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Chemical Process

Industries
(CHE-105)
Saqib Javed
Alkali Industry
(Caustic Soda, Soda Ash)
NaOH, Na2CO3

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Introduction
• Sodium hydroxide, also known as Caustic Soda
• It is a highly caustic metallic base.
• It is a white solid available in pellets, flakes, granules,
and as a 50% saturated solution.
• Sodium hydroxide is soluble in water, ethanol and
methanol.
• This alkali is deliquescent and readily absorbs
moisture and carbon dioxide in air.

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Uses
Caustic is consumed in large
quantities in the manufacture of:

• Rayon
• Explosives
• Soap
• Paper
Chemicals
• Petroleum Refining

Soap
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Methods of Manufacture
Caustic soda is one of the main products from soda ash
and is frequently made in the soda ash plant.
1. Chemical: Lime Soda Process
2. Electrochemical: Chloro Alkali Process
• Mercury Cell Process
• Diaphragm Cell Process
• Membrane Cell Process

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Chemical Process…Lime Soda Process
• Previously made by Causticization of soda ash with
lime
• Na2CO3 + Ca(OH)2 → 2 NaOH + CaCO3
• Only 10% NaOH solution obtained

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Lime Soda Process

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Lime Soda Process
• Fresh lime, make-up lime is fed along with some
of the soda ash solution to a combination
classifier-slaker. Milk of lime is formed.
• Grit is removed from the slurry by the classifier.
• The soda solution is causticized with a slight
excess of lime in three agitators in series.
• The sludge in the bottom of the first thickener is
pumped with a diaphragm pump to the second
thickener.
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• In 2nd thickner, filtrate and water are added. The
overflow from this thickener is used as a weak liquor
to make up the original soda solution.
• The sludge from the second thickener is filtered on
and washed.
• The filtrate is returned to the second thickener.
• The cake is calcined in the limekiln.

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Electrolysis of Brine – Most popular method

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CHLOR-ALKALI PROCESS
• It is an industrial process for the electrolysis of
sodium chloride solution (brine).
• Three important chemicals, NaOH, Cl2, H2, can be obtained
by electrolyzing an aqueous NaCl solution (brine).

• This forms the basis of the chlor- alkali industry.

• Chlorine at Anode; Hydrogen along with alkali hydroxide at


cathode are produced.

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Chlor-Alkali
• The overall reaction for the electrolytic
production of caustic soda and chlorine is:
• 2NaCl (aq) + 2H2O Cl2 (g) + H2(g) + 2 NaOH(aq)
• Energy consumed in electrolysis of brine is the
product of the current flowing and the potential
of cell. E=VI
• Minimum voltage required for the process is
given by Gibbs-Helmholtz equation. 2.31 Volts

Expresses relation b/w electric energy


and heat of reaction of the system.

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MANUFACTURING PROCESS

• Brine Purification

• Brine Electrolysis

• Evaporation and Salt Separation

• Final Evaporation

• Finishing of Caustic soda

• Special Purification of Caustic soda


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Brine Purification
• Ca,Fe and Mg compounds plug the diaphragm
cell and will enhance Voltage consumption.
• Precipitation with Soda Ash is commonly used
to remove them.
• Sulfates may be removed by BaCl2.
• Brine is preheated with other streams.
Reduce Energy
Requirement
• Additional treatment with phosphates is
required for membrane cells.
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Brine Electrolysis
• 3.0 – 4.5 V per cell is used; whichever method is
adopted
• Monopolar – Cells connected in parallel and low
voltage applied to each cell
• Bipolar – Cells are connected in series and high voltage
applied

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Evaporation and Salt Separation
• The weak 10-15 % NaOH solution is evaporated to
around 50 % NaOH in a double or triple-effect
evaporator with salt separators, followed by a
washing filter.
• Salt crystallizes out and recycled into brine.
• The liquid Caustic may be sold, after thorough
settling, as liquid caustic soda in tanks or in drums

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Final Evaporation
• Cooled and settled 50% caustic may be concentrated
in a single-effect evaporator to 70 – 75% NaOH using
steam.
• Strong caustic must be handled in steam-jacketed
pipes to prevent solidification
.

