Sub. Title P.

N
1.1 Introduction ……………………………………... 1
Caustic Soda Production
1.2 ……………………………………... 2
Methods
Production of caustic Soda
1.2.1 ……………………………………... 2
by Lime
Production of Caustic
1.2.2 ……………………………………... 3
Soda by Loewig’s process
Production of Caustic
1.2.3 ……………………………………... 4
Soda by Electrolysis
1.2.3.1 Membrane Cell ……………………………………... 6
1.2.3.2 Mercury Cell ……………………………………... 8
1.2.3.3 Diaphragm Cell ……………………………………... 9
Selection of production
1.3 ……………………………………... 12
method
1.4 Properties of Caustic Soda ……………………………………... 13
1.4.1 Physical Properties ……………………………………... 13
1.4.2 Chemical Properties ……………………………………... 14
1.5 Uses of Caustic Soda ……………………………………... 16

1
Fig. Title P.N
Production process of
1 sodium hydroxide and ……………………………………... 4
chlorine by electrolysis
Process flow chart of a
2 ……………………………………... 7
membrane process
3 Membrane cell ……………………………………... 8
Mercury process for chlor-
4 ……………………………………... 8
alkali
process flow chart for a
5 ……………………………………... 9
mercury cell process
6 Diaphragm Cell ……………………………………... 10
Process flow chart of a
7 ……………………………………... 11
diaphragm process
Whitish pellets of Caustic
8 ……………………………………... 14
soda

2
Chapter One
Introduction

3
1.1 Introduction

Sodium Hydroxide (NaOH), also known as lye and caustic soda, is

an inorganic compound with the formula (NaOH). It is a white solid ionic
compound consisting of sodium cations (Na+) and hydroxide anions (OH−) and it
belongs to strong basis. Sodium hydroxide is a highly caustic base and alkali that
decomposes proteins at ordinary ambient temperatures and may cause
severe chemical burns. It is highly soluble in water, and readily
absorbs moisture and carbon dioxide from the air. It forms a series
of hydrates NaOH.nH2O. The monohydrate NaOH.H2O crystallizes from water
solutions between 12.3 and 61.8 °C. The commercially available "sodium hydroxide"
is often this monohydrate, and published data may refer to it instead of
the anhydrous compound. As one of the simplest hydroxides, it is frequently utilized
alongside neutral water and acidic hydrochloric acid to demonstrate the pH scale to
chemistry students. Pure sodium hydroxide, it does not found in nature, but is manu-
factured on a large scale from fairly readily obtainable raw materials and is used in
numerous chemical processes. Because of its corrosive action on many substances.
Sodium hydroxide solution is one of the oldest man-made chemicals. The reaction
of sodium carbonate with calcined limestone (causticization of soda) was already
known in early Afro-Oriental cultures. Alabaster vessels containing 3% sodium
hydroxide solution have been found in Egyptian tombs dating from 3rd century B.C.
near the Pyramid of Cheops. The first written records of caustic soda production
during the early years A.D. came from Egypt and India. Sodium hydroxide is used in
many industries: in the manufacture of pulp and paper, textiles, drinking
water, soaps and detergents, and as a drain cleaner. Worldwide production in 2004
was approximately 60 million tons, while demand was 51 million tons.

4
1.2 Caustic Soda Production Methods
1.2.1 Production of caustic Soda by Lime
Sodium hydroxide (NaOH) from limestone (CaO). This study aims to
synthesize NaOH from limestone (Lime) by burning (big stone) 6 grams of
powder CaO with 100 ml of Aqueous little by little so as to form a porridge of
𝐶𝑎(𝑂𝐻)2 . 𝐶𝑎𝑂 which has dissolved in Aqueous In addition to forming 𝐶𝑎(𝑂𝐻)2 ,
the mixing of CaO with Aqueous aims to make the CaO that formed the solution
more reactive because the liquid form so easily react with 𝑁𝑎2 𝐶𝑂3 solution. Then
prepared a solution of 𝑁𝑎2 𝐶𝑂3 by dissolving 10.6 grams of 𝑁𝑎2 𝐶𝑂3 powder into
100 ml of Aqueous while heated.
Reaction between 𝑁𝑎2 𝐶𝑂3 and 𝐶𝑎(𝑂𝐻)2 . Heating is done to facilitate the powder
𝑁𝑎2 𝐶𝑂3 dissolve in Aqueous. Furthermore, the 𝐶𝑎(𝑂𝐻)2 slurry is mixed into
𝑁𝑎2 𝐶𝑂3 solution while remaining heated. The equation of the reaction occur is:
𝐶𝑎𝑂(𝑠) + 𝐻2𝑂 (𝑙) → 𝐶𝑎(𝑂𝐻)2 (𝑎𝑞)

𝑁𝑎2 𝐶𝑂3 (𝑎𝑞) + 𝐶𝑎(𝑂𝐻)2 (𝑎𝑞) → 2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐶𝑎𝐶𝑂3 (𝑠)

