8/20/15

LECTURE20:
HYDROCHLORIC ACID
SULFURIC ACID

CHEMICAL TECHNOLOGY (CH-206)

Department of Chemical Engineering

HYDROCHLORIC ACID (HCL)

8/20/15

Hydrochloric acid (HCl), also known as muriatic

acid, is a solution of hydrogen chloride in water.
HCl exists in solid, liquid, and gaseous states and
is water soluble in all proportions.

HYDROCHLORIC ACID (HCL):

PROPERTIES
Molecular formula

HCl

Molecular weight

36.5gm/mole

Appearance

Colourless liquid

Odour

Boiling point

85 0C

Melting point

1140C

Density

Solubility

Forms azeotropic mixture with water, containing 20.24% HCl which boils at 110 0C.

Commercially available in 27.9%, 31.5% and 35.2%wt HCl solution in water.

8/20/15

Pungent

1.179gm/mL (35.2% HCl )

:

Extremely soluble in water

Anhydrous HCl is available in steel cylinders because completely dry HCl is not
very reactive. But dry HCl often reacts only in the presence of catalysts.
HCl solution in a polar solvent is strong acid and, therefore, an aggressive
reagent.
3

HYDROCHLORIC ACID (HCL):

PROCESSES
8/20/15

Synthesis from hydrogen and chlorine

From salt and sulfuric acid
As by-product from chemical processes
From incineration of waste organics
Hydrochloric acid solutions

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

Raw materials

8/20/15

Basis:

1 ton of HCl (98% yield)

Hydrogen 28.21 kg
Chlorine 999.21 kg

Sources of raw material

Both

hydrogen and chlorine can be obtained during electrolysis of

brine for manufacturing of NaOH.
Hydrogen can also be synthesized from following methods:
Lane process or iron steam process
Steam hydrocarbon process
Liquefaction of coal gas and coke oven gas
Bosch process or water gas-steam process

Reaction
H2 + Clall
2HCl
Hreacts
= 43.9
kcals
2
To ensure
the
chlorine
with
hydrogen, excess of 10% hydrogen
compare to chlorine is charged from the bottom of combustion chamber.

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

8/20/15

2400 C
O

Block diagram of HCl manufacturing

process

6
Process diagram of HCl manufacturing process

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

8/20/15

The combustion chamber is made of structural carbon or lined

with silica bricks provided with cooling device which may
consist even of cold-water circulation in the shell.
The combustion chamber and length of ducting should be
sufficiently specious, which leads the gas to absorber,
otherwise hydrochloric acid will contain free chlorine.
The burning of hydrogen is started by igniting the burner
with an external air-hydrogen torch.
Dry Cl2 is passed into the combustion chamber, where
hydrogen burns in an atmosphere of Cl2 to produce HCl.

The exothermic nature of the direct combination of both gases

(H2 and Cl2) is such as to raise the temperature of the
reagents, and the reaction products to a point where they are
incandescent.
The reaction is carried out at 2400 0C with greenish flame.

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

8/20/15

The gases are always kept above dew point to avoid

corrosion.
The combustion chamber is then cooled externally by
water and gas tight lid is fitted at the top of the
reactor which suddenly opens to allow the gases to
escape in case of emergency.
Hydrochloric acid gas is cooled absorbed in water or
dilute HCl solution by passing through cooler and
absorber through the connecting pipe.
The strength of acid produced is generally 32-33 %.
The heat of absorption of HCl in water is removed by
spray of cold water outside the absorber.
The solution of HCl flows into a storage tank.

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

Anhydrous hydrogen chloride

8/20/15

Hot

gases originating from combustion chamber are

passing over anhydrous CaCl2 or washing them with
98% sulfuric acid and then cooled and compressed to 60
atm pressure.
The cooled and compressed gas having 99.9% purity is
filled in steel cylinders.

In another process, combustion gas is absorbed into

water and distilled to 36% concentration of HCl.
If

it is desired to obtain 97% HCl at the top of the

column. The 35% acid is cooled to 120C and aqueous
liquid containing 50% HCl is left to condense, while
residual gases, when they have been de nebulized as
compressed to 60 atm are of purity exceeding 99.5%.

