1.

ABSTRACT
I

did

my

second

summer

TIC. A.S aimed to get the insight of

college

lesson

up

to

the

6th

This report contains what I have

of my summer practice done in a

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practice in TOROS TARIM SANAYI. VE

actual practice in factory related with
semester.
learnt from the first until twentieth day
factory. It also contains the short history

and description of the company and

all the plants exist in the company.

Finally, this report also contains what

I have done in the company along with

the calculation, which is material balance calculations in the drying tower and energy
balance calculations in the melter and furnace which exist in the sulfuric acid plant.

2. DESCRIPTION OF THE
2.1 NAME AND LOCATION OF
TOROS TARIM SANAYI.
Tower, 4. Levent ili, stanbul.
Samsun retim Tesisleri, where
Tekkekoy 55 Samsun, Turkey.
2.2 HISTORY AND GENERAL
A company of Tekfen
agricultural industry group with

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COMPANY
THE COMPANY
VE TIC. A.S. is located in Tekfen
One of the branch, TOROS TARIM
I did is located at Sanayi Mahallesi,
INFORMATION
Holding, Toros

Agri

is

leading

its turnover, product / service range and

market share. The first production plant located in Ceyhan was established in 1974.
Toros Agri holds 38% of the installed fertilizer production capacity in Turkey with 1930
million tons. It offers a wide range of product portfolio to the farmers in addition to
fertilizer such as micro element plant nutrition products and specialty fertilizer.
The company sustains its fertilizer production activities in three different plants
located in Ceyhan, Mersin and Samsun. Toros Agri has a strong infrastructure thanks to
its nationwide distribution network, 7 regional offices, product warehouses with 550.000
tons capacity and close to 1200 dealers over the country. Toros Agri, operating in the
fields such as production of chemical fertilizers, techno agriculture, seed and seeding
production, terminal operations, pilotage-tugboat and ship agency services, is one of the
largest industrial enterprises in Turkey. Toros Agri is a pioneer in its sector with its
farmer-friendly applications, sense of quality, operational standards and innovative
products.
Samsun Plant was acquired via privatization in 2005. After modification and
rehabilitation, the plant resumed production in 2006. The additional capacity as well as
having a second terminal on the black sea coast, gave the company the edge it needed
in the market. The plant is located approximately 15 km away from Samsun on a
1.370.000 m2 land and has a production capacity of 3000.000 tons/year for compound
fertilizers, 227.000 tons/year for DAP and 188.000 tons/year for phosphoric acid.
2.3 PRODUCT SPECIFICATION
TOROS TARIM has 2 mainly products of fertilizer. They are DAP (Diammonium
Phosphate) and NPK (Nitrogen, Phosphors, Potassium). Beside product, TOROS
TARIM also has their raw material plants in order to produce fertilizer products. They are
ammonia, sulfuric acid and phosphoric acid plant. Raw materials taking from outside are
2

solid sulfur, phosphate rocks,

substances.
2.4 ORGANIZATIONAL
Having

brief

SAN. VE TIC. A.S. consists of :

Type of employee
Enigneer
Chemical engineer
METU CHE graduates
Technicians
Chemistry technicians
Workers
Administrative and other staff

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liquid ammonia and some chemical

STRUCTURE
organizational structure, TOROS TARIM

Number of employees
30
11
1
22
1
114
9

2.5 EVALUATION OF THE PLANTS ACTIVITY AREA

2.5.1 SE (Salk, Emniyet, Cevre) Department)
The first day of summer practice is done in SE (Salk, Emniyet, Cevre) / Health,
Safety, Environment department. TOROS TARIM considers safety, environmental impact
and quality standards in all aspects of its activities from production to distribution to
application for its employees, customers and the society it belongs to. TOROS TARIM
has slogan Being a leader and best in its fields adopted the principle of reaching
impeccability in occupational health and safety issues and aims having safe, secure and
healthy environment for its employees. TOROS TARIM adopts the HSE principles of IFA
(International Fertilizer Association) and applies the standard mentioned in Work Safety
Handbook. Raw Materials of hazardous used are below:
Ammonia (NH3)
Hazard Statements:

Flammable
May cause frostbite
May form explosive mixtures in air
Harmful if inhaled

Cause severe skin burns and eye damage

Very toxic to aquatic life

Sulfuric Acid (H2SO4)

Hazard Statements:
Causes severe skin burns and
May cause respiratory imitation
Reacts violently with water
Phosphoric Acid (H3PO4)

Hazard Statements:
May be corrosive
Causes severe akin burns and
2.5.2 Maintenance
My second day was

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eye damage

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eye damage
Department
done in maintenance department. Aim

of maintenance department is to create safe work environments for workers and staffs
involved in the maintenance equipment within regular maintenance program, low-cost
and high quality, and good performance in order to reach the target and the amount of
production.
Maintenance departments vision:
To strengthen safety work
To control products produced and used
To minimize breakdown system, to maximize maintenance equipment
To prevent damaged systems and analyze unseen fault
To minimize amount of emergency fault by MAXIMO program
2.5.2
Technical Services Finance and Administrative Affairs
My third day was done technical services. Technical services includes control
chief, purchasing chief and project engineering.
Control chiefs aim is to make continuous production and minimize shutdown
time. To reach this aim this department conducts prediction maintenance. It also use
technological instruments.
Purchasing Chiefs aim is to conduct with buying material needed by samsun
management and / or the services desired quality at the best time and the most
economical way.
Project Engineerings aim is to satisfy project demands required for the
implementation of the project within Samsuns business also to estimate investment
budgets of the required things for the approval process after the preliminary study being
carried out in the following years.
2.5.3 Process and Plan Department
Process and plan department is responsible for calculation of fertilizer material
balances and researching for new fertilizer composition
4

Process
and
plan
1. Production planning and
2. Unit consumption of
3. Controlling
of
4. Planning
of
truck
5. Unit cost of fertilizer
6. Daily plant report
7. Data controlling by the
Planning) system
8. Controlling of electricity
Reports of process and plan
1. Daily plan report
2. Bagging stock report
3. Tank depot stack report
4. Yearly inventory report

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departments responbility :
monitoring
production and raw material controlling
warehouses for production continuity
shipment
help of ERP (Enterprise Resource
and natural gas consumption
department :

(physically counting of products and

raw material)

3. PROCESS FLOWCHART AND DESCRIPTION

TOROS TARIM has 4 main production units. They are DAP fertilizer unit, NPK
fertilizer unit, phosphoric acid unit and sulfuric acid unit. The main raw materials used to
produce NPK and DAP fertilizer are sulfuric acid, phosphoric acid and ammonia.
3.1. AMMONIA STORAGE STATION
TOROS AGRI has three big refrigerated ammonia tanks. Two of them have
capacity of 15000 MT and 8000 MT, respectively. One of them is an existing spherical
ammonia tank which is delivered from the two refrigerated tanks. Moreover, TOROS
also has ship unloading facilities, ammonia vapor re-liquefaction system, send-out
system and other plants components and equipment required for a safe and reliable
operation.
3.1.1 AMMONIA STOREHOUSE
The 3 big refrigerated ammonia tanks are storages to store ammonia as
one of raw materials for fertilizer. The storages are designed in accordance with
5

API 620 and attached

temperature and liquid
arranged with a pressure
0

of -33 to 50 C.
3.1.2

AMMONIA REKeeping
tanks is very important.
lead the liquid ammonia

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with devices to measure pressure,

level.

