INDUSTRIAL

ACIDS and BASES

CARPENA, JEMMEL
MERCADAL, SOMER
OLIVA, PAULINE AUREA
RAMOS, JAYVEE
TOPIC OUTLINE
I. SULFURIC ACID
A. BRIEF HISTORY AND INTRODUCTION
B. PRODUCTION AND SYNTHESIS
1. LEAD CHAMBER PROCESS
2. THE CONTACT PROCESS
II. SODIUM HYDROXIDE
A. BRIEF HISTORY AND INTRODUCTION
B. PRODUCTION AND SYNTHESIS
1. MEMBRANE CELL PROCESS
2. MERCURY CELL PROCESS
3. DIAPHRAGM CELL PROCESS
TOPIC OUTLINE
III. AMMONIA
A. INTRODUCTION
B. RAW MATERIALS
C. PRODUCTION AND SYSNTHESIS
1. KELLOG PROCESS
2. HABER PROCESS
IV. HEALTH AND ENVIRONMETAL HAZARDS
TOPIC OUTLINE
I. SULFURIC ACID
A. BRIEF HISTORY AND INTRODUCTION
B. PRODUCTION AND SYNTHESIS
1. LEAD CHAMBER PROCESS
2. THE CONTACT PROCESS
BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID (H2SO4) General Properties
Colorless
Odorless
Very corrosive
Sometimes referred to as “oil of vitriol”
Has a very strong affinity with water
BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID (H2SO4)
Unknown origin
One of the most widely used
acids today
Produced by Johann Van
Helmont (1600) using
destructive distillation of green
vitriol or ferrous sulfate.
BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID (H2SO4)
17th century – Johann Glauber produced
sulfuric acid by burning sulfur and KNO3
together in a presence of steam.
1704 – Joshua Ward commercially developed
the process invented by Glauber.
1746 – John Roebuck developed the Lead
Chamber Process
1831 – The contact process was first
discovered by Phillips, an Englishman
BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID USES
Used to produce phosphoric acid,
ammonium phosphate that important
components of fertilizers.
Used in metal processing such as copper
and zinc.
Used to make caprolactam that is used to
produce TiO2 that is used as a pigment.
BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID USES
MAJOR US MARKETS FOR SULFURIC
ACID
Phosphate Fertilizer Petroleum Refinery Chemicals
Ore Processing Pulp & Paper Paints and Pigments
Nitrogen Fertilizer Steel pickling Others

13%

2%
1%
2%
2%
7%

6% 61%
6%

Shreves, 5th ed.

BRIEF HISTORY AND INTRODUCTION
SULFURIC ACID PRODUCTION STATISTICS
World Production (2012) – 231 million
tonnes
Producing Countries Output
1. China 74 million tonnes
2. U.S. 37 million tonnes
3. India 16 million tonnes
4. Russia 14 million tonnes
5. Morrocco 7 million tonnes
Table 1. Top sulfuric acid producing countries from Merchant
Research and Consulting Ltd. 2011-2012. These number are
expected to soar up to 260 million tones in 2018.
PRODUCTION AND SYNTHESIS
GENERAL PROCEDURE ON THE MANUFACTURE
OF SULFURIC ACID
1. Extraction of sulfur
2. Conversion of sulfur to sulfur dioxide
3. Conversion of sulfur dioxide to sulfur trioxide
4. Conversion of sulfur trioxide to sulfuric acid
PRODUCTION AND SYNTHESIS
LEAD CHAMBER PROCESS (yields 62% - 78% Sulfuric acid)
Raw Materials:
- Sulfur
- Air
- Nitrogenous oxides (active catalyst)
Lead Chamber Process Diagram
Lead Chamber Process
COMBUSTION CHAMBER
1. Sulfur is burned with excess air to
produce sulfur dioxide ( SO2)
2. The gases produced are filtered to
remove solid particles.
3. The flue gas (composed of SO2, O2, and
N2) then enters the nitre pots where
NO2 and NO are mixed
4. The mixture of gases will enter the
glover tower made from brick and is
acid-resistant.
Lead Chamber Process

