ChE 150

Chemical Process Industries

2nd Semester AY 2021-2022

AJERO | BERNALDEZ | BUSTAMANTE | CABUG | GONZALES |

JANABAN | MORCILLA
GROUP 1 BSChE

Chemical Industry:
PRODUCTION OF SULFURIC ACID

I. OVERVIEW

It is difficult to believe that a very active chemical such as sulfuric acid is at the
same time one of the most widely used and most important technical products. It enters
into many industries, though infrequently appearing in the finished material. It is employed
in the manufacture of fertilizers, leather, and tin plate, in the refining of petroleum, and in
the dyeing of fabrics.

ORIGIN

The origin of the first sulfuric is unknown, but it was mentioned as far back as the
tenth century. Its preparation, by burning sulfur with salt pepper, was first described by
Valentinus in the fifteenth century. In 1746, Roebuck of Birmingham, England, introduced
the lead chamber process.
The contact process was first discovered in 1831 by Phillips, as an Englishman,
whose patent included the essential features of the modern contact process, namely, the
passing of a mixture of sulfur dioxide and air over a catalyst, followed by the absorption
of the sulfur trioxide in 98.5 – 99 percent sulfuric acid.

However, Peregrine Phillips’ invention was not a commercial success for more
than 40 years, probably because of these reasons;
 There was a lack of demand for strong acid
 Inadequate knowledge of catalytic gas reactions
 Slow progress of chemical technology

(The contact process has been improved in all details and is now one of industry’s
low-cost, automatically controlled, continuous process.)

PROPERTIES OF SULFURIC ACID

Sulfuric acid is a strong dibasic acid. In addition, it is also an oxidizing and

dehydrating agent, particularly toward organic compounds. Its dehydrating action is
important in absorbing water formed in such chemical conversions as nitration,
sulfonation, and esterification, thus ensuring high yields.

Solutions of sulfuric acid may be concentrated economically to about 93% by

weight of H2SO4. Stronger acids may be made by dissolving sulfur trioxide in 98 – 99
percent acid. Sulfuric acid forms many hydrates that have fairly definite melting points, as
shown in the table below.

Hydrates of Sulfuric acid

Formula Melting Point, ˚C Specific Gravity
Sulfuric acid, fuming H2S2O7 35 1.2920˚
100% H2SO4 10.37 1.83418˚/4
Monohydrate H2SO4 • H2O 8.48 1.84215˚/4
Dihydrate H2SO4 • 2H2O - 38.57 1.6500˚/4
The irregularities in the relation between strengths of the sulfuric acids and the
corresponding specific gravities and freezing points are due to these hydrates.

Sulfuric acid is widely sold in the form of various solutions of H2SO4 in water, or of
SO3 in H2SO4. The latter, called oleums, are marketed on the basis of the percentage of
SO3 present; 20% oleum mean that, in 100 kg, there are 20 kg of SO3 and 80 kg of H2SO4.
This 20% oleum, if diluted with water to make 100% acid (monohydrate), would
furnish 104.5 kg total weight. Previously, when much of the acid was made by the
chamber process, solutions of sulfuric acid in water were sold according to their specific
gravity or their Baumé (Bé˚) degrees. The table shown below illustrates the standard
sulfuric acids of commerce.

Commercial Strengths of Sulfuric acid

Degrees Bé˚, Specific Gravity, Sulfuric
15.6˚C 15.6˚C acid, %
Battery acid 29.0 1.250 33.33
Chamber acid, fertilizer acid, 50˚ 50 1.526 62.18
acid
Glover or tower acid, 60˚ acid 60 1.706 77.67
Oil of Vitriol (OV), concentrated 66 1.835 93.19
acid 66˚ acid
95% acid 1.841 98.0
100% H2SO4 1.835 100.0
20% oleum, 104.5% acid 1.915 104.5
40% oleum, 109% acid 1.983 109.0
66% oleum 1.992 114.6

For sulfuric acid, the usual temperature to which specific gravity, or Baumé (Bé˚)
degrees, are referred is 15˚C. The specific gravity of sulfuric acid increases gradually to
1.844 at 15˚C for 97% acid, after which it decreases to 1.839 at 15˚C for 100% acid.
As contact plant acid has displaced chamber plant acid, the H2SO4 percentage is normally
specified.
Acid containing 93.19% (66˚Bé acid) is the normal acid of commerce in North
America, its freezing point (-7˚C) is lower than that of 96% acid. This acid is cheap to
transport as it has little water and can be stored and shipped in steel tanks and
containers.
Acid of somewhat higher strength (about 95% H2SO4) is normally used in Europe.
Lesser quantities of 98% acid and oleum are shipped.
Acid of 93% H2SO4 strength is completely suitable for fertilizer manufacture, which
is the major use for sulfuric acid.

