, filter, chelating tower, clarifier and tank do not have
any heat duty.
R-101 Brine reactor
Based on the calculation, during the precipitation, the heat is released, and hence cooling
water is required to supply to the reactor to maintain the temperature of input and output
stream of brine reactor.

EZ-102 Electrolyser
Based on the calculation for electrolysis process, the process is endothermic process. But based
on the “Fundamentals of renewable energy process”[25], the process is neither endothermic
and exorthemic process and the certain amount of power will convert into the heat and must be
removed. Due to the absence of better information to predict the power lost to the surrounding
from electrolyser, we assume 20% of power will be converted into the heat.

124
Power required to supply to electrolyser
Based on the Faraday’s 2nd law of electrolysis,
1. The weights of substances formed at an electrode during electrolysis are directly
proportional to the quantity of electricity that passes through the electrolyte.[26]
2. The weights of different substances formed by the passage of the same quantity of
electricity are proportional to the equivalent weight of each substance.[26]
𝑄 𝑀
𝑚 = ( )( )
𝐹 𝑍
Where Q is electrical charge (coulombs), m is mass (gram), M is molar mass (grams per
mole), F is Faraday constant (96500Cmol-1), z is the electron transfer per ions.
Assuming time operating voltage is 2.0V
The calculation of voltage required is calculated based on the amount of chlorine gas
produced.
Faraday charge (2electrons are transferred per Cl-)
7988𝑚𝑜𝑙𝑥2𝐹
=
𝑚𝑜𝑙
=15976F
Charge in coulombs unit
96500c/F x 15976F=1541684000c
Duration of electrolysis
=1 HOUR = 3600s
Current required
=1541684000Asec/3600sec
=428245.56A
Power assumption in kW
=428245.56A x 2.0VX24hrs=20555.56kWh
*The power calculated is seemed too high and we suggest that maybe it cannot just simply
calculate by using Faraday’s 2nd law of electrolysis, the designing of electrolyser may reduce
the power required for electrolysis process.

125
Determination of final temperature of aqueous sodium hydroxide after dilution in T 301
tank

Figure 11: relative enthalpy against percent NaOH

From the diagram, the final temperature of 26.67℃ 50wt%NaOH after it is diluted by 26.67℃
water at to 15.5wt% is 48.88℃. Since the temperature of NaOH is too high for the chlorination,
a heat exchanger is installed after the dilution of NaOH.
Chlorination tower
𝐶𝑙2 (𝑔) + 2𝑁𝑎𝑂𝐻(𝑎𝑞) → 𝑁𝑎𝑂𝐶𝑙(𝑎𝑞) + 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂(𝑙) + 24700 𝑐𝑎𝑙𝑜𝑟𝑖𝑒𝑠 [1]
The heat duty we get from the calculation is positive enthalpy, this mean that the chlorination
reaction is endothermic. However, theoretical, this reaction is exothermic. The calculation is
incorrect. There are 24700 calories will released as heat for every one mole of production of
sodium hypochlorite at 25℃.[1] Due to the fact that we neglected the effect of heat of mixing.
Especially for sodium hydroxide, which will release a lot of heat when mixing with water
solution and the heat capacity as aqueous form is highly differently with pure solid or liquid
form.
The actual calculation should be done by treating sodium hydroxide as aqueous solution which
produce the aqueous solution with sodium hypochlorite & sodium chloride and pure water.
Since we neglect the heat of mixing in the calculation due to in the absence of data for heat of
mixing and formation of aqueous solution which containing both sodium hypochlorite and
sodium chloride, we determine the enthalpy for each pure component (Chlorine gas (gas form),
sodium hydroxide (l) and water (l) to produce pure NaOCl (l), pure NaCl(s) and water (l).)

126
Chapter 4: Justification on Aspen Plus Simulation

The completed process flow diagram (PFD) were divided into 3 Skid which consist of
skid 1, skid 2 and skid 3. Skid 1 is for water purifying before seawater enters electrolyzer.
Then, skid 2 is the electrolysis of the purified seawater and purification of NaCl and Cl 2. Skid
3 is the process of chlorination of NaOH and Cl2 into HOCl. The simulation was divided based
on these 3 skids to ease data generation and analysis process.

Aspen Simulation was done with some exception of unit operation. The unit operation that
cannot be simulated and reasons are:

Table 13: Unit operation that can’t be simulated using Aspen

Code Unit Reason

Operation

ST-101 Strainer Strainer functions to remove large particles inside seawater before
water purification. Strainer unit operation was not in Aspen
template. Then, Aspen required molecular weight of a component
to be simulated. However, large particles that was removed by
strainer were only common large particles which does not consist
specific molecular weight. Large particles also not involved in the
reaction and were assumed 100% removed.

C-101 Clarifier Clarifier functioned to remove solid particles produced in brine

reactor by sedimentation process. Clarifier was not in Aspen
Simulation template. Hence, all the solid produced inside Brine
Reactor were assumed 100% removed inside leaf filter which
should be second purification process.

127
F-102 Pre-coating Pre-coating Filter helps to remove released cellulose when the
Filter pressure inside pressure leaf filter is too high. Cellulose acts as
filter aid inside pressure leaf filter which replace the torn part of
leaf during filtration. It was in solid state at standard temperature
and pressure and required user defined data for Aspen Simulation.
Then, data inserted ran fail because Aspen cannot verify the data.
However, cellulose is negligible because it does not affect the
production of product.