Glover Tower
For concentration of chamber acid and denitration
1. The burner gases (mixture of SO2,O2,N2,NO2,NO) then goes to the
bottom of the glower tower with temperatures 450-650oC.
Lead Chamber Process

1
2

Glover Tower
2. The hot gases are then washed with nitrous vitriol (nitrated acid,
sulfuric acid mixed with nitric oxide and nitrogen dioxide). The burner
gases temperature will drop to 70-80 oC.
Lead Chamber Process

1
2
3

Glover Tower
3. The heat removed from the burner gases will vaporize water from
the chamber acid (62%-68%), producing a more concentrated acid.
Meanwhile, the nitrogen oxides dissolved is stripped from the acid
and is carried to the lead chamber.
Lead Chamber Process

1
2
3

Glover Tower
4. Burner gasses then leaves the glover tower to enter the Lead
Chamber
Lead Chamber Process

Lead Chamber (3 -12 chamber connected in series)

The gases that leaves the glover tower (mixture sulfur dioxide
and trioxide, nitrogen oxides, nitrogen, oxygen, and steam) will
now enter a series of lead chamber where low pressure steam
and water are sprayed through spray nozzles
Lead Chamber Process
The following reactions take place in the chamber:
NO + ½ O2 -----> NO2
NO2 + NO + H2O -----> 2 HNO2
SO2 + H2O -----> H2SO3
2 HNO2 + 2 H+ -----> 2 NO + 2 H2O
H2SO3 -----> HSO3- + H+
NO+ + HSO3- -----> NOSO3- + H+
NO+ + NOSO3- -----> 2NO + SO3
SO3 + H2O -----> H2SO4

Overall Reaction: SO2 + ½ O2 + H2O -----> H2SO4

Lead Chamber Process

Chamber Acid
The sulfuric acid formed (62% - 68%) condenses on the walls
of the chamber and collects on the chamber floor. The acid
then goes to a storage tank, before going back to glover tower
for further purification.
Lead
2 Chamber Process
 The gasses from the chamber will
enter the Gay-Lussac tower and the
washed with concentrated acid.
 Unreacted sulfur dioxides and
nitrogen oxides will be dissolved in the
acid to form nitrous vitriol (to be used
in glover tower)
 The waste gases are released to the
atmosphere.
Lead
2 Chamber Process

The final product acid (78%) cooled from glover

tower is fetch from the Glover-Gay Lussac
stream.
PRODUCTION AND SYNTHESIS
SINGLE ABSORTION CONTACT PROCESS
This process can achieve up to 98 % conversion
efficiency.
The SO2 content of the inlet gases in about 6% -
10%
The catalyst contain alkali and vanadium oxides
PRODUCTION AND SYNTHESIS
Modern Contact Process
PRODUCTION AND SYNTHESIS
DOUBLE ABSORPTION CONTACT PROCESS
 Conversion efficiency can be up to 99.5%
 The inlet gases contain 6-12% SO2
 Arrangement of contact beds and contact time
affects the efficiency
 The absorption of the sulfur trioxide brings about a
considerable shift in the reaction equilibrium
towards the formation of SO3, resulting in
considerably higher overall conversion efficiencies
when the residual gas is passed through one or two
secondary contact beds.
SINGLE ABSORPTION CONTACT PROCESS
4

3
5
2

1
6
SINGLE ABSORPTION CONTACT PROCESS
1. SULFUR BURNING – sulfur and sulfide ores are
burned in excess air to produce sulfur dioxide.
S(s) + O2(g) ---> SO2(g)

For pyrite (sulfide ore)