The normal strength of commercial oleums fall into three categories, expressed as
percent free sulfur trioxide: 10 – 35 %, 40%, and 60 – 65 %.
The freezing point of 35% oleum is about 29˚C, and of 40% oleum about 34˚C.
Consequently, small amounts of nitric acid are sometimes added (where this is tolerable)
to these grades to inhibit freezing during winter shipment.

II. MARKET PLAYERS

Sulfuric acid referred as universal chemical, king of chemicals due to the numerous
applications for sulfuric acid as a raw material or processing agent. Sulfuric acid is the
most commonly used chemical in the world and used in almost all industries like the
following:
 Pulp and paper bleaching
 Sugar bleaching
 Water treatment
 Amino acid intermediates
 Regeneration of ion exchange resins

Major Markets for Sulfuric Acid

Figure 1. Forecasted market revenue of sulfuric acid in the United States from 2019 to
2025, by application
(in million U.S. dollars)
-Data by Statista (2019)

This statistic shows the forecasted market revenue of sulfuric acid in the United
States from 2019 to 2025, by application. It is forecasted that the market revenue of
sulfuric acid used in metal processing applications will amount to some 125 million U.S.
dollars in 2025.

Chemical Manufacturing
As a highly important chemical compound, sulfuric acid is used in the
manufacturing process of a number of well-known chemicals including
hydrochloric acid, nitric acid, phosphoric acid, and many other industrial
chemicals.
 Fertilizers
 Electronics
 Sulfonation agents
 Coloring agents (paints and pigments)

Oil Refining
The process of refining crude oil requires the use of an acid as a catalyst
and Sulfuric acid is often used for this purpose. It is used in an SAAU or sulfuric
acid Alkylation Unit.
Metal Processing
‘Pickling’ is a term used to describe the treatment of metals to remove
impurities, rust or scale from the surface, such as in steel making. Today, the use
of sulfuric acid for this purpose has decreased a little as the industry now favors
the use of hydrochloric acid. Although hydrochloric acid is more expensive than
sulfuric acid, it produces results more quickly and minimizes the loss of base metal
during the pickling process.
The Manufacturing of Rayon
The textile Rayon is made from cellulose fibers derived from wood. These
are dissolved in a solution of Tetra Amine Copper (II) to produce a thick blue liquid
which is then injected into sulfuric acid to form Rayon fibers. Rayon is considered
to be a good semi-synthetic textile and can rival silk for drape and luster. Indeed,
it is sometimes referred to as ‘art silk’. It is easily dyed and the fabric is soft, cool
and smooth. However, unlike silk, Rayon does not insulate body heat so is perfect
for use in humid and hot countries.
 The Manufacturing of Lead-Acid Type Batteries
Sealed-unit lead-acid type batteries are used in the automotive industry for
cars and trucks. Sealed-unit lead-acid type batteries were invented in 1859 by
Frenchman Gaston Plants. Sulfuric acid is used in a dilute form to act as an
electrolyte to allow the flow of electrons between the plates in the battery. Sulfuric
acid used in this way is commonly called Battery Acid. It can vary in strength
according to the battery manufacturer but is generally between 28 to 32 percent or
between 4.2 to 5 Molar.
Potato Harvesting
Potato farmers employ specialist contractors to spray their fields of potatoes
before harvesting so that the green tops die back and blacken within a day or two.
This helps to dry out the stem and prevents them from becoming tangled in the
harvesting equipment. The usual method of spraying potato tops is with a solution
of sulfuric acid.
The Manufacturing of Medicines
Chemotherapy drugs are used to treat various types of cancer. Cancer cells
are more sensitive to DNA damage than normal cells so in chemotherapy
treatment cancer cells are destroyed by damaging their DNA. This process is
known as alkylation of DNA and a type of drug known as alkylating antineoplastic
agents are used. Sulfuric acid is used in the manufacturing process of such drugs.

Sulfuric Acid Market Volume

In 2020, China produced around 17 million metric tons of sulfur, making it by far
the world's leading sulfur producer. Sulfur is one of the most common chemical elements
found in nature. It is a pale yellow, tasteless, and odorless brittle solid commonly found in
volcanic regions and hot springs. Nowadays very little sulfur is mined from nature, as
most of the production is recovered due to environmental reasons. Byproduct elemental
sulfur recovered from natural gas and petroleum is the main source of sulfur worldwide.
Sulfur in the U.S.

The United States is the second-largest producer of sulfur worldwide, ahead

of Russia and Saudi Arabia. In 2020, sulfur production in the U.S. reached 8.1
million metric tons. From those, roughly 94 percent were recovered elemental
sulfur. Apart from being one of the main sulfur producers, the United States’ sulfur
consumption is also one of the highest in the world, reaching 9.8 million metric tons
in 2020.