The obtained NaOH solution, solution then tested for its acidity by using a universal
indicator. It is known that the pH of NaOH solution is 13.
pH Test Using Universal indicator. This shows that the obtained NaOH solution is a
very strong base. Testing of subsequent NaOH filtrate using USO4 solution, CuO
black deposits are formed when the NaOH filtrate is added to CuSO4 solution while
heated. At first when the NaOH filtrate was incorporated into CuSO4 solution
formed a light blue precipitate which was a precipitate of Cu(OH)2
2𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐶𝑢𝑆𝑂4 (𝑎𝑞) → 𝐶𝑢 (𝑂𝐻 )2 (𝑠) + 𝑁𝑎2 𝑆𝑂4 (𝑎𝑞)

5
Test NaOH Product Using 𝐶𝑢𝑆𝑂4 Since the heating applied to the mixture causes
the water content contained in the 𝐶𝑢(𝑂𝐻)2 precipitate to evaporate to form Cu
which is brown and directly oxidized to CuO which is a black precipitate according
to:
𝐶𝑢(𝑂𝐻)2 (𝑠) → 𝐶𝑢(𝑠) → 𝐶𝑢𝑂(𝑠)
Furthermore, to determine the levels of NaOH obtained, done titration of NaOH
solution using Titration HCl 1 M.
NaOH titration using HCl 1 M
Append 3 drops pp indicator added to NaOH solution, thus formed a pink solution.
Titration is done until the color changes in NaOH solution from pink to clear color.
The titration was diluted 3 times and the HCl volume was used 11.1 ml, 10.9 ml and
11.0 ml respectively. From the average data, it is found that the concentration of
NaOH obtained is 1.10 M.
1.2.2 Production of Caustic Soda by Loewig’s process
Loewig’s process for caustic soda preparation depends on the formation of sodium
ferrate (𝑁𝑎2 𝐹𝑒2 𝑂4 ), which is then decomposed with water. The soda liquors are
mixed with ferric oxide, and the mass evaporated to dryness and calcined at a bright
red heat, usually in a revolving furnace. By the calcination, a reaction between the
sodium carbonate and the iron oxide is brought about, carbon dioxide escaping and
sodium ferrate remaining in the furnace. The mass is washed with cold water until
all soluble matter is removed; then water at 900 C is run over the sodium ferrate, by
which it is decomposed, caustic soda formed, and iron oxide regenerated; the last is
returned to the calcining process. The ferric oxide used is a natural iron ore, very
clean and free from silica or other impurities; that made by calcining a precipitated

6
ferric hydroxide is not well adapted to the process, as it gives a product difficult to
lixiviate.
1.2.3 Production of Caustic Soda by Electrolysis
The chlor-alkali process is an industrial process for the electrolysis of sodium
chloride. It is the technology used to produce chlorine and sodium hydroxide (caustic
soda), which are commodity chemicals required by industry.
In this process is used a brine (an aqueous solution of NaCl), as feedstock of
the chlor-alkali industry, in this case will be production of the chlorine, caustic soda
(sodium hydroxide), soda ash (sodium carbonate), and a wide range of other
products that can be used as raw material in other processes and industries.
Caustic soda (sodium hydroxide or NaOH) is most commonly manufactured by
the electrolysis of a sodium chloride (NaCl) solution, as the co-products formed from
the electrolytic production of caustic soda are chlorine and hydrogen.

Fig. 1 Production process of sodium hydroxide and chlorine by electrolysis.

7
There are three major production methods in the production of caustic soda by the
electrolysis and as the follows:
1. Membrane cell process
2. Diaphragm cell process
3. Mercury cell
These processes above will be discussed in details
Three production methods are in use. While the mercury cell method
produces chlorine-free sodium hydroxide, the use of several tones of mercury leads
to serious environmental problems.
In a normal production cycle a few hundred pounds of mercury per year are emitted,
which accumulate in the environment. Additionally, the chlorine and sodium
hydroxide produced via the mercury-cell chloralkali process are themselves
contaminated with trace amounts of mercury.
The membrane and diaphragm method use no mercury, but the sodium
hydroxide contains chlorine, which must be removed. Saturated brine is passed into
the first chamber of the cell where the chloride ions are oxidized at the anode, losing
electrons to become chlorine gas:
2𝐶𝑙– → 𝐶𝑙2 + 2𝑒 –
At the cathode, positive hydrogen ions pulled from water molecules are reduced by
the electrons provided by the electrolytic current, to hydrogen gas, releasing
hydroxide ions into the solution:
2𝐻2 𝑂 + 2𝑒 – → 𝐻2 + 2𝑂𝐻 –
The ion-permeable ion exchange membrane at the center of the cell allows the
sodium ions (Na+) to pass to the second chamber where they react with the hydroxide