HYDROCHLORIC ACID (HCL): PROCESSES

SYNTHESIS FROM HYDROGEN AND CHLORINE

8/20/15

Engineering aspect
The combustion chamber and ducting to absorber
should be sufficiently specious for avoiding wall
effect.

If

the walls of reactor in which chain reactions takes place

by their varying nature, development, shape and
orientation as to affect the chain carriers is called wall
effect.

The wall tends to interrupt the process by promoting

the chain breaking reaction (termination reactions).
Physico chemically, chain terminators act as a third
body in a system which already consists of the
reactant bodies.

10

HYDROCHLORIC ACID (HCL): PROCESSES

THE SALTSULFURIC ACID PROCESS

Raw materials
Basis:

1 t Hydrochloric acid
Sodium Chloride: 3206 kg (from sea water, salt lake
and sub soil water)
Sulfuric acid: 2688 kg (by Contact process)

8/20/15

Reaction
NaCl + H2SO4 NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl
11

HYDROCHLORIC ACID (HCL):

PROCESSES

THE SALTSULFURIC ACID PROCESS

8/20/15

Block diagram of HCl manufacturing process

12

Process diagram of HCl manufacturing process

HYDROCHLORIC ACID (HCL):

PROCESSES

THE SALTSULFURIC ACID PROCESS

8/20/15

Salt (NaCl) and sulfuric acid are charged to the furnace.

It is desirable to keep one of the components in the
reaction mixture in a liquid form in both steps.
The first step is carried out at the lower temperature
compare to second step.
During the liquefaction of NaHSO4, which is required to
carry out in second step, material is heated up to 400 0C.
Sodium sulfate in form of sludge is collected from the
bottom of the furnace.
The product and unconverted sulfuric acid is sent to
further processing in which recovery of sulfuric acid and
hydrochloric acid in cooling tower and absorber,
respectively.

13

HYDROCHLORIC ACID (HCL):

PROCESSES
As by-product from chemical processes
Over

90% of the hydrogen chloride produced as a byproduct from various chemical processes.
The crude HCl generated in these processes is generally
contaminated with impurities such as unreacted chlorine,
organics, chlorinated organic and entrained catalyst
particles.
A wide variety of techniques are employed to treat these
HCl streams to obtain either anhydrous HCl or
hydrochloric acid.
Some of the processes in which HCl is produced as byproduct is the manufacture of chloro-fluoro-hydrocarbons,
manufacture of aliphatic and aromatic hydrocarbons,
production of high surface area silica, and the manufacture
of phosphoric acid and esters of phosphoric acid.

8/20/15

14

HYDROCHLORIC ACID (HCL):

PROCESSES
From incineration of waste organics
Environmental

regulations regarding the disposal of

chlorine-containing organic wastes have motivated
the development of technologies for burning or
paralyzing the waste organics and recovering the
chlorine values as hydrogen chloride.
Several catalytic and non-catalytic processes have
been developed to treat these wastes to produce
hydrogen chloride.

8/20/15

15

HYDROCHLORIC ACID (HCL):

PROCESSES
From hydrochloric acid solutions
Gaseous

hydrogen chloride is obtained by partially

stripping concentrated HCl acid using an absorber
desorber system.
The stripper is operated at a pressure of 100200 kPa
(12 atm) for improved recovery of HCl.
The overhead vapors consisting of 97% HCl and 3%
H2O is cooled to remove most of the water as
concentrated HCl, and the residual water vapor is
removed by drying the gas with sulfuric acid.

8/20/15

16

HYDROCHLORIC ACID:
APPLICATIONS
8/20/15

Anhydrous HCl is consumed for its chlorine value, whereas

aqueous hydrochloric acid is often utilized as a nonoxidizing acid.
Used in metal cleaning operations, chemical
manufacturing, petroleum well activation, and in the
production of food and synthetic rubber.
Used for the manufacture of chlorine and chlorides, e.g.
Ammonium chloride used in dry cell.
In the manufacture of glucose from corn starch.
For extracting glue from bones and purifying boneblack.
A saturated solution of zinc chloride in dilute HCl is used
for cleaning metals before soldering or plating.
It is also used in medicine and as laboratory reagent.
Aqua regia used for dissolving metal.