Global Sulfuric Acid Market

Most of the global sulfur production is transformed into sulfuric acid, an

important commodity chemical with many applications. Sulfuric acid is extensively
 used as a battery component, in fertilizer manufacturing, metal ore leaching, and
as an intermediate chemical in the production of numerous other compounds. In
2020, the global market volume of sulfuric acid amounted to 256 million metric
tons, and it is forecast to increase to approximately 295 million metric tons in 2026.
By that same year, the market value of sulfuric acid is expected to surpass 11.5
billion U.S. dollars.

Figure 2. Sulfur production worldwide in 2020, by country

(in 1,000 metric tons)
-Data by Statista (2019)
LOCAL MANUFACTURERS & SUPPLIERS
1. Chemphil Manufacturing Corp.
Sulfuric acid plants established in Pasig, Taguig, and Batangas, Philippines

2. SBS Philippines Corporation

The Company was incorporated on 17 July 2001 and was formerly known as
Sytengco Philippines Corporation. The Company’s principal place of business is
at No. 10 Resthaven Street, San Francisco Del Monte, Quezon City, Philippines.

3. Emerald Chemicals, Inc.

4. Marubeni Philippines Corporation

FOREIGN MANUFACTURERS & SUPPLIERS

1. BASF SE (Badische Anilin- und Soda-Fabrik.)
 BASF SE is a German multinational chemical company and the largest
chemical producer in the world. The BASF Group comprises subsidiaries and joint
ventures in more than 80 countries and operates six integrated production sites
and 390 other production sites in Europe, Asia, Australia, the Americas and Africa.

2. Du Pont Company

American corporation engaged primarily in biotechnology and the

manufacture of chemicals and pharmaceuticals. DuPont now makes a broad array
of industrial chemicals, synthetic fibres, petroleum-based fuels and lubricants,
pharmaceuticals, building materials, sterile and specialty packaging materials,
cosmetics ingredients, and agricultural chemicals. It has plants, subsidiaries, and
affiliates worldwide.

3. Southern States Chemical

A family owned company, is the largest ISO 9001 Certified manufacturer

and supplier of sulfuric acid for industrial use in the Southeastern United States.

4. Dow Chemicals Company

 The Dow Chemical Company is an American multinational chemical
corporation headquartered in Midland, Michigan, United States and is a subsidiary
of Dow Inc. The company is among the three largest chemical producers in the
world. Dow manufactures plastics, chemicals, and agricultural products.

5. Aarti Limited Industries

It is one of India's leading manufacturers, exporters & suppliers of Sulfuric Acid

which is most commonly used in dyes, pigments, and agro chemicals.

6. Aurubis

With an output of more than 2 million t, Aurubis is one of the largest producers and
an important supplier to the global market.

7. PVS Chemicals Inc. (U.S.)

8. Chemtrade Logistics (Canada)
9. Shandong Lubei Chemical (China)
10. Shrieve (North America)
Shrieve is a leading supplier of Sulfuric Acid, Sulfur and Chemicals across North
America and our name has become synonymous with these chemical building
blocks.

11. Feralco Limited (UK)

Feralco Ltd is a major supplier of Sulphuric Acid . The company has a well
developed infrastructure to import, store and re-distribute the product to end-
users.

III. RAW MATERIALS

RAW MATERIALS / MANUFACTURE

When the sole problem involved was forming H2SO4 at a reasonable concentration
from SO2 generated by burning sulfur or pyrites and when energy was cheap, plants were
uncomplicated.
When energy prices increased sharply, the high-level energy resulting from the
oxidation of sulfur and sulfur dioxide became a valuable commodity.
Major changes in plant design were instituted to use this heat generate high-
pressure steam for generating electrical energy, thereby maximizing energy recovery
while minimizing process energy use.
This combination of a chemical plant and electrical (or steam) generation is known
as cogeneration. A modern sulfuric acid plant is, therefore, an electrical generating
system.

IV. MANUFACTURING Process

Manufacturing of Sulfuric Acid can be classified based on the raw materials used such
as:
 Elemental Sulfur
 Sulfur Ores
 Spent Acid
 Gases (H2S)
Elemental Sulfur
Production plant of 98.5% Sulfuric Acid (commercial grade) operating on sulfur as raw
material comprises the following sections:
1. Sulfur Feeding Section
2. Waste heat recovery section
3. SO2 conversion section
4. Acid towers section
5. Acid Cooling and storage/handling section
6. Plant infrastructure (electrical/civil/water treatment, etc.)

1. Sulfur Burning Section

Melter generates heat through the installed steam coils where solid sulfur is fed on
its grids with the help of an agitator that regulates the rate at which the sulfur is melted.
Once the sulfur is liquefied after melting, it is then pumped to the pressure leaf filter for
the purification process and is stored in a chamber containing steam coils. The sulfur
burner will be preheated to a high temperature by oil firing before the liquefied sulfur is
fed which causes the production of sulfur dioxide by instantaneous ignition. Drying tower
that contains an air blower supplies dried air to the burner generating gases with 10-
10.5% sulfur dioxide at temperatures ranging from 950-1000 ℃ .