8
ions to produce caustic soda (NaOH). The overall reaction for the electrolysis of
brine is thus:
2𝑁𝑎𝐶𝑙 + 2𝐻2𝑂 → 𝐶𝑙2 + 𝐻2 + 2𝑁𝑎𝑂𝐻
A membrane cell is used to prevent the reaction between the chlorine and hydroxide
ions. If this reaction were to occur the chlorine would be disproportionate to form
chloride and hypochlorite ions:
𝐶𝑙2 + 2𝑂𝐻– → 𝐶𝑙− + 𝐶𝑙𝑂– + 𝐻2𝑂
Above about 60 °C, chlorate can be formed:
3𝐶𝑙9 + 6𝑂𝐻 – → 5𝐶𝑙– + 𝐶𝑙𝑂3– + 3𝐻2𝑂
Because of the corrosive nature of chlorine production, the anode (where the
chlorine is formed) must be made from a non-reactive metal such as titanium,
whereas the cathode (where hydrogen is forms) can be made from a more easily
oxidized metal such as nickel.
1.2.3.1 Membrane Cell
In the membrane cell, the anode and cathode are separated by an ion-permeable
membrane. Saturated brine is fed to the compartment with the anode (the anolyte).
A DC current is passed through the cell and the NaCl splits into its constituent
components. The membrane passes Na+ ions to the cathode compartment
(catholyte), where it forms sodium hydroxide in solution. The membrane allows only
positive ions to pass through to prevent the chlorine from mixing with the sodium
hydroxide. The chloride ions are oxidised to chlorine gas at the anode, which is
collected, purified and stored. Hydrogen gas and hydroxide ions are formed at the
cathode. The diagram below shows the process flow chart of membrane process

9
 Fig. 2 Process flow chart of a membrane process
The membrane process is summarized in the diagram below. The cathode and
anode compartments are separated by a water-impermeable membrane. This means
that ions can pass, but water cannot. Concentrated sodium chloride solution
(NaCl(aq)) flows though the anode compartment and water flows though the cathode
compartment. The sodium ions and hydroxide ions combine in the cathode
compartment to produce sodium hydroxide.

10
 Fig. 3 Membrane cell

1.2.3.2 Mercury Cell

In the mercury-cell process, also known as the Castner-Kellner process, a saturated

brine solution floats on top of the cathode which is a thin layer of mercury. Chlorine
is produced at the anode, and sodium is produced at the cathode where it forms a
sodium-mercury amalgam with the mercury. The amalgam is continuously drawn
out of the cell and reacted with water which decomposes the amalgam into sodium
hydroxide and mercury. The mercury is recycled into the electrolytic cell. Mercury
cells are being phased out due to concerns about mercury poisoning from mercury
cell pollution such as occurred in Canada

Fig. 4 Mercury process for chlor-alkali

11
The process chart for the above process is shown below:

Fig.5 process flow chart for a mercury cell process

1.2.3.3 Diaphragm Cell

In the diaphragm cell process, there are two compartments separated by a permeable
diaphragm, often made of asbestos fibers. Brine is introduced into the anode
compartment and flows into the cathode compartment. Similarly to the Membrane
Cell, chloride ions are oxidized at the anode to produce chlorine, and at the cathode,
water is split into caustic soda and hydrogen. The diaphragm prevents the reaction
of the caustic soda with the chlorine. A diluted caustic brine leaves the cell. The
caustic soda must usually be concentrated to 50% and the salt removed. This is done

12
using an evaporative process with about three tons of steam per tons of caustic soda.
The salt separated from the caustic brine can be used to saturate diluted brine. The
chlorine contains oxygen and must often be purified by liquefaction and evaporation.

A process flow chart is used to describe the process of diaphragm cell and amongst
the two (2) other manufacturing process of caustic soda it’s the most suitable and
generally accepted process.

Fig. 6 Diaphragm Cell.

13
Fig. 7 Process flow chart of a diaphragm process.

14
 Mercury
Caustic quality High, <30 ppm NaCl 5-
150 µg Hg/l (Before
treatment the Hg level is
between 2.5-25 mg Hg/l)
Caustic concentration 50%
Chlorine quality Contains low levels of
oxygen (< 0.1%) and
hydrogen
Brine feedstock Some purification
required but depends on
purity of salt or brine used
Variable electric load Good variable electricity
performance load performance, down
to 30 % of full load
possible for some cell
rooms, which is very
important in some
European countries
Table 1.1: Main characteristics of the different electrolysis processes after [Kirk-
Othmer, 1991], [Lindley, 1997], [Ullmann’s, 1996] and other sources
Diaphragm
1.0-1.5% by weight NaCl
(Before treatment the
NaCl content is about
18%) 0.1% NaClO3 Not
suitable for some
applications
12%, requires
concentration to 50% for
some applications
Oxygen content between
1.5-2.5%
Some purification
required but depends on
purity of salt or brine used
Tolerates only slight
variation in electricity
load and brine flows in
order to maintain
diaphragm performance
Membrane
High, <50 ppm NaCl
33%, requires
concentration to 50% for
some applications
Oxygen content between
0.5% and 2%, depending
on whether an acidified
electrolyte is used
Very high purity brine is
required as impurities
affect membrane
performance
Variable electricity load
performance less than for
mercury (40-60%
depending on design
load), affects product
quality, and efficiency at
lower loads

1.3 Selection of production method:

The cause of using membrane is:

1 - Membrane cells are very flexible in use.

2 - Cells can be connected together to give whatever capacity is required.

3 - Small users of chlorine, such as paper mills (where chlorine is used as a bleach).

4 - Can have one or two cells working on site.

5 - Can work for long period up to 3 years depending on the purity of the raw
material.