4FeS2(s) + 11O2(g) ---> 2 Fe2O3(s) + 8SO2(g)
The sulfur dioxide containing mixture is cleaned and
dried
2. HEAT REMOVAL - Heat exchangers remove heat
from the gas mixture and recovered to produce steam.
SINGLE ABSORPTION CONTACT PROCESS
3. CATALYTIC CONVERSION OF SO2 to SO3 – this is a
reversible exothermic reaction in the presence of
vanadium pentoxide catalyst.
2SO2(g) + O2(g) <---> 2 SO3(g) ΔH = 196 kJ mol-1
Equilibrium consideration (Le Chatelier’s Principle)
- cheap and easy way to convert SO2 to SO3
- higher proportions of oxygen will favor the
forward reaction BUT SO3 produced is not
significantly higher
- More oxygen will pass over the catalyst which
has nothing to react with
SINGLE ABSORPTION CONTACT PROCESS
3. CATALYTIC CONVERSION OF SO2 to SO3 – this is a
reversible exothermic reaction in the presence of
vanadium pentoxide catalyst.
Temperature
considerations – since the
forward reaction is
exothermic, it will be
much favored at lower
temperature.
SINGLE ABSORPTION CONTACT PROCESS
3. CATALYTIC CONVERSION OF SO2 to SO3 – this is a
reversible exothermic reaction in the presence of
vanadium pentoxide catalyst.
2SO2(g) + O2(g) <---> 2 SO3(g) ΔH = 196 kJ mol-1
Pressure considerations – The reaction is carried out
at pressures close to atmospheric (1 – 2 atm)
- an increase in pressure will favor the reaction
with less number of molecules
- very small improvements are achieved by
increasing the pressure; it is not worth the
expense of producing high pressure gasses.
SINGLE ABSORPTION CONTACT PROCESS
3. CATALYTIC CONVERSION OF SO2 to SO3 – this is a
reversible exothermic reaction in the presence of
vanadium pentoxide catalyst.
2SO2(g) + O2(g) <---> 2 SO3(g) ΔH = 196 kJ mol-1
The catalyst (V2O5) – this only speeds up the reaction
but has no effect of the position of the equilibrium
- no reaction in any sensible time will happen
without the catalyst.
4. The heat of reaction is them removed the the
action of heat exchangers.
SINGLE ABSORPTION CONTACT PROCESS
5. CONVERSION OF SO3 to H2SO4 – this cannot be
carried out by just adding water because the reaction
is uncontrollable. SO3 is dissolved in concentrated
H2SO4 (absorber acid: approx. 99wt%) to produce
oleum.
H2SO4(l) + SO3(g) ---> H2S2O7(l)
6. Dilution of oleum – water can be safely added to
oleum to produce concentrated sulfuric acid (99-
99.5% concentration)
H2S2O7(l) + H2O(l) ----> 2H2SO4(l)
SINGLE ABSORPTION CONTACT PROCESS
ACID SCRUBBING – to prevent the escape acidic stack
gases into the atmosphere (which in turn causes acid
rain), the gases pass through acid scrubbers usually
made of bases like sodium carbonate (Na2CO3)

Some unreacted SO2 can be recycled back to the

catalytic converter.
DOUBE ABSORPTION CONTACT PROCESS
Detailed flow diagram of Double Contact Process
DOUBE ABSORPTION CONTACT PROCESS
Manufacturing Process Comparison
Manufacturing Process Pros Cons
Lead Chamber Process  Plants are relative less • Produces only 78% in
complicated strength.
Single Absorption Contact • Produces higher • Plants are more
Process / concentrations of complicated
sulfuric acid. • Requires extensive gas
Double Absorption • Heat generated from purification when using
Contact Process burning sulfur are sulfide ores
recovered to be used in • Acid scrubbers are
melting sulfur and to required to prevent the
produce electricity escape of acidic gases
minimizing the energy into the atmosphere.
cost of production
• Stack emissions are
reduced in the Double
Absorption.
DOUBE ABSORPTION CONTACT PROCESS
Follows almost the same process as the
single absorption.
Uses two absorbing towers (the intermediate
absorption tower and the final absorption
tower)
Significantly reduces the emission of SO2 into
the atmosphere.
Conversion efficiency is 99.5%
THE ACID RAIN
Acid Rain can
accelerates
chemical
weathering in
stone
monumnets
TOPIC OUTLINE
II. SODIUM HYDROXIDE
A. INTRODUCTION
B. RAW MATERIALS
C. PRODUCTION AND SYSNTHESIS
1. CLHLORALKALI PROCESS
a. MEMBRANE CELLS
b. MERCURY CELLS
c. DIAPHRAGM CELLS
A BIG LYE!
A ‘BASIC’ HISTORY OF NaOH
• Prior to 1791 Sodium Hydroxide did not
exist in any recognizable form
• In the 1600s, Sodium Carbonate was the
alkali used for saponification in
production of soap
• Marseilles soap
• “Dying art of true soap boiling”
• LeBlanc process(1791) & Solvay
process(1860) to produce Sodium
Carbonate
• Marius Fabre— a company that still uses
Sodium Carbonate to produce soap
Sodium Hydroxide