2. Waste Heat Recovery Section

All the gases from the burning process are supplied in the waste heat recovery section
and are subjected to cooling lowering its temperature from 390-410 ℃ while others are
converted into high pressure steam. The gases will be exposed in a multistage conversion
system, frequently having four or five stages with three passes in the first converter and
one or two passes in the second. Steam superheater may be used to deliver the steam
to neighboring industries or to generate superheated steam for other purposes.

3. SO2 Conversion Section

Conversion of sulfur dioxide into sulfur trioxide can be represented by a catalytic gas
phase chemical equilibrium reaction:
SO2 + 12O2 ↔ SO3         ∆H = -99 kJ mol-1

Whereas its conversion can be represented as:

Conversion achieved = SO2 in - SO2 out SO2 inx 100

Le Chatelier-Braun principle states that varying the conditions of a system after it

is subjected to stress, will disturb the dynamic equilibrium thus, the system itself will adjust
to counteract the change that occur. This is one among the thermodynamic and
stoichiometric considerations in maximizing the generation of sulfur trioxide. Known
methods in maximizing production are:
 Removal of heat – for an exothermic reaction (such as for SO3),
temperature reduction will increase formation.
 Increase in oxygen gas input concentration.
 Removal of SO3 from the reaction zone.
 Using catalyst that will decrease the working temperature.
 Raising system input pressure.
 Increasing reaction time.
 Increasing the pressure of converter.

Usually, first and last passes of the converter contain ring type vanadium pentoxide
fused with cesium while the other passes have conventional vanadium pentoxide rings
that act as catalyst. The heat dissipated from the first pass will be recovered by a second
waste heat boiler. A Hot Heat Exchanger (HHE) accepts the gases from the second pass
before feeding to the third pass having Cold Heat Exchanger (CHE) ahead and then into
the economizer. Gases from the first three passes will be brought to the Inter Pass
Absorption Tower (IPAT) where all acid mist are removed completely through the candle
type demisters to keep the quality of the catalyst in the later passes. Cooling the gases
from the fourth pass is carried out through a dry air injection facility with temperatures
ranging from 380-390 ℃ which also helps in maximizing the formation of SO3 from SO2 .
Another economizer is provided after the fifth pass that enables preheating of boiler feed
water. The gases are then transferred to the absorption tower.
Plate heat exchangers are used to cool down the circulating sulfuric acid from the
drying tower, inter pass absorption tower, and final absorption tower exchanging heat with
the cooling water, that is cooled in a separate cooling tower.
4. SO3 Absorption
Absorption of SO3 allows the formation of sulfuric acid added with right amounts
of water to sustain its concentration.
The following factors have considerable effect on the efficiency of absorption
operation:
 H2SO4 concentration of the absorbing liquid from 98.3 to 98.7 %.
 Liquid temperature of 70℃ to 120℃ .
 Heat of absorption removed by Plate Heat Exchanger (PHE) for sulfuric
acid coolers.
 Moisture content in the raw gas producing fine gas mist particles that
made absorption process difficult.
 Existence of acid mist filter to remove mist of sulfuric acid in the system.
 Temperature if inlet gas.
For a battery grade sulfuric acid plant, the gases from the CHE or economizer after
the third pass are fed first into the 25% oleum tower before the IPAT by which the boiled
oleum generates SO3 vapors where some are absorbed in a glass/Teflon-lined steel (MS-
PTFE) and the rest are fed to the IPAT.

AVAILABLE TECHNIQUES
Sources of Sulfur Dioxide
 Sulfur burning
 Pyrites roasting
 Metal sulfide roasting and smelting
 Sulfuric acid regeneration
 Metal sulfate roasting
 Combustion of H2S or other sulfur-containing gases
Sulfuric acid production
 Divided into two groups depending on the concentration of SO2 in the gas
stream.
For stronger gas processes:
i.SCSA (6-8%)
ii.DCDA (8-11%)
For weak gas processes:
i.Based on oxidation by H2O2
ii.Based on activated carbon

A. Combustion of Sulfur
Natural deposits or desulfurization of natural gas or crude oil are the
sources of sulfur combustion, which is done in a one- or two- stage sulfur
combustion units operating at temperature ranges of 900-1050 ℃. Each unit has
combustion chamber with process gas cooler, where combustion gases typically
contains 11 vol.% of SO2 with low O2content. Generally, the gases are diluted to
10-11% before it proceeds to the conversion process and adequate amounts of
O2 is maintained for efficient formation of SO3.
B. Pyrites Roasting