Moreover,

the

storages

are

of -50 to 160 mbarg and a temperature

LIQUEFACTION SYSTEM
ammonia in liquid phase in the storage
However, heat entered into the tank can
evaporates then the tank pressure will

increase. To keep tank

pressure within normal operating range

it is necessary to extract

the evaporated ammonia as well as the

displaced ammonia vapor out the bank. The evaporated ammonia is re-liquefied
and sent back to the storage tank. Therefore, a refrigeration system is needed. It
consists of compressor, condenser and economizer.
There are 3 ammonia compressors. They are base load compressor,
peak shaving compressor and spare capacity compressor. The compressor
normally control the tank pressure at 35 mbarg. When the tank pressure
approximately at 50 mbarg, the base load compressor is started. If heat entered
is higher than the
capacity of one compressor, the peak shaving compressor is automatically
started at a pressure approximately 55 mbarg. Under normal storage operation
only one compressor is required to deal with the vapor generation. If the tank
pressure decreases to around 20 mbarg, both the base load and peak shaving
compressor should stop. When there are a further decrease in tank pressure of
around 10 mbarg, all compressors and pumps and all shut down valves in the
lines connected to the tank should be terminated. The tank is protected by a
vacuum breaker when the tank pressure drops below -2.5 mbarg. A sufficient
cooling water flow is available. This cooling water has a supply temperature
which is lower or equal to 28 0C.
The evaporated tank is extracted from the tank by the oil injected in every
compressors and the compressed oil and ammonia will be separated by the oil
separators. Then ammonia gas is liquefied by ammonia condensers against
cooling water. After that, a part stream the ammonia condensate which is
6

subcooled is flashed into

evaporated against the
ammonia is sent back to
The
two
ammonia
pump

3.1.3

to

the

and
heat
Finally, ammonia

distribute to DAP and

THE SHIP
The
ammonia

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the shell side of economizer where it is

tube

side.

Then

the

subcooled

the storage tanks.

refrigerated ammonia tank transfers
spherical ammonia tank by the help of
exchanger with the liquid of methanol.
inside the spherical tank is ready to

TORO
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NPK units.
UNLOADING OPERATION
stored in the tank is supplied as liquid

product from ammonia

carriers. The operation has to keep

freezing

prevent thermal stress in the pipelines.

in

order

to

When the vapor is generated during the chilling operation, it is extracted by the
ammonia compressors, re-liquefied and sent back to the storage tank. During
chilling and ship unloading operation the tank pressure is maintained at
approximately 50 mbarg. The system is ready after the ship unloading line is
chilled to -200C. The sample is taken then analyzed to verify the quality of
ammonia. The ship unloading arm needs to be cooled down to operation
temperature so that the unloading rate is set to a relative small amount of
ammonia.

Ammonia Tank 1

Ammonia Tank 2

AMMONIA TANK 1
AND 2
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C
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HEAT
EXCHANGER
WITH METHANOL

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CONDENSERS

ECONOMIZERS

Ammonia
Tank 3
DAP and NPK
UNITS

(Fig. 1 Flowchart of Ammonia Plant

3.2. SULFURIC ACID PLANT
TOROS also produce
and DPK fertilizer. Sulfuric

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Station)

sulfuric acid as raw materials for NAP

Acid Unit: It has a capacity of 726,000

tons (100% H2SO4)/year. DBI

was built by TEKFEN, the construction

unit which owns the process

license. It was designed to produce

2,200 tons (100% H2SO4) per

day and was used in 2015. Sulfuric Acid

Unit's raw material is solid sulfur. In addition, with the use of sulfuric acid unit, the
waste heat (steam) that comes out will be converted to electrical energy by way of
turbines.
3.2.1. SOLID SULFUR FEEDING
Solid sulfur is loaded by a loader into the solid sulfur storage hopper then
fed by means of the solid sulfur extraction conveyor. The free acidity present in
the sulfur is neutralized with lime stored in the hopper.

3.2.2. SULFUR MELTING, FILTRATION, STORAGE AND FEEDING TO FURNACE

The solid sulfur coming from solid sulfur weighing conveyor is fed into the
sulfur melting tank where it is continuously melted and is kept stirred by melting
tank mixer to increase the efficiency of the heat transfer to reduce ash settling.
The heat required for melting operation is provided by low pressure saturated
steam (6 barg at saturation), circulated in the tank. The condensate coming from
this section is not recovered in the condensate network because of possible
contamination of the boiler feed water. The condensate is collected into the
condensate tank, where it is cooled to 40 0C by mixing with sea water. After
melting, remove the impurities contained in the liquid sulfur. The liquid sulfur is
filtered by filters then the filtrated molten sulfur is sent directly to the storage
8

tanks. Those tanks are

to keep the conditions at
the product to the sulfur
Chemical reaction : S(L) +
3.2.3. THE SULFUR
The molten sulfur
MECS

design,

which

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operated with pressure of 3 barg steam

140 0C. Sulfur burner feed pumps feed
furnace.
Q --------- S(S)
COMBUSTION
is sprayed in special sulfur burners by
obtain

fine

particles

of

sulfur

by

mechanical atomization.