17

8/20/15

SULFURIC ACID (H2SO4)

18

SULFURIC ACID (H2SO4): PROCESSES

The Industrial manufacture of sulfuric acid is
done mainly by two processes

8/20/15

The

Lead Chamber process

The Contact process

19

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS
Raw Materials
Basis:

1 ton Sulfuric acid (98% yield)

Sulfur 400kg
Air
399kg

Reaction
S + O2 SO2

8/20/15

H = 70.9kcals

4FeS2 + 11O2 2Fe2O3+ 8SO2

SO2 + NO2 SO3 + NO
SO3 + H2O H2SO4
NO + O2 2NO2

H = 92.0kcals

H = 27.12kcals

NaNO3 + H2SO4 NaHSO4 + HNO3

2HNO3 + 2SO2 2SO3 + H2O + NO + NO2
NO + NO2 + 2H2SO4 2NO.HSO4 + H2O
2ON.O.SO2OH + H2O H2SO4 + NO2 + NO

20

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

21

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

22

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

Sulfur dioxide is obtained by burning sulfur or by roasting pyrites.

There are two function of burner

To

oxidize sulfur to maximum extent

To produce and constant supply of gas containing maximum
concentration of SO2

The burner of the furnace should expose large surface of melted

sulfur and should be provided secondary air in order to burn
sublimed burner.
At about 4000C, pyrite (FeS2) decompose in to FeS and sulfur
vapour, the later oxidized to SO2 in presence of excess air.

The residual FeS also oxidizes to Fe2O3 and SO2.

Iron oxide (Fe2O3) slightly catalyzed oxidation of SO2 to SO3.

Burner gas should contain sufficient oxygen for carry out further
oxidation of SO2 to SO3.

23

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

The mixture of SO2, Oxides of nitrogen and air is then

passed to series of rectangular vessels made of lead
(lead chamber: 1545 m length, 67 m width and 7 m
length and 36 in numbers).
The chambers are arranged in two parallel rows.
Steam from low pressure boiler or pure filtered water is
sprayed from top of the chamber.
Mixture of gases is converted into H 2SO4 having 6570%v strength is collected at the bottom of the chamber.
Dilute sulfuric acid obtained in any of the chamber is
called chamber acid.
A part of chamber acid is pumped to Glower tower, and
the rest is sent for concentration.

24

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

The nitric acid produced reacts with SO 2 to give mixture

of nitric oxide (NO) and nitrogen dioxide (NO 2) which
are carried with burner gases.

8/20/15

The burner gases which contain SO 2, N2, O2 and dust or

fine particle of pyrites are passed through dust chamber
followed by Cottrell electrical precipitator or centrifugal
separator in order to remove dust or fine particle of ore.
Dust chambers are provided with horizontal shelves or
baffles followed by filtration through crushed coke or
similar material.
Burner gases further are passed through niter oven
made of cast iron in which equimolecular proportion of
NaNO3 and H2SO4 is heated.

25

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

The burner gases they pass through Glower tower (5 m 2 and 10

15 m high), which is packed with flint stone, quartz, tile or acid
resisting bricks.
The packing in the tower is loosely stacked at the bottom to
facilitate mixing of hot gases.
The hot burner gases passed to this tower is at 450650 0C and
dilute H2SO4 from the lead chamber and nitrosyl sulfuric acid
from Gay-Lussac tower are made to trickle down the Glower
tower by means of sprayers.
The burner gases are cooled down to 70-80 0C, dilute chamber
acid is concentrated up to 78% and nitrosyl sulfuric acid (nitrous
vitriol) is denitrated by action of water.
The tower acid is drawn off from the bottom of the tower and
collected in the container called acid egg.
The acid from base of Glower tower is cooled to 40 0C by air
coolers.

26

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

Dilute acid may be further concentrated into Glower

tower.

8/20/15

The unabsorbed remaining gases contain oxides of

nitrogen and SO2 from lead chamber are then passed
through Gay-Lussac tower at the top of which Glower
acid is sprayed to recover oxides of nitrogen.
The oxides of nitrogen recovered in the form of
nitroso sulfuric acid are pumped to Glower tower to
again regenerate oxides of nitrogen.
When pyrite is used as raw material, the chamber
acid may contain arsenious oxide (from pyrite), lead
sulfate from lead chamber are removed by treatment
of H2S and dilution of acid respectively.