Gases originally from pyrite ores roasted in fluidized beds usually

have unnecessary unburnt particles and dust but is removed through cyclones,
bag filters, and electrostatic precipitators. Auxiliary heaters or heat exchanging with
hot gases is used to increase the temperature of the gas that would allow maximum
conversion of SO3 from SO2. To regulate the temperature of the process gas and
for fixed SO2/O2 ratio, air injection is used if necessary.
C. Metal Sulfide Roasting and Smelting
Metallurgical processes often produce sulfur dioxide in the roasting process
of metal sulfides by which its concentration tells the total volume of gases in the
system. Equipment and facilities such as converter, heat exchanger, and
absorption tower may vary depending on the gas volume inlet. Once the gas exits
from the IPAT, it is reheated before entering the last stages of the converter
through exchanging heat from hot gases of the second and third passes of the
catalyst. The heat and temperature is affected by the conversion of SO3 achieved
and percentage of SO2, respectively.
Sulfuric Acid as Byproduct from Copper Ore Smelters

Sulfur dioxide in great amounts can be achieved by the addition of oxygen-

rich air which often contains excess dust from the ores. It is removed through
scrubbers and electrostatic precipitators and the resulting product gas will be
deposited into the sulfuric acid plant.

Sulfuric Acid a Byproduct from Lead Production

Similar to the products produced in roasting copper and zinc sulfide,

desulfurization of lead ores produces SO2 in various concentrations. Also,
removing the dust requires the use of scrubbers and electrostatic precipitators and
is then reheated at a temperature desired for the conversion of SO2 to SO3. Higher
sulfur dioxide concentration of 9-10% demands the DCDA process while for small
concentration of SO2, a single absorption process with a good tail scrubber in
continuous operation is used. Oil firing burners may be required if necessary.
Lead ores are contaminated with mercury that is poisonous to vanadium
catalyst, thus scrubbing it with mercuric chloride and then recovering it by
chlorination also referred as Norwar process:

HgCl2 + Hg → Hg2Cl2
2Hg2Cl2 + Cl2 → 2HgCl2 + 2Hg

D. Sulfate Roasting

Sulfates such as iron sulfate can be decompose to modified furnaces that

operates greater than 700 °C and elemental sulfur cokes, pyrites, fuel oil are added
to aid in the process by retaining the high temperature. Commonly, the
concentration of SO2 produced is 6% but may still vary and is fed afterwards to
the waste heat recovery boiler (WHRB) where it is cooled to 350-400°C, then
cleaned, and finally admitted to sulfuric acid plant.

E. Combustion of Sulfur-Containing Gases

 Furnace with operating temperature of about 1,000 °C is used for the
combustion of hydrogen sulfide (H2S). Processing the gases into SO3 and H2SO4
may be may be achieve using either ways:
 dry process by which water is removed by condensation followed by
drying.
 wet process where processing the gases will require water and steam and
the absorption tower is replaced by a condenser to generate 96% sulfuric
acid.

F. Tail Gas Scrubbing

Abatement (other word) of SO2 involves the reaction of SO2 and a liquid solution
through the use of scrubber having liquid circulating in loop from the bottom where
the inlet gas is fed to the top of the tower. Controlling the pH and addition of less
basic liquid in the circulating medium are the common method to alter the SO2
concentration of the resulting product. Basic liquid that can be used are:
 Ammonia
 caustic soda
 magnesium
 calcium hydroxide
which resulted to byproducts such as: ammonium-, sodium-, magnesium-, or
calcium-, sulfate, sulfite, and bisulfite.
For sulfuric acid production, Venturi scrubber incorporated with lacked towers
where maintaining of pH (8-8.5) is easy to do with the help of caustic soda. Instead
of costly caustic soda, lime solution is used but because of the formation of
insoluble calcium salts in pipelines and spray nozzles, another way is to employ
dual alkali process through NaOH solution circulating in the system and then
regenerating it using lime.