In sulfur furnace, in presence of air,

previously dried in the

drying tower. The sulfur and air ratio is

controlled in order to give a gas containing 11.5% vol SO 2 max at 11020C

approximately. From furnace, the gas passes through the waste heat boiler
connected with steam drum, where it is cooled down to 420 0C approximately in
order to make efficient work in catalytic conversion.
The process gas enters the 1st pass from the bottom of the converter and
the SO2 is partly converted to SO3. The gas leaving the 1st pass, at about 6210C,
is cooled down to 4350C in the high pressure super heater and is fed to 2 nd pass.
The SO2/SO3 conversion proceeds in 2nd pass and the outlet gas is cooled by the
hot interpass heat exchanger (shell and tube design) before feeding the 3 rd pass
at 4350C. The SO2/SO3 gas reaches the 3rd pass of the reactor; after crossing it
most of the SO2 is converted to SO3 and the gas (after cooling in the cold
interpass

heat exchanger and in the pass economizer) is fed to interpass absorbing tower
(HRS unit). The remaining SO2 coming back from the interpass absorbing tower
is heated at a temperature value suitable for the last conversion reaction, by
crossing in countercurrent the cold/hot interpass heat exchanger, then the gas
reaches the 4th pass of the conversion reactor at 415 0C. The produced gas
leaving the reactor at 4330C is cooled in the 4th pass economizer to be sent to the
final absorption tower at 1350 C.

In the final absorption tower, The SO 3 is

absorbed by circulating H2SO4. After final absorption, the remaining gas goes to
9

stack

and

the

collected to the common

Chemical reaction : S(L) +
(FURNACE)
SO 2 +
(CONVERTER)
3.2.4. AIR DRYING AND SO3

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concentration H2SO4 increases is then

acid tank.
O2

---------------

SO2

O2 ------------ SO3 + Q

ABSORPTION

The atmosphere

air, after filtration in the inlet air filter,

has to be dried before its

utilization in the sulfur combustion.

Drying is done by the flowing air through the drying tower, where concentrated
sulfuric acid is circulated in countercurrent with the air, to remove its humidity.
The filtered air is fed to the sulfur furnace by the process air blower located
upstream the drying tower. The SO3 gas is absorbed in the final absorption tower
and in the interpass absorption tower (which is inside the HRS) and by circulating
H2SO4. There are 2 acid loops installed. The first at low temperature, which
circulates acid through drying and final absorption tower, the second at high
temperature, where acid is circulated through the interpass absorption tower. The
absorption heat is removed in the low temperature loop by the common acid
cooler, whereas in the high temperature loop heat is removed by the HRS boiler.
To establish these two circulations, two dedicated vertical pumps are installed.
The common acid cooler is cooled with sea water and it is equipped by an anodic
protection system to avoid corrosion. Cooling of sulfuric acid to 400 C is
accomplished by use of sea water. Acid temperature to drying tower and final
absorption tower is kept constant by controlling acid by pass of the acid cooler.
These towers are designed to operate with acid at 98.5% concentration and inlet
temperature of 820 0C. The concentration of inlet sulfuric acid is kept always at

98.5% concentration, which corresponds to the minimum partial pressure of SO3

at the equilibrium with the acid and then to maximum yield of absorption;
furthermore it corresponds to the minimum azeotrope point of the system
10