128
Skid 1: Seawater Purification

A B

Figure 12: Flowsheet of Water Purification Process (Skid 1)

129
Table 14: Steam Table of Water Purification Process (SKID 1)
Heat and Material Balance Ta
Stream ID 3 4 5 6 6A 6B 10 11
From E-101 NACLPRO1 R-101A R-101B F-101 F-101
To E-101 R-101A R-101A F-101 R-101B NACLPRO1 PB-101
Phase MIXED LIQUID LIQUID MIXED MIXED MIXED SOLID LIQUID
Substream: MIXED
Mole Flow kmol/hr
WATER 4745.782 4745.782 11.52429 4757.306 4757.306 4757.306 0.0 4757.3
SODIU-01 0.0 0.0 .3243886 4.8789E-17 4.8789E-17 4.8789E-17 4.8789E-17 4.8789E
CALCI-01 0.0 0.0 0.0 .3243886 .3243886 .3243886 .3243886
MAGNE-01 0.0 0.0 0.0 1.221364 0.0 1.221364 1.221364
SODIU-02 0.0 0.0 2.442729 0.0 2.442729 0.0 0.0
SULFU-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HYDRO-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MAGNE-02 1.221364 1.221364 0.0 0.0 1.221364 0.0 0.0
SODIU-03 16.63244 16.63244 0.0 18.79685 16.63244 16.63244 0.0 18.796
HYPOC-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HYDRO-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CHLOR-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CALCI-02 .3243886 .3243886 0.0 4.8789E-17 4.8789E-17 4.8789E-17 4.8789E-17 4.8789E
SODIU-04 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Total Flow kmol/hr 4763.960 4763.960 14.29141 4777.648 4777.927 4775.484 1.545753 4776.1
Total Flow kg/hr 86620.91 86620.91 339.6969 86906.43 86922.69 86779.93 103.6967 86802
Total Flow l/min 1911.310 1489.375 5.886323 1486.939 1491.828 1487.150 .7007712 1437.9
Temperature C 25.00000 60.00000 25.00000 59.97856 60.00000 60.00000 25.00000 25.000
Pressure bar 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 2.451662 2.4516
Vapor Frac 2.49462E-4 0.0 0.0 0.0 0.0 0.0 0.0
Liquid Frac .9997505 1.000000 1.000000 .9996765 .9999321 .9996763 0.0 1.0000
Solid Frac 0.0 0.0 0.0 3.23539E-4 6.78932E-5 3.23685E-4 1.000000
Enthalpy cal/mol -68826.01 -68139.04 -69304.94 -68233.14 -68161.75 -68217.30 -2.3500E+5 -68858
Enthalpy cal/gm -3785.279 -3747.498 -2915.732 -3751.091 -3746.684 -3753.986 -3503.009 -3788.7
Enthalpy cal/sec -9.1079E+7 -9.0170E+7 -2.7513E+5 -9.0554E+7 -9.0464E+7 -9.0492E+7 -1.0090E+5 -9.1354E
Entropy cal/mol-K -40.07325 -37.89471 -35.69165 -37.95220 -37.89913 -37.95225 -70.82425 -40.098
Entropy cal/gm-K -2.203940 -2.084126 -1.501585 -2.086408 -2.083222 -2.088505 -1.055740 -2.2063
Density mol/cc .0415418 .0533105 .0404650 .0535512 .0533788 .0535194 .0367631 .05535
Density gm/cc .7553362 .9693206 .9618254 .9741088 .9710982 .9725532 2.466253 1.0060
Average MW 18.18255 18.18255 23.76931 18.19021 18.19255 18.17197 67.08493 18.174
Liq Vol 60F l/min 1442.410 1442.410 4.559940 1448.295 1448.092 1447.208 7.700590 1440.5

130
 Heat and Material Balance Table
10 11 17 22 22A 23 24 25 ARNACL ARNACL2
101B F-101 F-101 PB-101 NACLPRO2 PB-101 ED-101 ED-101
CLPRO1 PB-101 ED-101 NACLPRO2 ED-101 NACLPRO1 NACLPRO2
XED SOLID LIQUID MISSING LIQUID LIQUID LIQUID LIQUID LIQUID LIQUID LIQUID

4757.306 0.0 4757.306 0.0 4757.306 4757.306 148.0685 4757.291 148.0829 0.0 0.0
.8789E-17 4.8789E-17 4.8789E-17 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
.3243886 .3243886 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
1.221364 1.221364 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
16.63244 0.0 18.79685 0.0 19.72430 18.79685 0.0 1.972430 17.75187 2.164405 .9274518
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
.8789E-17 4.8789E-17 4.8789E-17 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
4775.484 1.545753 4776.103 0.0 4777.030 4776.103 148.0685 4759.264 165.8347 2.164405 .9274518
86779.93 103.6967 86802.73 0.0 86856.93 86802.73 2667.496 85819.21 3705.217 126.4932 54.20258
1487.150 .7007712 1437.969 0.0 1438.080 1437.969 44.72855 1437.141 52.92768 1.264273 .5417434
60.00000 25.00000 25.00000 25.02477 25.00000 25.00000 25.02405 25.02405 25.00000 25.00000
1.013250 2.451662 2.451662 1.013250 2.451662 1.013250 1.013250 1.013250 1.013250 1.013250
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
.9996763 0.0 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000 1.000000
.23685E-4 1.000000 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
-68217.30 -2.3500E+5 -68858.56 -68865.22 -68858.56 -68725.85 -68739.42 -72349.34 -1.0317E+5 -1.0317E+5
-3753.986 -3503.009 -3788.770 -3787.507 -3788.770 -3814.864 -3812.072 -3238.146 -1765.340 -1765.340
9.0492E+7 -1.0090E+5 -9.1354E+7 -9.1381E+7 -9.1354E+7 -2.8267E+6 -9.0875E+7 -3.3328E+6 -62028.75 -26579.44
-37.95225 -70.82425 -40.09852 -40.09570 -40.09852 -40.11986 -40.11426 -39.56236 -27.65467 -27.65467
-2.088505 -1.055740 -2.206320 -2.205217 -2.206320 -2.226991 -2.224611 -1.770696 -.4731947 -.4731947
.0535194 .0367631 .0553570 .0553635 .0553570 .0551730 .0551936 .0522205 .0285329 .0285329
.9725532 2.466253 1.006080 1.006631 1.006080 .9939570 .9952539 1.166755 1.667535 1.667535
18.17197 67.08493 18.17439 18.18220 18.17439 18.01528 18.03203 22.34283 58.44247 58.44247
1447.208 7.700590 1440.594 0.0 1441.060 1440.594 44.54394 1432.142 53.46180 1.086788 .4656906