TECHNIQUES AVAILABLE FOR SULFURIC ACID MANUFACTURING

A. Single Contact Process

After dried dust-free SO2 is obtained, it is followed by oxidation process to

yield sulfur trioxide with an aid of alkali or vanadium oxides. Sulfuric acid in the
absorbers is absorbed (preexistence of oleum absorbers before the sulfuric acid
absorber if possible) and the presence of water in the absorber acid, made SO3 to
be converted into H2SO4. Addition of water or dilute sulfuric acid are the methods
to control the change in concentration of absorber acid at 99%. Generally, inlet gas
in a single contact process should have SO2 concentration of 6-10% in order to
obtain 98.5% to 99.1% conversion depending upon the efficiency of the design
and catalyst. In most cases, it is difficult to obtain a conversion of greater than 98%
but some employ the use of large amount of catalyst in the lass pass and operating
temperature of 410-415 °C.
B. Double Contact Process (Double Absorption)
One of the advantage of this process as compared to the single contact is
the degree of conversion obtained that is about 99.5%, which may vary depending
upon the organization of contact beds and contact time. The gas is cooled at
temperature ranges of 160-190 ℃ through the heat exchanger, and the resulting
sulfur trioxide will be contacted with 98.5-99.5% sulfuric acid by the intermediate
absorber. Note that an oleum absorber right before the intermediate absorber can
be installed if necessary. Addition of SO3 will disturb dynamic equilibrium causing
a shift favoring the formation of SO3, where its amount from the secondary stage
is brought to the final absorber.
For this process, 12 vol.% SO2 in the inlet gas is required to achieve a
conversion efficiency of 99.6% for a new plant which is in a daily basis. One of the
major inventions in this process is the candle type demister developed by
Monsanto (USA) that prevents 99.99% of mist above 1 μm which is known to
destroy heat exchangers and affect negatively the catalyst in the last two converter
passes .
C. Wet Contact Process (WCP)
WSP technology has its earlier application in treating lean hydrogen sulfide
gases wherein sulfur-containing feed gas is not required to be dried before the
conversion to sulfuric acid. After the roasting process, the dust and other particles
are removed by cyclones, bag filters, electrostatic precipitators, venture scrubber
etc. and the cleaned gas will be directed to the plant by an induced draft (ID) fan
that is also essential to overcome the pressure drop in the scrubbing process. The
gases will now be subjected to high temperature suitable for the conversion
process with an aid of a catalyst while hot gases coming out of the converter is
cooled by an incoming cold feed gas.
Water vapor present in the gases combines with the SO3 forming sulfuric
acid condensed on a special condenser modified to minimize the acid mist formed.
D. Cold Process using Liquid Sulfur Trioxide
As usual, the liquid sulfur is converted into liquid SO2 and then to liquid SO3
which does not require a special furnace for sulfur containing compounds. In this
manner of producing sulfuric acid, a very high pressure is used in reacting SO3
with water in comparison to the conventional approach. Using higher pressure is
economically wise as it improves the thermal efficiency and steam production.
Also, modern ways of recycling excess energy, sulfuric acid, and steam is
employed to increase the efficiency of both the reaction and the plant.
For a mixture subjected to high pressure, 98% sulfuric acid is stored under
agitation and measured amounts of liquid SO3 and water are mixed to yield sulfuric
acid. The mist eliminator recycles sulfuric acid to the converter at high pressure
which enhances the concentration of the acid. Steam produced is fed to process
 requirements such as generating electricity through a turbine. Sulfuric acid
subjected to high pressure should be directed to a pressure reducer which is
further sent to mist eliminator which deaerated and preheat the demineralized
water. The hot acid is cooled and finally directed to the storage tank.
Other benefits of cold process aside from the efficiency in generating
sulfuric acid at higher pressure are:
 Does not require the following equipment and facilities:
 special sulfur furnace;
 heat recovery system;
 multi-pass static converter;
 counter current heat exchanger;
 inter-pass absorption tower (IPAT);
 drying tower (DT);
 final absorption tower (FAT);
 mist eliminator;
 acid coolers; and
 alkali scrubber
which lower the cost in equipment and smaller space occupied.

INNOVATIONS AND MODIFICATIONS IN MANUFACTURING H2SO4

A. Process Improvements
The following are utilized to improve the conversion and heat recovery but
at the same time minimize the cost of production and capital requirement:
 Using atmospheric cooling ducts for hot gases
 Implement air injection to control gas temperature.
 Use of pre-heater such as hot gas or air heat exchangers that
simultaneously recover heat as hot air to control gas temperature.

B. Modifying Double Contact Double Absorption DCDA Process

Certain modifications are the following:
 (2+2) DCDA two catalyst passes preceding the IPAT and two passes
following it.
 (3+1) DCDA three catalyst passes preceding the IPAT and one pass
following it.
 (3+2) DCDA three catalyst passes preceding the IPAT and two
passes following it.
C. Catalyst
 Nitrogen oxides for old chamber process
 Platinized asbestos for contact process SCSA
 Vanadium pentoxide based with cesium compounds for both DCDA
and SCSA processes.
  Improved shapes:
 Pellets—with sizes of 6–8 mm diameters and 8–12 mm lengths
 Rings—hollow pellets which had gas contact surfaces inside and
on the outer surface for better catalytic action.
 Star/daisy shapes—these have even more surface area and
hence better catalytic action.

CONTACT PROCESS EQUIPMENT

A. Burners
used in treating solid raw materials such as sulfur and some sulfides that
is favorable to be stored in molten condition before it is converted into
sulfur dioxide. The material is then pump by heating lines to the storage
tank and the burners sprayed it to the furnace. The efficiency of the
burner is based on the concentration of SO2 in the material after the
process. In the present, plants have been producing 8-11%
SO2depending upon several factors.

B. Heat Exchangers and Coolers

The purpose of this equipment is to subject the gas to a temperature
that will favor the rate of reaction before it is directed to the first pass
converter. Usually, the temperature is adjusted to 425-440°C which
speed up the reaction and the gas are cooled down between the catalyst
to achieve higher conversion. Methods such as use of cold air, boilers,
steam superheater, or tubular heat exchangers is employed for better
efficiency.