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H2SO4/H2O which gives

control of concentration
drying/absorption section
amount

of

make-up

analyzer, which allows

concentration.
Chemical reaction : SO 3

TORO
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AGRI

the optimum efficiency in drying. The

of

the

sulfuric

acid

in

the

is achieved by adding the proper

water to the acid under control of an
high

accuracy

in

the

product

+ H2O --------- H2SO4 + Q

3.2.5. STEAM TURBINE

The

mechanical

work to the electrical generator, which

produce electrical energy at high voltage, exported to the external network are
provide by a turbine. The condensed steam recovered at the bottom of the
condenser is pumped by pumps to demi water storage tank. Beside HP (High
Pressure) steam, MP (Medium Pressure) steam (produced by HRS) is injected
into the turbine. Internal MP steam consumptions (for Sulfuric acid plant or other
uses) are lower than produced flow rate and therefore the available steam can be
used for energy recovery by expansion inside the turbine. Low pressure steam at
3.0 barg is extracted from a side extraction of the turbine in order to recover the
work coming from the enthalpy decrease from initial conditions (40 brag) for SAP
(Sulfuric Acid Plant) purposes.

SOLID SULFUR

11

Dry Air from drying tower

Steam In

Steam Out

MELTER

To steam

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SUPERHEATE
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Bypass

S
AGRI

WASTED
HEAT BOILER

1ST
CONVERTER
2nd
CONVERTER
3rd
CONVERTER
4th
CONVERTER

ECONOMIZER 2

Sulfuric acid

FINAL HOT INTERPASS

ABSORPTION HEAT

COLD INTERPASS
HEAT
ECONOMIZER 1

Sulfuric acid

STACK

HEAT RECOVERY
TOWER

Sulfuric acid
Low Pressure Steam

ACID TANK
Sulfuric acid
Sulfuric acid

(Fig. 2 FLOWCHART OF SULFUR AND SO2/SO3 CONVERSION)

3.3. PHOSPHORIC ACID PLANT

12

TOROS

has

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tons (100% P2O5)/year. It was

P2O5) per day and was used
as the raw material in the
Acid
be

Unit,
success

operation

of

the

produced

in

operating

the

chemical

TORO
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AGRI

Objectives: 1. To obtain a

phosphoric acid plant having 210,000

designed to produce 700 tons (100%
in 2015. Phosphate rock is being used
Phosphoric Acid Unit and in the Sulfuric
sulfuric acid is being used. In order to
phosphoric acid plant is the control and
reaction occurring in the attack system.
maximum extraction of P2O5 from the

rock
2. To provide a

easily filterable gypsum

3. To provide an easily washable gypsum so there will be a minimal

amount of Soluble P2O5 discharged with the waste gypsum.
When the gypsum produced is low in P 2O5, it will be easy to be filtered and washed
then the production rate and efficiency of the phosphoric acid plant are maximum.
Natural phosphate are mainly formed of fluorapatite, (Ca3(PO4)2).CaF2
The main attack reaction by the sulfuric acid is
Ca3(PO4)2 + 3 H2SO4 + 6 H2O ----- 3 CaSO4 . 2 H2O + 2 H3PO4 + heat
P2O5 losses will be either extraction losses occurring in the attack system or
water soluble losses occurring in the filtration section. There are two types of extraction
losses:
1. The first is due to the unreacted phosphate rock and is also called insoluble loss.
This loss results from in sufficient grinding or insufficient contacting of the
phosphate rock with the sulfuric acid.
2. The second type is the cocrystallized P2O5 and is also called citrate soluble P2O5
loss. This loss is due to formation of a solid solution of dicalcium phosphate
(CaHPO4.2H2O) in the gypsum.
To minimize citrate solube losses, a slight but definite excess of sulphate ions
(SO4) must be maintained through the attack and filtration system.

13

3.3.1. MILLING
Before coming to
should be reduced in
The rocks are fed with
3.3.2. REACTION

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the reaction, size of phosphate rocks

order to react optimal in attack section.
rod mills.