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Self Study
• Finishing of Caustic
• Special Purification of Caustic

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Process Chemistry

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Water
Salt (Rock)
Brine
Salt
(Recycled) Precipitants
Precipitation

Residue
Filtration

Heat Exchange
Hydrogen
Electrolytic Cell

Concentration Chlorine

Cooling

Storage NaOH
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Recycle Salt

Water NaOH
P-1 Ev-1
Rock Salt

Water Steam Out


RV-1
Sp-1 Steam In

Cl2

Cv-1 Salt
Ag-1
H2
Heated
Brine
H2 P-1
NaOH

H-1

Rock Salt ST-1

BT-1 H-2
Cl2 Pr-1 FR-1
H2 EC-1
NaOH
NaOH
ST-1
P-2 P-3 ST-2

Special Purification NaOH

Valve
Cooling Water Out
Heated
H-2
Cv-1 Salt
Cooling Water In
Cr-1
Ev-2

Brine
Steam Out FP-1 STT-1
Ag-1 Steam In

H2 CT-1
EC-1 Salt Out
CF-1 H-1
Fr-1

NaOH Liq NaOH

NaOH
BT-1 P-2 P-4
Pr-1 FR-1

Brine Preparation &


Pump Conveyor Agitator
Brine Electrolysis
Purification
Brine Tank Heat Exchanger Precipitator Filter Electrolytic Cell Storage Tank Separator Evaporator RoVac Settling Tank Flaker Finishing Pot
P(1-4) Cv-1 Ag-1 BT-1 H(1-2) Pr-1 Fr-1 EC-1 ST(1-2) Sp-1 Ev(1-2) RV-1 STT-1 Fr-1 PF-1
Centrifuge Cooling Tower Crystallizer
CF-1 CT-1 Cr-1

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Flow Sheet

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Final Product

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Chlorine Handling
• Hot chlorine evolved from the anode carries
much water vapor. It is cooled to condense
most of this vapor and then dried in a sulfuric
acid scrubber.
• The dried chlorine is compressed and heat' of
compression is removed progressively by
water.
• Liquefied chlorine must be cooled to as low as
-50°F and then stored.

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Types of Cells
• Mercury Cell

• Diaphragm Cell

• Membrane Cell

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Diaphragm Cell
• In the diaphragm cell process
– Positive electrode (made of titanium)
– Negative electrodes (made of steel)
– Separated by permeable diaphragm.
– Hydrogen is formed at negative electrode
• 2H2O(l) + 2e-  H2(g) +2OH-(ag)
– Chlorine is formed at positive electrode
• 2Cl-(ag)  Cl2(g) +2e-
• The Sodium hydroxide solution formed
accumulates in the cathode compartment and
is piped off.

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Diaphragm Cell
• The diaphragm is made of asbestos
– Sodium chloride solution can flow between the electrodes
– Chlorine and hydrogen gas can’t flow through( preventing
the OH- ions flowing towards the positive electrode)
• The Resulting solution contains about
– 10% sodium hydroxide
– 15% unused sodium chloride by mass
• The solution is concentrated by evaporation and the
sodium chloride crystallizes out leaving a 50%
solution of sodium hydroxide

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Advantages

• Diaphragm Permits the construction of


compact cells of lowered resistance as the
electrodes can be placed close together
• Diaphragm permits flow of brine from anode
to cathode and thus greatly lessens side
reactions
• Can run on dilute (20%), fairly impure brine
• Dilute brine produces NaOH 11% (NaCl 15%)

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Disadvantages
• Consumes lot of energy for evaporation
• For 1 ton of 50% caustic need 2600 kg of water to be
evaporated.
• Some amount of Chloride ion remains and is highly
objectionable to some industries
• Diaphragms become clogged with use and should be
replaced regularly

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Membrane Cells
• Uses a partially permeable ion exchange
membrane rather than asbestos
• Separate compartments by porous chemically
active plastic sheets; that allows sodium ions
to pass but reject hydroxyl ions.
• The membrane is made of a fluorinated
polymer and is permeable to positive ions but
not negative ions.