27

SULFURIC ACID (H2SO4): PROCESSES

THE LEAD CHAMBER PROCESS

8/20/15

Reason for obsolesce

The overall reaction consisting of number of
partial reactions which takes place in liquid
phase, the development of surfaces which are
covered in this liquid is a factor of fundamental
importance in promoting the synthesis of sulfuric
acid.
Maximum strength of sulfuric acid obtained by
chamber process is 78%.
However, in manufacture of some dyes and
chemical processes require more concentrated
H2SO4.

28

SULFURIC ACID (H2SO4): PROCESSES

THE CONTACT PROCESS
Raw Materials

Basis: 1 ton sulfuric acid (100%)

Sulfur dioxide or pyrite (FeS 2)
670kg
Air 14502200 Nm3
Catalyst
V2O5

8/20/15

Sources of raw material

Sulfur from mines

Sulfur or hydrogen sulfide recovered from petroleum desulfurization
Recovery of sulfur dioxide from coal or oil-burning public utility stack gases
Recovery of sulfur dioxide from the smelting of metal sulfide ores

2PbS + 3O2 2PbO + 2SO2

Isolation of SO2 from pyrite

Reactions (Temperature = 450 oC, Pressure = 1.21.5 atm)

S + O2 SO2 H = 71.2kcals
2SO2 + O2 2SO3 H = 46.3kcals
SO3 + H2O H2SO4

H = 31.1kcals

This process is strongly exothermic

29

SULFURIC ACID (H2SO4): PROCESSES

THE CONTACT PROCESS
Burning of sulfur
Burning

of sulfur in presence of dry air is carried out

in sulfur pyrite burner.
As SO2 is needed for the catalytic oxidation and
prevention of corrosion, dry air is used in the
combustion process.
If sulfur contains carbonaceous impurities, the
molten material has to be filtered to avoid poisoning
the catalyst and forming water from burning
hydrogen.

8/20/15

30

SULFURIC ACID (H2SO4): PROCESSES

THE CONTACT PROCESS

Catalytic oxidation of SO2 to SO3

The

catalytic reactor is designed as a four-stage fixed-bed

unit. The gas has to be cooled between each step.
Four passes, together with "double absorption, are necessary
for overall conversion of 99.5-99.8% (three passes, 97-98%).
The temperature rises to over 6000C with the passage of the
gas through each catalyst bed.
The doubled absorption consists of cooling the gases between
each bed back to the desired range by sending them through
the heat exchanger and then back through the succeeding
beds.
Between the third and fourth beds, the gases are cooled and
sent to an absorption tower. This is to shift the equilibrium
to the right by absorbing SO3.
The gases are then sent to the heat exchanger to warm them
to 410-4300C and then on to the fourth catalyst bed.

8/20/15

31

SULFURIC ACID (H2SO4): PROCESSES

THE CONTACT PROCESS
Hydration of SO3
After

the catalytic oxidation process, the resulting SO 3 is hydrated

by absorption in packed towers filled with 98-99% sulfuric acid.
This is the H2SO4 azeotrope of minimum total vapour pressure.
SO2 has a low solubility in 98% H2SO4. At lower acid
concentrations, sulfuric acid and SO3 form a troublesome mist and
at higher concentrations emissions of SO3 and H2SO4 vapour
become significant.
The absorption acid concentration is kept within the desired range
by exchange as needed between the H2SO4 in the drying acid vessel
that precedes the combustion chamber with the H2SO4 in the
absorption tower.
The acid strength can be adjusted by controlling the streams of
H2SO4 to give acid of 91 to 100% H2SO4 with various amounts of
added SO3 and water.
The conversion of sulfur to acid is over 99.5%.

8/20/15

32

SULFURIC ACID (H2SO4): PROCESSES

THE CONTACT PROCESS
Major engineering problems
Design

of multistage catalytic convertor for highly exothermic

reaction. Earlier two stage converter is used but nowadays the
design of three or four stages rather than conventional two
stage operation are developed.
To optimize space velocity in catalyst chamber because it deals
with pumping cost or fixed charges of reactor
Thin catalyst beds of 30-50cm height used to avoid above
difficulties. Yield can drop due to longitudinal mixing if the
convective gas velocity through the bed is low
Removal of heat of absorption of SO3 in acid. Pipe coolers with
water dripping over external surface have been replaced by
cast iron pipe with internal fins to promote better heat
transfer.
Pressure drop must be low, so, 8cm stacked packing is often
used.