131
Justification Aspen Simulation Skid 1

The mass balance obtained in Aspen is same as hand calculation mass balance. To get
the same mass balance, there were certain replacements that were needed to be made.
Crystallizer did not operate as per real process. To imitate the process inside crystallizer, box
A that consist of two crystallizers and additional of artificial NaCl stream (ARNACL) was
used. Precipitation process inside crystallizer produces magnesium hydroxide (MgOH),
calcium carbonate (CaCO3) and sodium chloride (NaCl). However, by using Aspen it is only
possible to produce one type of precipitant for each crystallizer. Then, additional second
crystallizer to produce another precipitant and an artificial stream of NaCl to follow as per real
precipitation process. The Chelating Resin Tower was imitated as normal separator as there is
only ion exchange process inside the unit operation. However, during ion exchange process to
remove Mg2+ ion, there are some NaCl being produced. Then, there was additional NaCl
(ARNACL2) stream input into the product stream of separator to illustrate the production of
NaCl inside the Chelating Resin Tower. Lastly, electrodialysis membrane is also imitated as
separator as the sole function of electrodialysis was to concentrate NaCl by removing pure
water before entering electrolyzer.

132
Skid 2: Electrolysis Process and Reactant Purification

Figure 123: Flowsheet of Electrolysis and Reactant Purification Process (SKID 2)

133
Table 15: Steam Table of Electrolysis Process

Stream ID 25 26 27 28 29 30 31 32
From EZ-201C EZ-201C EZ-201C EZ-201C CLMIX PB-201B
To EZ-201A EZ-201A CLMIX PB-201A EV-201 B6 CLMIX
Phase LIQUID LIQUID VAPOR VAPOR MIXED LIQUID MIXED MIXED
Substream: MIXED
Mole Flow kmol/hr
WATER 148.0685 91.34974 0.0 .9168962 144.7520 75.37648 1.327914 .4110
SODIU-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CALCI-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MAGNE-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-02 0.0 0.0 0.0 0.0 0.0 15.97640 0.0
SULFU-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HYDRO-01 0.0 0.0 0.0 0.0 2.396460 0.0 0.0
MAGNE-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-03 17.75155 0.0 0.0 0.0 1.775155 0.0 0.0
HYPOC-01 0.0 0.0 0.0 0.0 2.396460 0.0 0.0
HYDRO-02 0.0 0.0 7.988200 0.0 0.0 0.0 0.0
CHLOR-01 0.0 0.0 0.0 5.591740 0.0 0.0 7.988200 2.396
CELL 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CALCI-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-04 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Total Flow kmol/hr 165.8201 91.34974 7.988200 6.508636 151.3201 91.35287 9.316113 2.807
Total Flow kg/hr 3704.940 1645.691 16.10325 413.0027 2924.587 1996.938 590.3292 177.3
Total Flow l/min 52.92295 27.59494 3809.594 3076.349 1859.971 32.09663 12182.84 3313.
Temperature C 25.00000 25.00000 75.40912 75.40912 75.40912 75.40912 34.26395 25.00
Pressure bar 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 .3236194 .3236
Vapor Frac 0.0 0.0 1.000000 1.000000 .0252983 0.0 .9971755 .9282
Liquid Frac 1.000000 1.000000 0.0 0.0 .9747017 1.000000 2.82449E-3 .0717
Solid Frac 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Enthalpy cal/mol -72350.06 -68725.85 348.3787 -7739.103 -66767.53 -70369.77 -8193.927 -9248.
Enthalpy cal/gm -3238.133 -3814.864 172.8172 -121.9629 -3454.596 -3219.169 -129.3101 -146.4
Enthalpy cal/sec -3.3325E+6 -1.7439E+6 773.0329 -13991.95 -2.8065E+6 -1.7857E+6 -21204.32 -7212.
Entropy cal/mol-K -39.56385 -40.11986 1.078516 .5638831 -36.19021 -34.69057 1.704599 -1.062
Entropy cal/gm-K -1.770738 -2.226991 .5350099 8.88641E-3 -1.872506 -1.586971 .0269006 -.0168
Density mol/cc .0522205 .0551730 3.49477E-5 3.52617E-5 1.35594E-3 .0474363 1.27449E-5 1.41201
Density gm/cc 1.166772 .9939570 7.04504E-5 2.23752E-3 .0262063 1.036941 8.07597E-4 8.91854
Average MW 22.34314 18.01528 2.015880 63.45457 19.32716 21.85961 63.36647 63.16
Liq Vol 60F l/min 53.45732 27.48105 7.130507 5.016724 46.57762 28.23008 7.172182 2.155

134
 Heat and Material Balance Table
30 31 32 33 34 35 36 37 38 39 40 41
-201C EZ-201C CLMIX PB-201B PB-201B B6 B6 E-201 SPLITCL SPLITCL EV-201
-201A EV-201 B6 CLMIX PB-201A B6 E-201 SPLITCL
IXED LIQUID MIXED MIXED MIXED MIXED VAPOR VAPOR MIXED VAPOR VAPOR VAPOR VAPOR