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Advantages
• Purpose of membrane is to exclude OH- and Cl- ions from
anode chamber
• Thus making the product far lower in salt than that from a
diaphragm cell.
• Membrane cells operate using more concentrated brine and
produce purer and more concentrated product
• (30-35% NaOH containing 50 ppm of NaCl)
• Requires only 715 kg of water to be evaporated to produce 1
M ton of 50% NaOH.
Drawback:
• Membranes are more readily clogged than diaphragms, so
some of savings are lost

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Comparison of Cell Technologies
Mercury Diaphragm Membrane

Operating current density ( 8 - 13 0.9 - 2.6 3-5


kA/m2)

Cell voltage (V) 3.9 - 4.2 2.9 - 3.5 3.0 - 3.6

NaOH strength (wt%) 50 12 33-35

Energy consumption ( kWh/MT 3360 (10) 2720 (1.7) 2650 (5)


Cl2) at a current density of
(kA/m2)
Steam consumption (kWh/MT 0 610 180
Cl2) for concentration to 50%
NaOH
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Advantages & Disadvantages of
Electrochemical Methods
Process Advantages Disadvantages

Diaphragm •Use of well brine •Use of asbestos


Process • Low electricity consumption •High steam consumption
•Low purity caustic
•Low chlorine quality
Mercury •50% caustic direct from cell •Use of mercury
Process •High purity chlorine and •Expensive cell operation
hydrogen •Large floor space
•Simple brine purification •Costly environment
protection
Membrane •Low energy consumption •Cost of membrane
Process •Low capital investment •Use of solid salt, high purity
•High purity caustic brine
•Insensitivity to cell load •High oxygen content in
variations chlorine
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and shutdowns
Ammonia Soda (Solvay) Process
for Production of Soda Ash

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Properties Of Na2CO3
Physical Chemical
Odorless Thermal Decomposition at 1000 °C
and 200 Pa

Hygroscopic; Alkaline in
Na2CO3 Na2O+CO2
nature
M.P. 851 °C
M.wt = 106
Density@20°C=2.53 g/cm3

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Applications

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Raw Materials

Salt(Brine) Limestone(hard Coke


and strong)

Ammonia(as a
catalyst)

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Process Chemistry
Overall reaction
CaCO3 + 2NaCl Na2CO3 + CaCl2
This reaction takes place in a number of steps

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By Products

Ammonium Chloride

Calcium Chloride

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Manufacturing Process

• Brine preparation
• Purification of brine
• Ammonia absorption
• Precipitation of bicarbonate
• Filtration of bicarbonate
• Recovery of ammonia

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NaCl Ammoniated NH3
Brine
Limestone NaCl
H2O
CaCO3
NH3 NH3

CO2 Carbonating
Lime kiln
tower

CaO
H2O filter NH4Cl

Ammonia recovery
Ca(OH)2
Lime slaker

Product By-product
NaHCO3 CaCl2

Product 46
Na2CO3
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Cyclic process

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Unit Operations---Equipment
 Settling Vat
 Absorber
 Carbonator
 Rotary Vaccum Filter
 Lime Kiln
 Lime Slaker
 Gas Compressor
 Calciner

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Settling Vats
• They are used for brine purification before it
flows to the strong ammonia absorber

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Absorber
• NH3 is absorbed in
the purified brine.

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Carbonator
• Formation of (NH4)2CO3
• Formation of NH4HCO3

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Rotary Vacuum Filter
Ammonium Chloride
leaving with the product of
Carbonator is removed.

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Lime Kiln
• A lime kiln is used to produce quicklime
through the calcination of limestone. The
chemical eq. for this reaction is
• CaCO3 CaO + CO2

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Lime Slaker
• Lime Slaker is used to
make milk of lime by
adding water to calcium
oxide.

• Milk of lime is used to


recover Ammonia by
reacting with NH4Cl(liquor)

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Calciner
Calcination:
• Heating a substance
below its Melting point.
It is unit process.

• Conversion of Sodium-
Bicarbonate into
Sodium-Carbonate

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Storage Transportation

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Advantages of Solvay Process
• Can use low-grade brine
• Less electric power
• Less corrosion problems
• No co-products to dispose of
• Does not require ammonia plant investment
• With current fertilizer shortage, all of the
ammonium chloride will be used as a mixed
chemical fertilizer ingredient, so co-product
disposal no problem.

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Disadvantages of Solvay Process
• Higher Salt Consumption
• Higher investment in ammonia recovery unit.
• More steam consumption

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