8/20/15

33

SULFURIC ACID (H2SO4): PROCESSES

PROPERTIES

Physical Properties
Molecular

formula : H2SO4
Molecular weight :
98.08gm/mole
Appearance : Water white slightly viscous liquid
Boiling point : 2900C
Melting point :
100C
Density : 1.840gm/mL (liquid)
Solubility :
Miscible with water in all proportions
Viscosity : 26.7cP (200C)
Aq. H2SO4 solutions are defined by their H 2SO4 content in weightpercent terms.
Anhydrous (100%) sulfuric acid sometimes referred to as
monohydrate, which means that it is the monohydrate of SO 3.
Dissolve any quantity of SO 3, forming oleum (fuming sulfuric acid).
The physical properties of sulfuric acid and oleum are dependent on
H2SO4 and SO3 concentrations, temperature, and pressure.

8/20/15

34

SULFURIC ACID (H2SO4): PROCESSES

PROPERTIES: CHEMICAL PROPERTIES
Dehydrating agent
Has

a great affinity for water and the reaction is extremely

exothermic.
A large amount of heat is produce due to formation of mono and
dehydrates (H2SO4.H2O and H2SO4.2H2O) on mixing acid with water.
So while preparing dilute solutions of H 2SO4 the acid should be added
to water slowly with constant stirring. Never add water to the acid.
Used for drying almost all gases, except NH 3 and H2S.
Its corrosive action on skin is also due to dehydration of skin which
then burns and produces itching sensation.
Due to dehydrating property, it chars sugar to give carbon.

8/20/15

C12H22O11 12C + 11H2O

Also,

paper, starch, wood etc. are charred by conc. H 2SO4 due to the
removal of water. It is also used in removing water from various
substances such as oxalic acid and formic acid.

COOH-COOH H2O + CO + CO2

35

SULFURIC ACID (H2SO4): PROCESSES

PROPERTIES: CHEMICAL PROPERTIES
Oxidising agent
Gives

O2 on strong heating, hot conc. H2SO4 also acts

as an oxidising agent.

8/20/15

Pickling agent
Finds

application in pickling in which layers of basic

oxides are removed before electroplating, enameling,
galvanizing and soldering.

Acidic nature
Strong

dibasic acid and forms two series of salts with

alkalis. These are bisulfates (HSO4) and sulfates
(SO4-2).
36

SULFURIC ACID (H2SO4): PROCESSES

APPLICATIONS
In the fertilizer industry.
In

the production of phosphoric acid, which in turn used to manufacture fertilizers

such as triple superphosphate, mono and diammonium phosphates.
Used for producing ammonium sulfate.

Used as an acidic dehydrating reaction medium in organic chemical and

petrochemical processes involving such reactions as nitration,
condensation, and dehydration, as well as in oil refining, in which it is
used for refining, alkylation, and purification of crude-oil distillates
In the inorganic chemical industry e.g. in the production of TiO 2 pigments,
hydrochloric acid, and hydrofluoric acid
In the metal processing industry e.g. for pickling and descaling steel, for
leaching copper, uranium, and vanadium ores in hydro-metallurgical ore
processing, and in the preparation of electrolytic baths for nonferrousmetal purification and plating
Certain wood pulping processes in the paper industry require sulfuric
acid, used in textile and chemical fiber processes and leather tanning
In manufacture of explosives, detergents and plastics
In production of dyes, pharmaceuticals.

8/20/15

37

ACKNOWLEDGEMENT
Slides are developed from the following references:
Austin

G. T., "Shreves Chemical Process Industries",

Fifth edition, Tata McGraw Hill, NY.
Kent J.A., "Riegel's Handbook of Industrial
Chemistry, CBS Publishers.
Gopala Rao M. & Marshall Sittig, "Drydens Outlines of
Chemical Technology for the 21st Century", Affiliated
East West Press, New Delhi.
Mall I. D., "Petrochemical Process Technology",
Macmillan India Ltd., New Delhi.
http://nptel.ac.in/courses/103106108/24

8/20/15

38