15
1.4 Properties of Caustic Soda

Pure sodium hydroxide have a high affinity for water, so the physical and chemical
properties of the pure substance are difficult to determine,
Many of the data are obtainable only by extrapolating values for impure sodium
hydroxide. The same is true for the concentration dependent physical properties of
aqueous solutions of sodium hydroxide, since these solutions have a strong tendency
toward super saturation.

1.4.1 Physical Properties

MWt. 40
Appearance white, crystalline as in fig. 8
Density (liquid, 350 °C) mp (soda and 1.77 g/cm3 322 ± 2 °C
water free).
Density at 20 °C 1.208 g/cm3
Heat of fusion 6.77 k/mol
Boiling point at 0.1 MPa 1388 °C (calculated) 3.24 J/kg. K
Melting Point 318.4 ℃
Specific heat capacity at 20 °C 3644 J/(kg.k)
Thermal conductivity at 20 °C 0.658 W/(m.k)
Dynamic viscosity at 20 °C 3.3 mPa.s
Kinematic viscosity at 20 °C 0.000003 m2/s
Prandtl number at 20 °C 18.28
Coefficient thermal expansion at 20 °C 0.000504 1/k
Thermal diffusivity at 20 °C 1.495*10-7 m2/s

16
 Fig. 8 Whitish pellets of Caustic soda

1.4.2 Chemical Properties

1- Reaction with acids

Sodium hydroxide reacts with aprotic acids to produce water and the corresponding
salts. For example, when sodium hydroxide reacts with hydrochloric acid, sodium
chloride is formed:
𝑁𝑎𝑂𝐻(𝑎𝑞) + 𝐻𝐶𝑙(𝑎𝑞) → 𝑁𝑎𝐶𝑙(𝑎𝑞) + 𝐻2 𝑂
In general, such neutralization reactions are represented by one simple net ionic
equation:
− +
𝑂𝐻(𝑎𝑞) + 𝐻(𝑎𝑞) → 𝐻2 𝑂(𝑙)
This type of reaction with a strong acid releases heat, and hence is exothermic. Such
acid-base reactions can also be used for titrations. However, sodium hydroxide is
not used as a primary standard because it is hygroscopic and absorbs carbon dioxide
from air.

17
2- Reaction with acidic oxides
Sodium hydroxide also reacts with acidic oxides, such as sulfur dioxide. Such
reactions are often used to "scrub" harmful acidic gases (like SO2 and H2S) produced
in the burning of coal and thus prevent their release into the atmosphere. For
example,
2𝑁𝑎𝑂𝐻 + 𝑆𝑂2 → 𝑁𝑎2 𝑆𝑂3 + 𝐻2 𝑂

3- Reaction with amphoteric metals and oxides

Glass reacts slowly with aqueous sodium hydroxide solutions at ambient
temperatures to form soluble silicates. Because of this, glass joints and stopcocks
exposed to sodium hydroxide have a tendency to "freeze". Flasks and glass-lined
chemical reactors are damaged by long exposure to hot sodium hydroxide, which
also frosts the glass. Sodium hydroxide does not attack iron since iron does not have
amphoteric properties (i.e., it only dissolves in acid, not base). A few transition
metals, however, may react vigorously with sodium hydroxide.
In 1986, an aluminum road tanker in the UK was mistakenly used to transport
25% sodium hydroxide solution, causing pressurization of the contents and damage
to the tanker. The pressurization was due to the hydrogen gas which is produced in
the reaction between sodium hydroxide and aluminum:
2𝐴𝑙 + 2𝑁𝑎𝑂𝐻 + 6𝐻2 𝑂 → 2𝑁𝑎𝐴𝑙(𝑂𝐻)4 + 3𝐻2
4- Precipitant
Unlike sodium hydroxide, the hydroxides of most transition metals are insoluble,
and therefore sodium hydroxide can be used to precipitate transition metal
hydroxides. The following colures are observed: blue-copper, green-iron (II),
yellow/brown-iron (III). Zinc and lead salts dissolve in excess sodium hydroxide to
give a clear solution of 𝑁𝑎2 𝑍𝑛𝑂2 or 𝑁𝑎2 𝑃𝑏𝑂2 .

18
Aluminum hydroxide is used as a gelatinous flocculants to filter out particulate
matter in water treatment. Aluminum hydroxide is prepared at the treatment plant
from aluminum sulfate by reacting it with sodium hydroxide.
𝐴𝑙2 (𝑆𝑂4 )3 + 6 𝑁𝑎𝑂𝐻 → 2𝐴𝑙(𝑂𝐻)3 + 3𝑁𝑎2 𝑆𝑂4

5- Saponification
Sodium hydroxide can be used for the base-driven hydrolysis of esters (as in
saponification), amides and alkyl halides. However, the limited solubility of sodium
hydroxide in organic solvents means that the more soluble potassium hydroxide
(KOH) is often preferred.
1.5 Uses of Caustic Soda
Caustic soda, is used for many household and industrial purposes. The chemical
forms a strong alkaline solution when you mix it with water.

a) It is used for household purposes in cleaning

b) It is used in many industries like paper and pulp, textiles, and used in the
manufacturing of soaps, detergents and cleaners.
c) Since it is cheaply available, many educational institutions use it in student labs.
In labs, it is generally used to drive chemical reactions.
d) It is a very good neutralizing agent, especially when used for neutralizing acids
and also for refining petrol
e) It is used in oil refineries and for oil drilling, since it increases the viscosity and
prevents heavy materials from settling.
f) Sodium hydroxide is also used in the manufacturing process of soaps and
detergents.