144.7520 75.37648 1.327914 .4110173 .0113278 146.7488 .0654931 0.0 1.393407 0.0 0.0 0.0 39.9906
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 15.97640 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.2698E-1
0.0 0.0 0.0 0.0 0.0 0.0 .5894746 0.0 .5894746 0.0 0.0 0.0 0
2.396460 0.0 0.0 0.0 .2742882 .2742882 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
1.775155 0.0 0.0 0.0 0.0 1.775155 0.0 0.0 0.0 0.0 0.0 0.0 0
2.396460 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 7.988200 2.396460 0.0 0.0 0.0 7.988200 0.0 7.988200 .1461841 7.842016 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
151.3201 91.35287 9.316113 2.807477 .2856160 148.7982 .6549677 7.988200 1.982881 7.988200 .1461841 7.842016 39.9906
2924.587 1996.938 590.3292 177.3265 10.20480 2757.466 58.99524 566.4065 82.91797 566.4065 10.36524 556.0412 720.443
1859.971 32.09663 12182.84 3313.817 114.1157 413.9236 257.8958 10462.72 888.8914 3112.106 56.95153 3055.154 20707.5
75.40912 75.40912 34.26395 25.00000 25.00000 25.00000 25.00000 33.84010 33.84010 15.56000 15.56000 15.56000 108.600
1.013250 1.013250 .3236194 .3236194 1.013250 .3236194 1.013250 .3236194 .3236194 1.013250 1.013250 1.013250 1.01325
.0252983 0.0 .9971755 .9282320 .9858912 1.94859E-3 1.000000 1.000000 .3443005 1.000000 1.000000 1.000000 1.00000
.9747017 1.000000 2.82449E-3 .0717679 .0141087 .9980514 0.0 0.0 .6556995 0.0 0.0 0.0 0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0
-66767.53 -70369.77 -8193.927 -9248.355 -23628.82 -69042.30 -1.6385E+5 66.30686 -99815.99 -95.72401 -95.72401 -95.72401 -57098.7
-3454.596 -3219.169 -129.3101 -146.4222 -661.3331 -3725.657 -1819.076 .9351454 -2386.976 -1.350024 -1.350024 -1.350024 -3169.46
2.8065E+6 -1.7857E+6 -21204.32 -7212.374 -1874.659 -2.8537E+6 -29810.23 147.1312 -54978.68 -212.4062 -3.887034 -208.5192 -6.3428E+
-36.19021 -34.69057 1.704599 -1.062572 1.677146 -39.98352 -59.36924 2.493127 -44.65394 -.3010318 -.3010318 -.3010318 -8.64320
-1.872506 -1.586971 .0269006 -.0168228 .0469406 -2.157589 -.6591199 .0351613 -1.067844 -4.2455E-3 -4.2455E-3 -4.2455E-3 -.479770
.35594E-3 .0474363 1.27449E-5 1.41201E-5 4.17144E-5 5.99137E-3 4.23277E-5 1.27249E-5 3.71789E-5 4.27803E-5 4.27803E-5 4.27803E-5 3.21868E
.0262063 1.036941 8.07597E-4 8.91854E-4 1.49042E-3 .1110296 3.81260E-3 9.02261E-4 1.55471E-3 3.03335E-3 3.03335E-3 3.03335E-3 5.79855E
19.32716 21.85961 63.36647 63.16224 35.72908 18.53158 90.07351 70.90540 41.81691 70.90540 70.90540 70.90540 18.0152
46.57762 28.23008 7.172182 2.155458 .2482457 45.28310 .5466653 6.772702 .9461460 6.772702 .1239404 6.648761 12.0305

135
 39 40 41 42 43 44 45 REAC2 SEP1 SEP2
1 SPLITCL SPLITCL EV-201 EV-201 E-301 SPLNAOH SPLNAOH EZ-201A EZ-201B PB-201A
TCL E-301 SPLNAOH EZ-201B EZ-201C PB-201B
R VAPOR VAPOR VAPOR LIQUID LIQUID LIQUID LIQUID MIXED LIQUID MIXED

0.0 0.0 0.0 39.99069 35.38578 35.38578 34.94134 .4444454 223.4418 221.0454 147.1598
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 2.2698E-13 15.97640 15.97640 15.77574 .2006636 15.97640 15.97640 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.396460 .2742882
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 1.775155 1.775155 1.775155
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 2.396460 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 7.988200 7.988200 0.0
988200 .1461841 7.842016 0.0 0.0 0.0 0.0 0.0 7.988200 5.591740 2.396460
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
988200 .1461841 7.842016 39.99069 51.36218 51.36218 50.71707 .6451090 257.1698 257.1698 151.6057
6.4065 10.36524 556.0412 720.4435 1276.495 1276.495 1260.462 16.03277 5350.631 5350.631 2934.792
12.106 56.95153 3055.154 20707.59 19.77988 19.31278 19.07021 .2425685 15524.09 88.65424 3720.051
.56000 15.56000 15.56000 108.6000 108.6000 26.67000 26.67000 26.67000 85.00000 85.00000 25.00000
013250 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 .3236194
000000 1.000000 1.000000 1.000000 0.0 0.0 0.0 0.0 .1232651 0.0 .0190612
0.0 0.0 0.0 0.0 1.000000 1.000000 1.000000 1.000000 .8767349 1.000000 .9809388
0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0
.72401 -95.72401 -95.72401 -57098.73 -71717.33 -73126.56 -73126.56 -73126.56 -63903.87 -64222.76 -67935.08
350024 -1.350024 -1.350024 -3169.461 -2885.683 -2942.386 -2942.386 -2942.386 -3071.440 -3086.767 -3509.395
2.4062 -3.887034 -208.5192 -6.3428E+5 -1.0232E+6 -1.0433E+6 -1.0302E+6 -13104.06 -4.5650E+6 -4.5878E+6 -2.8609E+6
010318 -.3010318 -.3010318 -8.643207 -31.19652 -35.35351 -35.35351 -35.35351 -31.37096 -33.56535 -39.25130
455E-3 -4.2455E-3 -4.2455E-3 -.4797709 -1.255251 -1.422515 -1.422515 -1.422515 -1.507797 -1.613267 -2.027646
803E-5 4.27803E-5 4.27803E-5 3.21868E-5 .0432781 .0443248 .0443248 .0443248 2.76098E-4 .0483469 6.79228E-4
335E-3 3.03335E-3 3.03335E-3 5.79855E-4 1.075583 1.101598 1.101598 1.101598 5.74444E-3 1.005899 .0131485
.90540 70.90540 70.90540 18.01528 24.85281 24.85281 24.85281 24.85281 20.80583 20.80583 19.35806
772702 .1239404 6.648761 12.03053 16.19955 16.19955 15.99609 .2034664 87.56763 86.95494 47.43856