• Lye, Caustic Soda

• Odorless solid,
white cystalline
• Highly corrosive
• Soluble in water
Sodium Hydroxide
• Discovered by Humphrey
Davy(1807)
• A co-product from the
manufacture of chlorine
using a solution of
Sodium Chloride(brine)
• Chlor-alkali Process
Chlor-alkali Process: Sodium Hydroxide Production

• Electrolysis of Sodium Chloride

• Produces Chlorine, Hydrogen, and Sodium
Hydroxide
• Reaction:
– 2NaCl + 2H2O  2NaOH + Cl2 + H2
• Three Process:
– Membrance Cell Process
– Mercury Cell Process
– Diaphragm Cell Process
Membrane Cell Process
Membrane Cell Process

Source: Euro Chlor

www.eurochlor.org

MEMBRANE CELL
Membrane Cell Process
Membrane Cell Process
• A solution of 50% Sodium Hydroxide leaves the
process
• An approximate of 13% of Sodium Hydroxide is
produced in this process
• A selective membrane is utilized to separate
Chlorine and Sodium ions.
• Consumes the lowest electric energy among the
three cell process
Mercury Cell Process
• Also called Castner-
Kellner process
• Highest consumption of
electric energy among
the three cell process
• No steam is required to
concentrate caustic
solution
Mercury Cell Process

• In the mercury cell process:

– A mixture between sodium and mercury
which is called an amalgam at the cathode
– The amalgam reacts with the water in a
separate reactor called a decomposer
where hydrogen gas and caustic soda
solution at 50% are produced
 Mercury Cell Process

• Anode (positive electrode): Titanium

– Anode reaction (oxidation): 2Cl-(aq)  Cl2 + 2e-
• Cathode (negative electrode): Mercury flowing
along the bottom of cell
– Cathode reaction (reduction): Na+(aq) + e-  Na(s)
• Na(s) dissolves in the liquid mercury to form an
amalgam which is removed to the decomposer
 Mercury Cell Process

