Beruflich Dokumente
Kultur Dokumente
Industries
(CHE-105)
Saqib Javed
Alkali Industry
(Caustic Soda, Soda Ash)
NaOH, Na2CO3
1
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.
2
Uses
Caustic is consumed in large
quantities in the manufacture of:
• Rayon
• Explosives
• Soap
• Paper
Chemicals
• Petroleum Refining
Soap
3
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
4
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
5
Lime Soda Process
6
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.
7
• 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.
8
Electrolysis of Brine – Most popular method
9
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).
10
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
11
MANUFACTURING PROCESS
• Brine Purification
• Brine Electrolysis
• Final Evaporation
14
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
15
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
.
16
Self Study
• Finishing of Caustic
• Special Purification of Caustic
17
Process Chemistry
21
Water
Salt (Rock)
Brine
Salt
(Recycled) Precipitants
Precipitation
Residue
Filtration
Heat Exchange
Hydrogen
Electrolytic Cell
Concentration Chlorine
Cooling
Storage NaOH
22
Recycle Salt
Water NaOH
P-1 Ev-1
Rock Salt
Cl2
Cv-1 Salt
Ag-1
H2
Heated
Brine
H2 P-1
NaOH
H-1
BT-1 H-2
Cl2 Pr-1 FR-1
H2 EC-1
NaOH
NaOH
ST-1
P-2 P-3 ST-2
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
BT-1 P-2 P-4
Pr-1 FR-1
23
Flow Sheet
24
Final Product
25
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.
26
Types of Cells
• Mercury Cell
• Diaphragm Cell
• Membrane Cell
27
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.
28
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
29
30
Advantages
31
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
32
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.
33
34
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
35
36
Comparison of Cell Technologies
Mercury Diaphragm Membrane
39
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
40
Applications
41
Raw Materials
Ammonia(as a
catalyst)
42
Process Chemistry
Overall reaction
CaCO3 + 2NaCl Na2CO3 + CaCl2
This reaction takes place in a number of steps
43
By Products
Ammonium Chloride
Calcium Chloride
44
Manufacturing Process
• Brine preparation
• Purification of brine
• Ammonia absorption
• Precipitation of bicarbonate
• Filtration of bicarbonate
• Recovery of ammonia
45
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
47
Cyclic process
48
Unit Operations---Equipment
Settling Vat
Absorber
Carbonator
Rotary Vaccum Filter
Lime Kiln
Lime Slaker
Gas Compressor
Calciner
49
Settling Vats
• They are used for brine purification before it
flows to the strong ammonia absorber
50
Absorber
• NH3 is absorbed in
the purified brine.
51
Carbonator
• Formation of (NH4)2CO3
• Formation of NH4HCO3
52
Rotary Vacuum Filter
Ammonium Chloride
leaving with the product of
Carbonator is removed.
53
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
54
Lime Slaker
• Lime Slaker is used to
make milk of lime by
adding water to calcium
oxide.
55
Calciner
Calcination:
• Heating a substance
below its Melting point.
It is unit process.
• Conversion of Sodium-
Bicarbonate into
Sodium-Carbonate
56
Storage Transportation
57
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.
58
Disadvantages of Solvay Process
• Higher Salt Consumption
• Higher investment in ammonia recovery unit.
• More steam consumption
59