136
Justification Aspen Simulation Skid 2 (Electrolysis and Reactant Purification)

Electrolyzer unit operation is not in Aspen Simulation Template. To simulate the

process of electrolyzer, unit operation inside box C was used. First, the ion transfer through the
membrane to produce hydrogen gas (H2), chlorine gas (Cl2) and sodium hydroxide (NaOH)
was set into an equation and used it into a stochiometric reactor (RSTOIC) (EZ-101A). After
that, there was a second reaction occurring when Cl2 was dissolved into brine water to produce
hydrochloric acid (HCL) and hypochlorous acid (HOCL). Second reaction was simulated with
another RSTOIC (EZ-101B) because RSTOIC cannot detect a reaction that used another
product of reaction as its feed. The product of reactor also need to be separated using separator
(EZ-201C) because electrolyzer already separated the product of reaction with multiple
streams.

The depleted brine water consists of HCL and HOCL entering dechlorination tower.
The dechlorination tower simulated inside box D which consist of RSTOIC and separator.
RSTOIC will convert the HCl and HOCl into Cl2 and H2O through reverse reaction. The
process continues with separator to separate gas and liquid because RSTOIC cannot divide the
product into different phases. After that, separator was simulated for the process of absorption
where 86% Cl2 will be dried into 99% Cl2. Basically, the water will be removed to produce
more concentrated Cl2. Next, 32% NaOH produced will be concentrated into 50% using falling
film evaporator. Falling film evaporator was simulated using flash evaporator because it had
the same operating mechanism.

137
Skid 3: Chlorination Process

Figure 14: Flowsheet of Chlorination Process (Skid 3)

138
Table 16 Steam Table of Chlorination Process (Skid 3)

Heat and Material Balance Table

Stream ID 40 44 46 47 48 50 51
From T-301 B1 R-301 E-303
To R-301 T-301 T-301 B1 R-301 E-303
Phase VAPOR LIQUID LIQUID LIQUID LIQUID MIXED LIQUID
Substream: MIXED
Mole Flow kmol/hr
WATER 0.0 34.94134 156.0649 191.0063 191.0063 198.8483 198.8483
SODIU-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CALCI-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MAGNE-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-02 0.0 15.77574 0.0 15.77574 15.77574 .0917080 .0917080
SULFU-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HYDRO-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
MAGNE-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-03 0.0 0.0 0.0 0.0 0.0 7.842016 7.842016
HYPOC-01 0.0 0.0 0.0 0.0 0.0 0.0 0.0
HYDRO-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CHLOR-01 7.842016 0.0 0.0 0.0 0.0 0.0 0.0
CELL 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CALCI-02 0.0 0.0 0.0 0.0 0.0 0.0 0.0
SODIU-04 0.0 0.0 0.0 0.0 0.0 7.842016 7.842016
Total Flow kmol/hr 7.842016 50.71708 156.0649 206.7820 206.7820 214.6240 214.6240
Total Flow kg/hr 556.0413 1260.462 2811.554 4072.016 4072.016 4628.057 4628.057
Total Flow l/min 3055.154 19.00992 47.14412 65.56874 65.22655 3237.393 77.23321
Temperature C 15.56000 15.56000 25.00000 25.15107 15.56000 30.00000 30.00000
Pressure bar 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250 1.013250
Vapor Frac 1.000000 0.0 0.0 0.0 0.0 .0378617 0.0
Liquid Frac 0.0 1.000000 1.000000 1.000000 1.000000 .9621383 1.000000
Solid Frac 0.0 0.0 0.0 0.0 0.0 0.0 0.0
Enthalpy cal/mol -95.72401 -73320.16 -68725.85 -69852.69 -70030.21 -67353.77 -66684.82
Enthalpy cal/gm -1.350024 -2950.176 -3814.864 -3547.206 -3556.221 -3123.500 -3092.478
Enthalpy cal/sec -208.5192 -1.0329E+6 -2.9794E+6 -4.0123E+6 -4.0225E+6 -4.0155E+6 -3.9756E+6
Entropy cal/mol-K -.3010318 -36.01148 -40.11986 -38.91122 -39.51610 -38.16259 -37.49431
Entropy cal/gm-K -4.2455E-3 -1.448990 -2.226991 -1.975960 -2.006677 -1.769773 -1.738782
Density mol/cc 4.27803E-5 .0444654 .0551730 .0525611 .0528368 1.10492E-3 .0463151
Density gm/cc 3.03335E-3 1.105092 .9939570 1.035050 1.040480 .0238260 .9987191
Average MW 70.90540 24.85281 18.01528 19.69231 19.69231 21.56355 21.56355
Liq Vol 60F l/min 6.648762 15.99609 46.94954 62.94562 62.94562

139
Justification Aspen Simulation Skid 3 (Chlorination)

Skid 3 starts with the dilution of 50% NaOH into 15.5% NaOH inside dilution tank.
Dilution tank was simulated using mixer by addition of water. After that, NaOH with pure Cl2
will enter packed column reactor to produce sodium hypochlorite (NaOCl). Further conversion
continued inside buffer tank to make sure all Cl2 reacted. Packed column reactor and buffer
tank were simulated using RSTOIC with value of 1 fractional conversion of Cl2. It means that
all chlorine will be converted into NaOCl.