C. Converters
This involves the formation of sulfur trioxide from sulfur dioxide into after
sulfur is burned which aims to increase the conversion by taking the
following into account:
 Equilibrium is an inverse function of temperature.
 Rate of reaction is a direct function of temperature.
 Composition of the gas and amount of catalyst considerably
affect the conversion and kinetics of reaction.
 Removal of sulfur trioxide formed increases the sulfur dioxide that
can be converted since it is a reversible reaction.

Location Temperature °C Equivalent Conversion, %

Gas entering first pass 410.0
Gas leaving first pass 601.8
Rise in temperature 191.8 74.0
 Gas entering second pass 438. 0
Gas leaving second pass 485.3
Rise in temperature 47 3 18.4
Gas entering third pass 432
Gas leaving third pass 443
Rise in temperature 11 4.3
Gas entering fourth pass 427. 0
Gas leaving fourth pass 430.3
Rise in temperature 3.3 1.3
Total rise 253.4 98.0
Table 1: Temperature and Conversions in Each Stage of a Monsanto
Converter using relatively rich SO2gas from sulfur.

Converters are commonly made from cast iron and aluminum-coated steel, but currently
stainless steel is the most preferred over other materials of construction. Careful
optimization and minimizing pressure drop should be considered to maximize the yield.

D. Sulfur Trioxide Absorbers

A common practice to improve the absorption of sulfur trioxide is the use of
98.5-99% sulfuric acid due to its lower vapor pressure compared to its other
concentrations. The purpose the presence of sulfuric acid in the mixing of
SO3 with water is to minimize the acid mist formed. Usually, acid is
employed in intermediate or final absorber to ensure maximum absorption
efficiency. From time to time, the concentration of sulfuric acid increases
that it is discharged and diluted to be recirculated in the absorber and the
process continuous. The tower is made of steel lined with acid proof-brick
and packed with ceramic shapes to allow the contact of gas or liquid to the
absorbing acid.
E. Blowers
It is used to deliver the sulfur-containing gas such as SO2 and SO3 from
one process equipment to the other, installed at the flow. They are electric
motor- or steam turbine-driven single stage compressor made of cast iron,
cast steel, or fabricated steel. One blower can generate pressure up to 55
kPa that it is the major energy consumer in the plant.

F. Acid Pumps
 It functions as acid circulator around the drying and absorption towers
driven by electric motor or steam turbines comprising a centrifugal
submerged pump with vertical shaft made from cast iron and alloy impellers
and shafts. Pumps with horizontal pumps are used in transferring acids from
one place to another.

G. Sulfur Pumps
Similar with acid pumps, it also comprises a submerged centrifugal pumps
with vertical shaft of cast iron construction that delivers sulfur from the pit to
the sulfur burner. It has steam-jacket discharge piping that traps and
maintains heat to prevent the solidification of sulfur.

H. Acid Coolers
This removes the heat of absorption and sensible heat of the incoming gas
by cooling the acid circulating over the absorbing tower. Also, it removes
the heat of dilution and heat of condensation of moisture from incoming gas
or air by cooling the acid circulating over the drying tower. In the present,
shell-and-tube type heat exchangers of alloy steel are used instead of cast
iron where a certain coolant such as water is passed over this coils through
which the acid was pumped.

I. Gas Purification
Gases formed in the processes contains impurities (e.g. dust) that requires
purifiers such as waste heat boilers (heat recovery and gas cooling),
electrostatic dust precipitators (gas cleaning), scrubbing or wash towers
(gas cooling and dust removing), and electrostatic mist precipitator.

J. Materials of Construction
The most common materials for construction are steel and cast iron which
is best for gas or air and strong acid. Brick-lined steel is often incorporated
to the steel due to the corrosiveness and erosive effect of hot acid.
However, cast iron is not suitable for oleum tower for an unknown reason.
In gas purification system, steel is used for sulfur dioxide gas with
temperatures above the acid dew point. For temperatures below the acid
dew point, and for liquids, lead and lead-lined steel, with or without brick
lining, alloy steels, and plastic materials, are used.

K. Plant Cost
 It is difficult to estimate the general cost of the plant, considering diversity
in design and construction as well as the place of construction. For a
modern double-absorption sulfur-burning contact plant producing
1800t/day, 100% H2SO4 basis, may cost roughly $25 million in the early
1980s.

MANUFACTURE BY THE CONTACT PROCESS

Until 1900, no contact plant had been built in the United States, although this
process had become very important in Europe because of the need for oleums and for
high-strength acids for sulfonation, particularly in the dye industry.

A substantial number of contact plants were built in the period 1900 to 1925, using
platinum catalyst.
In the middle 1920s, vanadium catalysts came into use and have gradually
completely replaced platinum.
By 1930, the contact process could compete with the chamber process regardless
of the strength of acid desired.
Since the mid-1920s most new facilities built have used the contact process with
vanadium catalysts.
There have been many improvements both in equipment and catalyst. Parts of the
process vary considerably, depending upon the type of raw materials used. Typical
flowcharts are shown in the figures below.