19
g) Sodium Hydroxide is used along with sodium sulfide to separate lignin from
cellulose. It can also be used as a bleaching agent to bleach brown pulp.
Anhydrous sodium hydroxide can be used as a catalyst for preparing biodiesel
because it is cheaper than any other alkalizes.
h) It is used as cleaner in breweries and wineries and also for etching aluminum
surfaces, as it gives it a polished look.
i) Out of the many uses of sodium hydroxide one major use is that it can be used for
washing and chemical peeling of fruits and vegetables, chocolates and cocoa
processing, as well as soft drink processing.
References
1 - Sodium Hydroxide - Compound Summary". Retrieved June 12, 2012.
2 - Zumdahl, Steven S. (2009). Chemical Principles 6th Ed. Houghton Mifflin
Company.
3 - Cetin Kurt, Jürgen Bittner (2005), "Sodium Hydroxide", Ullmann's Encyclopedia
of Industrial Chemistry, Weinheim: Wiley-VCH,
4 - Kirk-Othmer Encyclopedia of Chemical Technology 5th edition (online, account
needed), John Wiley & Sons. Accessed November 21, 2005.
5 - Deming, Horace G. (1925). General Chemistry: An Elementary Survey
Emphasizing Industrial Applications of Fundamental Principles (2nd ed.). New
York: John Wiley & Sons
6 - Thacker, H. Leon; Kastner, Justin (August 2004). Carcass Disposal: A
Comprehensive Review. Chapter 6. National Agricultural Biosecurity Center,
Kansas State University, 2004. Retrieved 2010-03-08
7 - Morfit, Campbell (1856). A treatise on chemistry applied to the manufacture of
soap and candles. Parry and McMillan.

20
Caustic Soda Production Flow Sheet

21
 Chapter Two
Material Balance

22
Material Balance

Basis: 1500 Kg/hr of NaOH.

2𝑁𝑎𝐶𝑙 + 2𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐻2 + 𝐶𝑙2

Mwt 58.5 18 40 2 71
n(mole) 37.5 37.5 37.5 18.75 18.75
m(Kg/hr) 2193.75 675 1500 37.5 1331.25
* Sample Calculation:

𝑤𝑒𝑖𝑔ℎ𝑡 𝑚
𝑚𝑜𝑙𝑒𝑠 = ⇒𝑛=
𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑀𝑤𝑡

For NaCl:

1500
𝑛= = 37.5 𝐾𝑚𝑜𝑙𝑒/ℎ𝑟
40

𝑁𝑎𝐶𝑙(𝐾𝑔) = 37.5 × 58.5 = 2193.75 𝐾𝑔

𝐻2 𝑂(𝐾𝑔) = 37.5 × 18 = 675 𝐾𝑔/ℎ𝑟

𝐻2 (𝐾𝑔) = 18.75 × 2 = 37.5 𝐾𝑔/ℎ𝑟

𝐶𝑙2 (𝐾𝑔) = 18.75 × 71 = 1331.25 𝐾𝑔/ℎ𝑟

23
Assumption:

2193.75𝐾𝑔/ℎ𝑟 of NaCl

26 𝐾𝑔/ℎ𝑟 of 𝑁𝑎2 𝐶𝑂3

15
× 𝐹 = 2193.75
100

𝐹 = 14625 𝐾𝑔/ℎ𝑟

Overall Material Balance:

𝑚𝑖𝑛 = 𝑚𝑜𝑢𝑡

𝐹𝑒𝑒𝑑(𝐹) + 𝑁𝑎2 𝐶𝑂3 = 𝑆𝑙𝑢𝑑𝑔𝑒 + 𝑁𝑎𝐶𝑙

14625 + 26 = 𝑆𝑙𝑢𝑑𝑔𝑒 + 𝑁𝑎𝐶𝑙 ---------- eq (1)

Material Balance of NaCl:

𝑚𝑖𝑛 = 𝑚𝑜𝑢𝑡

2193.75 = 28% 𝑁𝑎𝐶𝑙 + 10% 𝑆𝑙𝑢𝑑𝑔𝑒

219375 = 28𝑁𝑎𝐶𝑙 + 10𝑆𝑙𝑢𝑑𝑔𝑒

219375−10𝑆𝑙𝑢𝑑𝑔𝑒
𝑁𝑎𝐶𝑙 = ----------eq (2)
28

On solving eq (1) and eq (2) we get:

𝑁𝑎𝐶𝑙 = 4022.056 𝐾𝑔/ℎ𝑟

𝑆𝑙𝑢𝑑𝑔𝑒 = 10602.944 𝐾𝑔/ℎ𝑟

24
Membrane Cell:

For 55% efficiency of Caustic Soda and Cl2

2𝑁𝑎𝐶𝑙 + 2𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐻2 + 𝐶𝑙2

Mass
1126.175 346.5 770 19.25 683.375
Flow(kg/hr)
Molecular
58.5 18 40 2 71
Weight
Moles
19.25 19.25 19.25 9.625 9.625
Flow(Kmole/hr)
Sample Calculation:

For NaOH :

∗ 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑁𝑎𝐶𝑙 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = 28% (𝑁𝑎𝐶𝑙)

∗ 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑁𝑎𝐶𝑙 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = 28% (4022.055) = 1126.175 𝐾𝑔/ℎ𝑟

1126.175
𝐶𝑜𝑛𝑣𝑒𝑟𝑡𝑖𝑛𝑔 𝑖𝑛𝑡𝑜 𝑚𝑜𝑙𝑎𝑟 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 = = 19.25 𝐾𝑚𝑜𝑙𝑒/ℎ𝑟
58.5

25
By Stoichiometry:

2𝑁𝑎𝐶𝑙 → 2𝑁𝑎𝑂𝐻 2𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 2𝐻2 𝑂 → 𝐻2 2𝐻2 𝑂 → 𝐶𝑙2

2 2 2 2 2 1 2 1
19.25 x 19.25 x 19.25 x 19.25 x
2 × x = 19.25 × 2 2 × x = 19.25 × 2 2 × x = 19.25 × 1 2 × x = 19.25 × 1
x = 19.25 Kmole/hr x = 19.25 Kmole/hr x = 9.625 Kmole/hr x = 9.625 Kmole/hr

But since we have for 55% efficiency for membrane cell

∗ 𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻 = 55%(19.25) = 10.587 𝐾𝑚𝑜𝑙𝑒/ℎ𝑟

By Stoichiometry:

2𝑁𝑎𝐶𝑙 → 2𝑁𝑎𝑂𝐻 2𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 2𝐻2 𝑂 → 𝐻2 2𝐻2 𝑂 → 𝐶𝑙2

2 2 2 2 2 1 2 1
10.587 x 10.587 x 10.587 x 10.587 x
2 × x = 10.587 × 2 2 × x = 10.587 × 2 2 × x = 10.587 × 1 2 × x = 10.587 × 1
x = 10.587 Kmole/hr x = 10.587 Kmole/hr x = 5.293 Kmole/hr x = 5.293 Kmole/hr

Material Balance out of Membrane Cell:

∴ 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑁𝑎𝑂𝐻 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 = 10.587 × 40 = 423.48 𝐾𝑔/ℎ𝑟

∴ 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑁𝑎𝐶𝑙 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 = 10.587 × 58.5 = 619.339 𝐾𝑔/ℎ𝑟

∴ 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐻2 𝑂 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 = 10.587 × 18 = 190.566 𝐾𝑔/ℎ𝑟

∴ 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐻2 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 = 5.293 × 2 = 10.587 𝐾𝑔/ℎ𝑟

∴ 𝑡ℎ𝑒 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑙2 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 = 5.293 × 71 = 375.803 𝐾𝑔/ℎ𝑟

26
Overall material balance over Evaporator:

Aq. NaOH (35% NaOH) = Aq. NaOH (50% NaOH) + Water Vapor

423.48 = 296.436 + 127.044

Material Balance on NaOH entering the Evaporator:

𝑚𝑖𝑛 = 𝑚𝑜𝑢𝑡

𝑝𝑢𝑟𝑒 𝑁𝑎𝑂𝐻 𝑜𝑢𝑡 𝑜𝑓 𝑎𝑞. 𝑁𝑎𝑂 = 35% (423.48) = 148.218 𝐾𝑔/ℎ𝑟

𝑤𝑎𝑡𝑒𝑟 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 𝑖𝑛 𝑖𝑛𝑐𝑜𝑚𝑖𝑛𝑔 𝑎𝑞. 𝑁𝑎𝑂𝐻 = 423.48 − 148.218 = 275.262 𝐾𝑔/ℎ𝑟

Material Balance on NaOH exiting the Evaporator:

𝑚𝑖𝑛 = 𝑚𝑜𝑢𝑡

Amount of NaOH obtained after 50% concentration is:

50% 𝑜𝑓 𝑎𝑞. 𝑁𝑎𝑂𝐻 = 148.218 𝐾𝑔/ℎ𝑟

148.218 = 0.5 × 𝑁𝑎𝑂𝐻

148.218
𝑁𝑎𝑂𝐻 = = 296.436 𝐾𝑔/ℎ𝑟
0.5

27
𝑊𝑎𝑡𝑒𝑟 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 𝑖𝑛 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑 𝑎𝑞. 𝑁𝑎𝑂𝐻(50%) = 296.436 − 148.218 = 148.218 𝐾𝑔/ℎ𝑟

𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑤𝑎𝑡𝑒𝑟 𝑣𝑎𝑝𝑜𝑟 = 275.262 − 148.218 = 127.044 𝐾𝑔/ℎ𝑟