140
Comparison of Simulation and Calculation Mass Balance

Table 17: Total Mass of Inlet for Simulation and Calculation:

Calculation
INLET (kg/hr)
1 5 9 16 23 26 33 35 46 SUM
90000 339.7045 5 191.158 2667.602 1645.757 10.20408 58.99618 2811.666 97730.08785
Simulation
INLET (kg/hr)
4 5 23 26 33 35 46 SUM
86620.91 339.6969 2667.496 1645.691 10.2048 58.99524 2811.554 94154
Table 18: Total Mass of Outlet for Simulation and Calculation:

Calculation
OUTLET (kg/hr)
1
2 7 10 2 17 24 27 34 37 39 51 41 45 SUM
3375. 59.381 21.776 182.64 85853. 16.104 2757.9 82.594 10.363 4629.6 718.90 16.04802 97730.08
72 49 03 5 17 94 21 48 66 35 66 2 947 785
Simulation
OUTLET (kg/hr)
10 17 24 27 34 37 39 41 45 51 SUM
103.69 85819. 16.103 2757.4 82.917 10.365 720.44 16.032
67 0 21 25 66 97 24 35 77 4628.05 94154

Comparison is made for balance of hand calculation and simulation. Total mass of outlet
and inlet of calculation were higher compared to simulation because it consists of solid that
couldn’t be simulated because of Aspen Simulation limitation.

141
Chapter 5: Utilities & Other Issues

5.1 Utility Stream Balance

5.1.1 Cooling & Heating Utilities

Table 19: Type of Heating and Cooling utilities used

Process
Heat Duty
Temperature (˚C)
Destination
No Unit Utility Type
Code
In Out MJ/hr

Cooling Oil
1 Brine Reactor R-101 Therminol LT 60.00 60.00 -1022447729.67
Superheated Steam
Superheated
3 Heat Exchanger 1 E-101 25.00 60.00 12557.82
Steam
Superheated
4 Evaporator EV-201 80.00 110.00 20469244.02
Steam
Cooling Water
Cooling
5 Heat Exchanger 2 E-201 70.00 15.56 -14.85
Water
Cooling
6 Heat Exchanger 3 E-301 110.00 26.67 -45940635.01
Water
Cooling
7 Heat Exchanger 4 E-302 48.89 15.56 -12807056.79
Water
Cooling
8 Heat Exchanger 5 E-303 26.67 20.00 -13698.87
Water
Cooling
9 Electrolyzer EZ-101 60 80 0.86
Water

The brine reactor and electrolyzer uses Therminol LT because it has large range of operating
temperature that become more stable fluid properties over a wide range temperature. The fluid was put
directly outside of the reactor. Hence, it is suitable to use Therminol LT because it has higher ability to
control temperature difference which can minimize thermal shock [14]. The other heat transfer medium
are superheated steam and cooling water which is water. Water is suitable to be used inside heat
exchanger because heat exchanger is used to heat up or cool down a stream. Stream usually flowing
with high velocity requires high heat transfer coefficient media to transfer the heat into the stream or
cool down the stream. Since heat exchanger also can be maintained easily as it was not as big as other
important unit operation, corrosion due presence was not an issue.

142
 Table 20: Calculation for Utility Molar Flow Rate Required
Utility
Inlet Outlet
Heat Duty of
Utility Molar Utility Mass Specific Utility Molar Utility Mass Specific Utility
Temperature Pressure Energy Flow Temperature Pressure Energy Flow
Flow Rate Flow Rate Enthalpy Flow Rate Flow Rate Enthalpy
(˚C) (bar) (MJ/hr) (˚C) (bar) (MJ/hr)
(kmol/hr) (kg/hr) (MJ/kmol) (kmol/hr) (kg/hr) (MJ/kmol)

Cooling Oil Cooling Oil

100.00 1.01325 179534280.89 24057593639.40 25.62 4599811903.85 120.00 1.01325 179534280.89 24057593639.40 31.32 5622259633.53 1022447729.67
Superheated Steam at 150 ˚C Superheated Steam at 100 ˚C
150.00 1.01325 6970.37 125578.16 50.01 348604.98 100.00 1.01325 6970.37 125578.16 48.21 336047.16 -12557.82
150.00 1.01325 11361702.94 204692440.22 50.01 568226214.05 100.00 1.01325 11361702.94 204692440.22 48.21 547756970.03 -20469244.02
Cooling Water at 25˚C Cooling Water at 50˚C
25.00 1.01325 7.88 141.96958 -285.84 -2252.47 50.00 1.01325 7.88 141.97 -283.96 -2237.62 14.85
25.00 1.01325 24371689.66 439080360.88187 -285.84 -6966403771.90 50.00 1.01325 24371689.66 439080360.88 -283.96 -6920463136.89 45940635.01
25.00 1.01325 6794194.58 122404209.59147 -285.84 -1942052579.35 50.00 1.01325 6794194.58 122404209.59 -283.96 -1929245522.57 12807056.79
25.00 1.01325 7267.31 130927.79388 -285.84 -2077286.89 50.00 1.01325 7267.31 130927.79 -283.96 -2063588.02 13698.87
25.00 1.01325 0.45 8.18617 -285.84 -129.88 50.00 1.01325 0.45 8.19 -283.96 -129.02 0.86

143
5.1.2 Electricity

Electricity is used in electrolyzer for the production of sodium hypochlorite. The total
electrical energy consumption of each of the equipment is calculated as below:

𝑘𝑊ℎ ℎ𝑜𝑢𝑟 𝑑𝑎𝑦𝑠

𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 ( ) = 𝑃𝑜𝑤𝑒𝑟(𝑘𝑊) × 24 × 350
𝑦𝑒𝑎𝑟 𝑑𝑎𝑦 𝑦𝑒𝑎𝑟

Total Electrical
Power Quantity Energy
Type of Utility Unit Code Consumption
(kWh/year)
kW
Electricity Electrolyzer EZ-102 20556.3 172672922.4

144
5.2 Waste Generation

In proposed sodium hypochlorite production plant, the wastes produced can be classified as
solid and liquid wastes, which require proper treatment and disposal according to the rules and
regulation following Environmental Quality (Sewage and Industrial Effluents) Regulations, 1979.