• In the decomposer, the amalgam reacts with water

to form sodium hydroxide, hydrogen gas and
mercury
– 2Na/Hg + 2H2O(l)  2Na+ + 2OH- + H2(g) + 2Hg(l)
– Sodium Hydroxide solution and Hydrogen gas are
collected
– Mercury is recycled through the electrolytic cell
Mercury Cell Process
Diaphragm Cell Process
• It is made of porous mixture of asbestos and
polymers.
• The solution can seep through it from the anode
compartment into the cathode side
• Diaphragm prevents hydroxide ions entering
anode compartment and prevents chloride ions
entering the cathode compartment.
• Can synthesize up to 99% Solution of NaOH
Diaphragm Cell Process
Diaphragm Cell Process
 Diaphragm Cell Process
• Anode (positive electrode): Carbon(graphite) or
Titanium coated with Ru-Ti oxide
– Anode reaction (oxidation): 2Cl-(aq)  Cl2(g) + 2e-
• Cathode (negative electrode): Steel mesh
– Cathode reaction (reduction): 2H2O(l) +2e-  H2(g)
+ 2OH-(aq)
Diaphragm Cell Process
• Na+ migrates across diaphragm to cathode
compartment combining with OH- to form NaOH
• Overall Cell Reaction:
– 2H2O(l) + 2Cl-(aq) 2Na+(aq)  2Na+(aq) + 2OH-(aq)
+ H2(g) + Cl2(g)
• Product contains sodium chloride and sodium
hydroxide. NaOH(s) can be crystallized out.
Uses of Sodium Hydroxide
• Organics (organic chemicals)
• Inorganic chemicals (paints, glass, ceramics)
• Fuel cell production
• Cosmetics
• Paper, pulp and cellulose industries
• Soaps and detergents
• Mineral oils (preparation of greases and fuel
additives)
Sodium Hydroxide Industries
• Airedale Chemical
– Industrial chemicals
– Phosphates
– Phosphonates
– Surfactants
– And many more…
• EUCOM
• Atlas Pellets Industries
Local Sodium Hydroxide Industries
• Mabuhay Vinyl Corporation
– Caustic Soda
– Hydrochloric Acid
– Chlorine
– Sodium Hypochlorite
• “The lone Chlor-alkali
producer in the Philippines”
• Supplies more than 50% of
the country’s requirement
TOPIC OUTLINE
III. AMMONIA
A. INTRODUCTION
B. RAW MATERIALS
C. PRODUCTION AND SYSNTHESIS
1. KELLOG PROCESS
2. HABER PROCESS
A. INTRODUCTION

• Ammonia(NH3 )
– It is the most
important
nitrogenous material.
It is a colorless gas
with characteristic
pungent smell.
– Commonly used as
fertilizers.
HISTORY

• JOSEPH
PRIESTLEY
–He was the first
to obtained
ammonia in pure
form(1774).
HISTORY
• HABER AND NERNST
– Made a careful
studies of the
equilibrium between WALTHER NERNTS
nitrogen and
hydrogen under
pressure to form
ammonia.
– Discovered several FRITZ HABER
suitable catalyst.
B. RAW MATERIALS:
• AIR

• WATER

• HYDROCARBONS
C. PRODUCTION AND SYNTHESIS
• 1. KELLOG PROCESS
KELLOG PROCESS
KELLOG PROCESS
1.) Manufacturing Process
Natural gas or naphtha is free form sulfur will
undergo desulfurization. Natural gas used is
mostly methane(CH4 ).
Desulphurizer with a ZnO catalyst .
Primary reformer with a nickel catalyst at 32 bar.
Gas leaving the primary reformer: 70%
H2 ,10% CO2 ,10% CO, and 10% methane.
KELLOG PROCESS
• Secondary reformer has NiO catalyst.
• Exit gas at 920°C in secondary
reformer:57% H2, 22% N2, 13% CO, 7%
CO2, 0.3% CH4.
KELLOG PROCESS
2.) Purification
At high temperature shift reaction enters
at 337°C with a catalyst of iron and
chromium oxide.
Catalyst: Fe, CrO
Low temperature shift reaction at 208°C
achieved by 3 heat exchanger.
Catalyst: Cu, Zn, Al
KELLOG PROCESS

The carbon dioxide dissolves in the

Potassium Carbonate to form Potassium
Bicarbonate.

Small traces of carbon dioxide and

hydrogen are converted to methane.
Catalyst:NiO2
KELLOG PROCESS

3.) Compresssion
After methanation at 2.75 MPa it is raised to
20 MPa.
KELLOG PROCESS

4.) Catalytic reaction

1 3
N2(g) + H2(g) ⇄ NH3(g)
2 2
∆H12℃ = -46.0kJ
∆H659℃ = -55.6kJ
• Exothermic
KELLOG PROCESS

5.) Recovery of ammonia formed

The ammonia is then recovered by
means of refrigeration or absorption.
KELLOG PROCESS

6.) Recirculation
Inerts feds contains CH4 , Ar, Ne, etc.
It is removed by purging.
HABER PROCESS
Haber- Bosch Process

• Also known as Haber ammonia process

or synthetic ammonia process.
• It works by fixing nitrogen from the air
with hydrogen from natural gas to
produce ammonia.
• Exothermic
1.) Mixing of water and methane

2.) Adddition of air

• 3.) It will undergo in the CATALYSOR
– Temperature: 400 ⁰C- 650⁰C
– Pressure: 200-400 atm
– Catalyst: Iron

4.) It is cooled to have a liquified ammonia.