Overall Material Balance over dryer

𝑚𝑖𝑛 = 𝑚𝑜𝑢𝑡

𝑤𝑒𝑡 𝐶𝑙2 + 𝐻2 𝑆𝑂4 (98% 𝑐𝑜𝑛) = 𝐷𝑟𝑦 𝐶𝑙2 + 𝐻2 𝑆𝑂4 (70% 𝑐𝑜𝑛)

375.803 + 98% (25 𝐾𝑔) = 𝐷𝑟𝑦 𝐶𝑙2 + 𝐻2 𝑆𝑂4 (70%) ---------- (1)

Material Balance of 𝐻2 𝑆𝑂4 over Dryer:

𝐼𝑛𝑙𝑒𝑡 𝐻2 𝑆𝑂4 (98% 𝑐𝑜𝑛) = 𝑂𝑢𝑡𝑙𝑒𝑡 𝑜𝑓 𝐻2 𝑆𝑂4 (70% 𝑐𝑜𝑛)

98% (25) = 70% 𝐻2 𝑆𝑂4

98 70 𝐻2 𝑆𝑂4
(25) = ( )
100 100 𝑍

𝑍 = 70% 𝐻2 𝑆𝑂4 = 35 𝐾𝑔/ℎ𝑟

Substituting in eq (1)

𝐷𝑟𝑦 𝐶𝑙2 = 365.303 𝐾ℎ/ℎ𝑟

28
Chapter Three
Energy Balance

29
3.1 Steam Required For Heating Brine

𝑚𝐶𝑃 ∆𝑇 = 𝑚𝑡 𝜆

4022.056 × 3.274 × (333 − 298) = 𝑚𝑡 × 2358.40

𝑚𝑡 = 195.423 𝐾𝐽/ℎ𝑟

3.2 Energy Balance on Membrane Cell

Assumption Datum temperature = 𝟐𝟓℃

Inlet Stream

Material Name Specific Heat at 60℃ Flow Rates 𝐾𝑔/ℎ𝑟

𝐻2 𝑂 4.185 𝐾𝐽/𝐾𝑔. °𝐾 346.5
Aq.NaCl Solution 3.247 𝐾𝐽/𝐾𝑔. °𝐾 1126.175

Outlet Stream

Material Name Specific Heat at 80℃ Flow Rates 𝐾𝑔/ℎ𝑟

𝐻𝑦𝑑𝑟𝑜𝑔𝑒𝑛(𝑔) 14.43 𝐾𝐽/𝐾𝑔. °𝐾 190.566
𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒(𝑙) 0.48 𝐾𝐽/𝐾𝑔. °𝐾 375.803
𝑁𝑎𝑂𝐻(35% 𝑏𝑦 𝑤𝑡) 3.594 𝐾𝐽/𝐾𝑔. °𝐾 423.48
Depleted Brine 3.247 𝐾𝐽/𝐾𝑔. °𝐾 619.339

For Input Stream

𝑎𝑞. 𝑁𝑎𝐶𝑙 = 𝑚𝑐𝑃 ∆𝑇

𝑎𝑞. 𝑁𝑎𝐶𝑙 = 1126.175 × 3.247 × (333 − 298) = 127984.158 𝐾𝐽/ℎ𝑟

𝐻2 𝑂 = 𝑚𝑐𝑃 ∆𝑇

𝐻2 𝑂 = 346.5 × 4.187 × (333 − 298) = 50777.842 𝐾𝐽/ℎ𝑟

30
𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝐼𝑛𝑝𝑢𝑡 = 127984.158 + 50777.842

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝐼𝑛𝑝𝑢𝑡 = 178762 𝐾𝐽/ℎ𝑟

For Outlet Stream

𝐻2 = 𝑚𝑐𝑃 ∆𝑇

𝐻2 = 190.566 × 14.43 × (353 − 298) = 151242.705 𝐾𝐽/ℎ𝑟

𝐶𝑙2 = 𝑚𝑐𝑃 ∆𝑇

𝐶𝑙2 = 375.803 × 0.48 × (353 − 298) = 9921.1992 𝐾𝐽/ℎ𝑟

𝑎𝑞. 𝑁𝑎𝑂𝐻 = 𝑚𝑐𝑃 ∆𝑇

𝑎𝑞. 𝑁𝑎𝑂𝐻 = 423.48 × 3.594 × (353 − 298) = 83709.291 𝐾𝐽/ℎ𝑟

𝐷𝑒𝑝𝑙𝑒𝑡𝑒𝑑 𝐵𝑟𝑖𝑛𝑒 = 𝑚𝑐𝑃 ∆𝑇

𝐷𝑒𝑝𝑙𝑒𝑡𝑒𝑑 𝐵𝑟𝑖𝑛𝑒 = 619.339 × 3.247 × (353 − 298) = 110604.655 𝐾𝐽/ℎ𝑟

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 151242.705 + 9921.1992 + 83709.291 + 110604.655

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 355477.850 𝐾𝐽/ℎ𝑟

2𝑁𝑎(𝑠) + 2𝐻2 𝑂 → 2𝑁𝑎𝑂𝐻 + 𝐻2 𝑂 ∆𝐻 = −368.4 𝐾𝐽/𝑔𝑚𝑁𝑎

𝐷𝑒𝑝𝑙𝑒𝑡𝑒𝑑 𝐵𝑟𝑖𝑛𝑒 = 110604.655(50% 𝑏𝑦 𝑤𝑡 𝑜𝑓 𝑁𝑎𝐶𝑙)