Formula:

𝑋 𝑡𝑜𝑛 24 ℎ𝑜𝑢𝑟𝑠 350 𝑑𝑎𝑦𝑠

× × = 𝑋 𝑡𝑜𝑛⁄𝑦𝑒𝑎𝑟
ℎ𝑜𝑢𝑟 1 𝑑𝑎𝑦 1 𝑦𝑒𝑎𝑟

5.2.1 Solid Wastes

Table 20: Solid Waste generated

SOLID
Quantity
Component kg/hr kg/year ton/hr ton/year
Magnesium Hydroxide 566.8449 4081283.63 0.566845 4081.284
Calcium Carbonate 258.3439 1860076.36 0.258344 1860.076
Cellulose 5 36000 0.005 36
Total 830.1889 5977359.99 0.830189 5977.36

Generally, the solid wastes consist of magnesium hydroxide and calcium carbonate precipitated
out from the seawater purification process. The cellulose comes out from precoating filter after
being used as a precoat in the pressure leaf filter. These solids can actually be recovered as
coagulants for lime softening process, hence proper management and handling of sludge is of much
importance. The sludge consisting of magnesium hydroxide and calcium carbonate could be
injected with CO2 gas to selectively dissolves Mg (OH)2.

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The chemical reactions for sludge carbonation are as such;

𝑀𝑔(𝑂𝐻)2 + 2𝐶𝑂2 ⇌ 𝑀𝑔(𝐻𝐶𝑂3 )2

𝑀𝑔(𝑂𝐻)2 + 𝐶𝑂2 ⇌ 𝑀𝑔𝐶𝑂3 + 𝐻2 𝑂

The magnesium bicarbonate recovered in the filtrate can be used in lime-soda softening
process. As for calcium carbonate, it is possible in any large plants to reduce the amount of waste
solids by slurrying the filter cake and separating the raw water from calcium carbonate by flotation.
The purified calcium carbonate will then be dewatered and recalcined as high quality
quicklime[27].

As for cellulose, the waste disposal approaches are usually in landfills, incineration,or being
recycled in cement and ceramic plant. However, researchers are considering the usage of cellulose
sludge as construction materials as an alternative of better waste management[28].

5.2.2 Liquid Wastes

Table 21: Liquid waste generated
LIQUID
Quantity
Component kg/hr kg/year ton/hr ton/year
Hydrochloric Acid 100 720000 0.1 720
Water 1004693 7233786996 1004.693 7233787
Sodium Chloride 2489.738 17926116 2.489738 17926.12
Total 1007282 7252433112 1007.282 7252433

The liquid wastes (wastewater) produced are mainly from the de-chlorination tower.
Hydrochloric acid is considered dangerous and harmful. According to OSHA regulatory status,
this product is considered as ‘hazardous chemical’ under 29 CFR 1910 1200(Hazard
Communication). If being mindlessly disposed without any prior treatment, this chemical may
affect the acidity in water with risk of harmful effects to aquatic organisms. The disposed HCl
should be properly labeled and disposed by hazardous waste contractor. As for sodium chloride, it
is advisable to hire a licensed professional waste disposal service to dispose of this product.

146
The waste may be dissolved in a combustible solvent or absorbed onto a combustible material and
burned by a chemical incinerator. The storage of the disposed chemicals should be in an assigned
area that is away from populated area and well-ventilated. It is also imperative to obtain permission
from the local wastewater treatment facility and be in compliance with local and State environment
regulations.

147
Chapter 6: References

1. SPA, C.E., Sodium hypochlorite plant.

2. Jaipur, M. Project Report on Chloro Caustic Group. [cited 2017 14/9/2017]; Available
from: https://www.slideshare.net/pintujain/project-report-on-chloro-caustic-group.
3. Paidar, M., V. Fateev, and K. Bouzek, Membrane electrolysis—History, current status
and perspective. Electrochimica Acta, 2016. 209(Supplement C): p. 737-756.
4. Manas Chanda, S.K.R., Plastics Technology Handbook. 1998: CRC Press. 1214.
5. O'Brien, T.F., Bommaraju, Tilak V., Hine, Fumio, Handbook of Chlor-Alkali
Technology. Vol. Volume II: Brine Treatment and Cell Operation. 2005: Springer
Science & Business Media.
6. H, P.E., Manufacture of sodium hypochlorite. 1972, Google Patents.
7. Australian Stainless Steel Development Association. 2017 [cited 2017 2nd November];
Available from: https://www.assda.asn.au/benefits-of-stainless-steel.
8. O'Neal Steel. 2017 [cited 2017 4th November]; Available from:
http://www.onealsteel.com/carbon-and-alloy-steel.html.
9. Supra Alloys. 2017 [cited 2017 7th November]; Available from:
http://www.supraalloys.com/titanium-grades.php.
10. kimihiko Sato, H.M., High Performance Ion Exchange Membrane for Industrial Use.
Polymer Journal, 1990. Vol. 23: p. 531-540.
11. Voutchkov, N., Desalination Engineering Planning and Design. 2013, New York:
McGraw Hill. 642.
12. CHLORINE PROCESSING. CHLORALKALI TECHNOLOGY 2011 [cited 2017 10
NOVEMBER]; Available from: http://chloralkalitechnology.blogspot.my/p/chlorine-
processing.html.
13. Garrett, D.E., Chemical Engineering Economics. 1989, New York: Van Nostrand
Reinhold
14. Agency, U.S.E.P., Magnesium Carbonate - A Recycled Coagulant From Water
Treatment 1975.
15. Modolo, R., et al., Construction materials as a waste management solution for cellulose
sludge. Waste Management, 2011. 31(2): p. 370-377.
1. Voutchkov, N., Desalination Engineering Planning and Design. 2013, New York:
McGraw Hill. 642.
2. SPA, C.E., Sodium hypochlorite plant.
3. Jaipur, M. Project Report on Chloro Caustic Group. [cited 2017 14/9/2017]; Available
from: https://www.slideshare.net/pintujain/project-report-on-chloro-caustic-group.
4. Paidar, M., V. Fateev, and K. Bouzek, Membrane electrolysis—History, current status
and perspective. Electrochimica Acta, 2016. 209(Supplement C): p. 737-756.
5. Manas Chanda, S.K.R., Plastics Technology Handbook. 1998: CRC Press. 1214.
6. O'Brien, T.F., Bommaraju, Tilak V., Hine, Fumio, Handbook of Chlor-Alkali
Technology. Vol. Volume II: Brine Treatment and Cell Operation. 2005: Springer
Science & Business Media.
7. H, P.E., Manufacture of sodium hypochlorite. 1972, Google Patents.