COMPANIES
Health and Environmental Hazards
Sulfuric Acid
Sodium Hydroxide
Ammonia
Personal Protective Equipment, PPE
• Refers to clothing, helmets goggles, other garments, or equipment
designed to protect the wearer’s body from injury or infection.

• TYPES
– Respirators – serve to protect the user from breathing in
contaminants in the air
– Skin Protection – creates a barrier between the skin and the
agent
– Eye Protection – protects the eyes from particles, light, wind,
heat or sea spray
– Ear Protection – protects the ear from the elements and high
levels of noise
– Ensemble – sets of PPE worn together in combination
Ammonia, hazards
Ammonia, NFPA 704
Flammability
1– Must be pre-heated before ignition can
occur
1 Flash point (93 C)
Health
3 0 3– Short exposure could cause temporary of
residual injury
Reactivity
0– Normally stable, even under fire exposure
conditions, and is not reactive to water
Special
Ammonia, first aid measures
Ammonia, fire fighting measures
Ammonia, spill measures
Sulfuric Acid, hazards
Sulfuric Acid, NFPA 704
Flammability
0– Will not burn

0 Health
3 2 3– Short exposure could cause temporary of residual
injury
W Reactivity
2– Undergoes violent chemical change at elevated
temperatures and will react violently with water
Special
W– Reacts with water unusually or dangerously
Sulfuric Acid, first aid measures
Sulfuric Acid, fire fighting measures
Sulfuric Acid, spill measures
Sodium Hydroxide Hazards
Sodium Hydroxide, NFPA 704
Flammability
0– Will not burn

0 Health
3 1 3– Short exposure could cause temporary of
residual injury
ALK Reactivity
1– Normally stable, but can become unstable
at elevated temperatures and pressures
Special
ALK – Alkaline
Sodium Hydroxide First Aid Measures
Sodium Hydroxide, Fire Fighting Measures
Sodium Hydroxide Spill Measures
GHS Pictograms

• Compressed Gas

• Very hazardous to aquatic life

• Corrosive

• Toxic
References
1. Shreves
2. King Mathew J. et al. Sufuric acid manufacture analysis control and optimization. Elsevier
Ltd. California. 2013
3. Buchel K.H., Woditsch M.P. Industrial inorganic chemistry.Wiley VCH. New York. 2000
4. Kent, James A. Handbook of industrial chemistry and biotechnology 12th ed. Springer
Science + Business Media. New York. 2012
5. Ali, M.F., et al. Handbook of industrial chemistry. McGraw Hill. New York, 2005.
6. http://www.inclusive-science-engineering.com/manufacture-of-h2so4-by=chamber-
process/
7. http://www.soapalooza.com/blog/2014/02/the-big-lye-history-of-sodium-hydroxide-as-
we-know-it-today/
8. http://www.eurochlor.org/the-chlorine-universe/how-is-chlorine-produced.aspx
9. http://www.ausetute.com.au/chloralkali.html
10. http://www.mvc.com.ph/
11. https://www.chemguide.co.uk/inorganic/group7/diaphragmcell.html
12. https://www.airedalechemical.com
13. http://www.eucom.rs/en/trading-goods/base-chemicals
References
14. https://pubchem.ncbi.nlm.nih.gov/compound/ammonia
15. https://www.sigmaaldrich.com/catalog/product/aldrich/294993
16. https://www.sigmaaldrich.com/catalog/product/sigald/84724
17. https://www.sigmaaldrich.com/catalog/product/sigald/415413