0.5 × 110604.655 × −368.4 = −20373377.45 𝐽/ℎ𝑟

3.3 Energy Balance on Dryer

Inlet Stream

Material Name Specific Heat at 80℃ Flow Rates 𝐾𝑔/ℎ𝑟

𝑎𝑞. 𝑁𝑎𝑂𝐻 (35% 𝑏𝑦 𝑤𝑡) 3.594 𝐾𝐽/𝐾𝑔. °𝐾 148.218

Outlet Stream

31
 Material Name Specific Heat at 110℃ Flow Rates 𝐾𝑔/ℎ𝑟
50% 𝐶𝑎𝑢𝑠𝑡𝑖𝑐 𝑆𝑜𝑑𝑎 3.564 𝐾𝐽/𝐾𝑔. °𝐾 296.436
Material Name Latent Heat at 110℃ Flow Rates 𝐾𝑔/ℎ𝑟
𝑆𝑡𝑒𝑎𝑚 2231.86 𝐾𝐽/𝐾𝑔 94.127

For Input Stream

𝑎𝑞. 𝑁𝑎𝑂𝐻 (35% 𝑏𝑦 𝑤𝑡) = 𝑚𝑐𝑃 ∆𝑇

𝑎𝑞. 𝑁𝑎𝑂𝐻 (35% 𝑏𝑦 𝑤𝑡) = 148.218 × 3.564 × (353 − 298) = 29053.692 𝐾𝐽/ℎ𝑟

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝐼𝑛𝑝𝑢𝑡 = 29053.692 𝐾𝐽/ℎ𝑟

For Outlet Stream

50% 𝐶𝑎𝑢𝑠𝑡𝑖𝑐 𝑆𝑜𝑑𝑎 = 𝑚𝑐𝑃 ∆𝑇

50% 𝐶𝑎𝑢𝑠𝑡𝑖𝑐 𝑆𝑜𝑑𝑎 = 296.436 × 3.564 × (353 − 298) = 58107.384 𝐾𝐽/ℎ𝑟

𝑆𝑡𝑒𝑎𝑚 = 𝑚𝑐𝑃 ∆𝑇

𝑆𝑡𝑒𝑎𝑚 = 94.127 × 2231.86 × (353 − 298) = 11554305.74 𝐾𝐽/ℎ𝑟

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 58107.384 + 11554305.74

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 11612413.13 𝐾𝐽/ℎ𝑟

3.4 Energy Balance on Dryer

Inlet Stream

Material Name Specific Heat at 80℃ Flow Rates 𝐾𝑔/ℎ𝑟

𝑊𝑒𝑡 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 0.48 𝐾𝐽/𝐾𝑔. °𝐾 375.803
𝐻2 𝑆𝑂4 (98% 𝑏𝑦 𝑤𝑡) 1.465 𝐾𝐽/𝐾𝑔. °𝐾 25

Outlet Stream

32
 Material Name Specific Heat at 80℃ Flow Rates 𝐾𝑔/ℎ𝑟
𝐷𝑟𝑦 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 0.48 𝐾𝐽/𝐾𝑔. °𝐾 365.303
𝐻2 𝑆𝑂4 (70% 𝑏𝑦 𝑤𝑡) 2.177 𝐾𝐽/𝐾𝑔. °𝐾 35

For Input Stream

𝑊𝑒𝑡 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 = 𝑚𝑐𝑃 ∆𝑇

𝑤𝑒𝑡 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 = 375.803 × 0.48 × (353 − 298) = 9921.1992 𝐾𝐽/ℎ𝑟

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝐼𝑛𝑝𝑢𝑡 = 9921.1992 𝐾𝐽/ℎ𝑟

For Outlet Stream

𝑊𝑒𝑡 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 = 𝑚𝑐𝑃 ∆𝑇

𝑊𝑒𝑡 𝐶ℎ𝑙𝑜𝑟𝑖𝑛𝑒 = 365.303 × 0.48 × (353 − 298) = 9644 𝐾𝐽/ℎ𝑟

𝐻2 𝑆𝑂4 (70%) = 𝑚𝑐𝑃 ∆𝑇

𝐻2 𝑆𝑂4 (70%) = 35 × 2.177 × (353 − 298) = 4190.725 𝐾𝐽/ℎ𝑟

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 9644 + 4190.725

𝑇𝑜𝑡𝑎𝑙 𝐻𝑒𝑎𝑡 𝑂𝑢𝑡𝑝𝑢𝑡 = 13834.725 𝐾𝐽/ℎ𝑟

𝑅𝑒𝑎𝑐𝑡𝑒𝑑 𝑚𝑜𝑙𝑒𝑠
%𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑁𝑎𝐶𝑙 = × 100
𝑇𝑜𝑡𝑎𝑙 𝑚𝑜𝑙𝑒𝑠
127984.158 − 38036.844
%𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 𝑁𝑎𝐶𝑙 = × 100
127984.158

33