148
8. Australian Stainless Steel Development Association. 2017 [cited 2017 2nd November];
Available from: https://www.assda.asn.au/benefits-of-stainless-steel.
9. O'Neal Steel. 2017 [cited 2017 4th November]; Available from:
http://www.onealsteel.com/carbon-and-alloy-steel.html.
10. Supra Alloys. 2017 [cited 2017 7th November]; Available from:
http://www.supraalloys.com/titanium-grades.php.
11. kimihiko Sato, H.M., High Performance Ion Exchange Membrane for Industrial Use.
Polymer Journal, 1990. Vol. 23: p. 531-540.
12. CHLORINE PROCESSING. CHLORALKALI TECHNOLOGY 2011 [cited 2017 10
NOVEMBER]; Available from: http://chloralkalitechnology.blogspot.my/p/chlorine-
processing.html.
13. Garrett, D.E., Chemical Engineering Economics. 1989, New York: Van Nostrand
Reinhold
14. Mudyawabikwa, B., et al., Methylene blue removal using a low-cost activated carbon
adsorbent from tobacco stems: kinetic and equilibrium studies. Water Science and
Technology, 2017. 75(10): p. 2390-2402.
15. Mitko, K., W. Mikołajczak, and M. Turek, Electrodialytic concentration of NaCl for the
chlor-alkali industry. Desalination and Water Treatment, 2015. 56(12): p. 3174-3180.
16. Jain, P., Project report on Chloro Caustic Group.
17. Balagopal, S., et al., Electrolytic process to produce sodium hypochlorite using sodium
ion conductive ceramic membranes. 2008, Google Patents.
18. Foo, K.Y. and B.H. Hameed, Microwave assisted preparation of activated carbon from
pomelo skin for the removal of anionic and cationic dyes. Chemical Engineering Journal,
2011. 173(2): p. 385-390.
19. Application note pH in brine treatment and dechlorination. 2017 [cited 2017
16/11/2017]; Available from: http://www.barbenanalytical.com/files/Chlor-
alkali_AN_RevA.pdf.
20. J.P.Holman, Heat transfer. 2010, Mc Graw Hill.
21. Acids and Bases-Weak Acid Ka Values. [cited 2017 16/11/2017]; Available from:
https://www.thoughtco.com/acids-and-bases-weak-acid-ka-values-603973.
22. Perry, R.H., D.W. Green, and J.O. Maloney, Perry's Chemical Engineers' Handbook.
1997: McGraw-Hill.
23. Felder, R.M. and R.W. Rousseau, Elementary principles of chemical processes. 2000:
John Wiley.
24. Thomas F. O'Brien, T.V.B., Fumio Hine, Handbook of Chlor-Alkali Technology: Volume
1: Fundamentals. Vol. 1. 2005, New York: Springer. 443-463.
25. Rosa, A.d., Fundamentals of renewable energy process. 2009, USA: Elsevier.
26. Electrolytic cell and electrolysis.
27. Agency, U.S.E.P., Magnesium Carbonate - A Recycled Coagulant From Water
Treatment 1975.
28. Modolo, R., et al., Construction materials as a waste management solution for cellulose
sludge. Waste Management, 2011. 31(2): p. 370-377.

149
Chapter 7: Appendix

7.1 Meeting Minute

Date: 24th October 2017 Time: 9pm

Venue: Café Lembaran
Attendance:
Ng Zhi Heng, Fakhira, Engku and Joanna
Agenda:
1. Task 2 leader was appointed. Zhi Heng as task 2 leader.
2. Task delegation to everyone.
3. Mass Balance (MB) & Energy Balance (EB) everyone must do.
4. Joanna to prepare letter to be sent to Jabatan Alam Sekitar & Sumber Asli
___________________________________________________________________________
Date: 1st November 2017 Time: 9pm
Venue: Café Lembaran
Attendance:
Ng Zhi Heng, Fakhira, Engku and Joanna
Agenda:
1. Material of construction done
2. MB calculation in progress as we’re finding seawater composition.
3. Find thermodynamic data for EB calculation
4. Edited PFD diagram as to what Dr.Syamsul advice to.

150
Date: 4th November 2017 Time: 9pm
Venue: Café Lembaran
Attendance:
Ng Zhi Heng, Fakhira, Engku and Joanna
Agenda:
1. Economic potential calculation in progress.
2. Clarifier, pressure leaf filter and membrane electrolyzer efficiency needed for MB
calculation.
3. Heat of dilution needed for EB calculation
4. Membrane which is polymer, molecular weight is needed for MB calculation

___________________________________________________________________________

Date: 7th November 2017 Time: 8.30pm

Venue: Café Lembaran
Attendance:
Ng Zhi Heng, Fakhira, Engku and Joanna
Agenda:
1. MB calculation reaching completion but overall couldn’t tally.
2. Started off with Aspen simulation to gain similar equipments to be simulated.
3. EB calculation started off but still in need of NaOCl data.

151
Date: 12th November 2017 Time: 9pm
Venue: Café Lembaran
Attendance:
Ng Zhi Heng, Fakhira, Engku and Joanna
Agenda:
1. MB calculation completed.
2. Question 4 waste generation in progress.
3. Question 1 economic potential also in progress as it requires MB calculation values.
4. EB calculation still ongoing.

152