Sulfur-burning single-absorption contact sulfuric acid plant with air injection

(dilution) cooling between stages

Sulfur-burning plants are the simplest and cheapest since special purification of
burner gases to protect the catalyst is not required.
In the single-absorption configuration, which was the normal procedure until the 1970s,
little attention was directed to planning efficient heat recovery so that all heat evolved by
combustion and conversion could be recovered in the form of relatively high-pressure
steam.

Sulfur-burning double-absorption contact sulfuric acid plant

The contact process has been gradually modified to use double absorption (also
called double catalyst), which increases yields and reduces stack emission of
unconverted SO2.
Recently, U.S. government regulations have specified maximum allowable emissions of
SO2 from acid plants and require that all new plants either use the double-absorption
process or else be fitted with stack gas scrubbing systems to achieve comparable
emission levels.

Ore-roasting single-absorption contact sulfuric acid plant

When using other raw materials such as sulfide ores and spent or sludge acids,
extensive gas purification is required and the heat evolved in the catalytic conversion.
The heat evolved in roasting the ore or in the burning the spent acids usually is recovered
in the form of low-pressure steam.
 For sulfur burning plants, allowable emissions are equivalent to 99.7% conversion
of SO2 and for plants using smelter gases to about 99.0 – 99.5 percent conversion.
Conversion using the single-absorption contact process were typically about 97 –
98 percent.

V. WASTE TREATMENT

Sulphuric acid, commonly used in the manufacturing of fertilizers, explosives, other acids
and glue, is considered a toxic substance under the Agency for Toxic Substances and
Disease Registry (ATSDR), so treatment and disposal of wastes that contain sulphuric
acid are controlled by national regulations such as the Department of National Resources
under the DAO 92-92, Administrative Order 36, Series of 2004 which states that sulfuric
acid with a pH ≤2.0, is considered hazardous waste.

The main focus of sulphuric acid wastes treatment with regards to environmental
impact is to lessen the acid content as to not induce pollution and degradation in the
ecological context. Environmental regulation agencies must provide proper disposal
practice(s) of this chemical. Since sulphuric acid is not advised to be put in a landfill, the
following disposal methods are most used: (1) placing sulphuric acid wastes in sealed
containers and absorbed in vermiculite (hydrous silicate which expands when heated),
dry sand, or earth. (2) Another disposal method is by neutralization of the acid before it is
then discharged (one such way is by putting the acid waste into soda ash and slaked lime
before being flushed with large amounts of water).

There are methods that convert used sulphuric acid to a useable quality, which
costs less compared to procuring virgin (new) acids. This is another poignant concern
with the chemical’s waste treatment, more specifically its recovery for reuse. This is done
because some agencies restrict the amount of sulphuric acid forms that can be emitted
to the environment, and/or to be more economically sound since neutralization of the acid
costs more. The recovery is mainly done via concentration, which is feeding used acid to
a reactor in order to remove impurities and yield an output that is mostly (about 93% or
higher) sulphuric acid.
 For an Air-blown Concentrator, hot combustion gases are blown counter-current
to the sulfuric acid in two compartments in the concentration drum and remove water as
they bubble through the acid. Off-gases from the first compartment pass through the 2nd
compartment along with a portion of the hot gases from the combustion furnace. Some
of the sulfuric acids were entrained as a mist, therefore, the hot gases needed to pass
through a venturi scrubber and a cyclone separator, and washed with feed acid or water,
to remove the acid mist before it is discharged to the atmosphere. This procedure using
an air-blown concentrator yields an acid with a final concentration of 93% or slightly
higher. Hot gases, aided by the oxidizing action of the hot sulfuric acid, burn out any
impurities that may be found in spent acid being concentrated. If spent acid from
petroleum purification is being handled, the flow from the rear to the front compartment
passes through an intermediate storage tank, wherein a skimmer is used to remove some
of the non-volatile carbonaceous impurities. The concentrating compartments of the steel
drum are lined with lead and acid-proof masonry. And in this type of process, the boiling
point of the acid is reduced as low as 60℃ for a concentration of the acid of about 93%
by the effect of hot air reducing the partial pressure of the water vapor above the acid.

On the other hand, Simonson-Mantius vacuum concentrators, operates at

pressures lower than 675 Pa or 0.0067 atm and have been used long to concentrate
sulfuric acid with a concentration of about 93%. The Simonson-Mantius vacuum
concentrators use steam in tantalum indirect heaters to vaporize the water from the acid
which is maintained under vacuum. Using the vacuum, it lowers the boiling point of the
acid. Any noxious vapors are carried out of the concentrators are removed in the
condensers. With this process, no acid fumes or mist escapes to the atmosphere.
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