After leaving from

milling, phosphate sand comes to the

reaction section in order

to react with concentrated sulfuric acid

and phosphoric acid. The reactor maintains an agitated reaction volume in

circulation. Aim of reactor is the P2O5 content in slurry liquid phase around 2628% according to the used phosphate.
This section designed to produce phosphoric acid at a minimum
concentration of 28% P2O5. The temperature maintains at 72 760 C.
3.3.3. FILTRATION
The slurry is fed to one Tilting Pan Filter, fitted with a vacuum box and
one external filter separator.
Any entrained droplets from this separator are routed to the Recycled
Acid Buffer Vessel. Vacuum vapor from the filter separator pass to the filter
condenser where the gasses are scrubbed and vapor condensed by the use of
sea water. The remaining gases pass through a Final Acid Trap in order to
capture any eventual droplet before going to vacuum pump. The filter is fitted
with a filter fume hood which is vented to the gas scrubbing system and also an
acid brick lined channel under filter which catches any drops.
The initial filtrate of product acid sometimes cloudy with solids and always
slightly diluted by diluted by water of the cells and the cloth weave is discharged.
This liquor will be recycled to the attack reactor via recycled acid buffer vessel so
that this does not affect the quality of the product acid.

14

The weak acid

filter acid pump to the
recorder.
gypsum

After
is

counter-

final stage wash prior to

from the flash cooler pre-

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equivalent to the production is fed by

weak acid maturation tank via a flow
separation of the mother liquor, the
currently washed in two stages. The
gypsum discharge is fed with water
condenser.

The filtrate from the final

cake wash drains from the distributor to

the suction of the weak

acid wash pump which pumps the

filtrate to form the first

cake wash. The filtrate from this wash

drains from the filter distributor to the recycled acid buffer vessel.
The gypsum after the two-stage washing is discharged to the gypsum
cake discharge hopper and re-slurryfied.
If the solid content is too high, there is problem of viscosity. If the solid is
too low, residential time decreases and there are small size of crystals and bad
filtration. Bad filtration indicate that move water stays in cake makes less water
returns to attack reactor. As a result, %P2O5 in attack filtrate process then crystal
get smaller and difficult to filtrate.
P2O5 Recovery =

Quantity of P 2 O5rockQuantity of P2 O 5cake

x 100
Quantity of P 2O 5rock

%CaO(rock) Quantity of cake

=
=RF
%CaO (Cake) Quantity of rock
RF: Quantity of gypsum produced by ton of dry phosphate rock
3.3.4. CONCENTRATION
Two lines of vacuum concentration operate in parallel to concentrate a
total of P2O5, from 28% to 52% phosphoric acid. Weak acid 28% P2O5, which is
stored in the acid storage area, is pumped by the weak acid transfer pump to
concentration to the evaporator where the boiling temperature of the acid is
15

controlled. The vacuum

sprays

sea

water

to

pass trough the outlet

The

water

from

the

gravity to the sea water

condenser
avoid
can

contains

that
be

before

this

acid

removed

by

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system consists of a condenser which

remove the condensable gases. They
draining to the condenser seal tank.
condenser
return.

seal

The

tank

gases

overflows
going

to

by
the

small quantities of P2O5 droplets. To

pollutes the sea water, these droplets
praysep

droplet

separator

situated

the

condenser.

Acid is recirculated by an axial-flow

recirculation

pump

through the heat exchanger and back to

the evaporator. The recirculation rate is calculated to ensure the difference

of temperature which is acid inlet to acid outlet of about 3 0 C. Typically the inlet
and outlet temperatures are 850 and 880 C respectively.
EVAPORATED WATER

Weak Acid

EVAPORATOR
PRODUCT CONCENTRATED ACID

Steam LP

Condensates

H
E
A
T
E
X
C
H
A
N
G
E
R

pump

(Fig. 3 Basic Principles of Concentration)

Cake wash Water

16

Phosphates

H2SO4

Attack Disgestion

Recycles Acid

Product Acid

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FILTRATION

TORO
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(Fig 4 Filtration Diagram Flow)

3.4. NPK FERTILIZER PLANT
Raw materials are 48 54 % phosphoric acid, liquid anhydrous ammonia,
sulfuric acid, potash (KCL), urea and filler as main raw materials. Additional chemicals
and utilities are defoamer, coating oil, natural gas, raw water, instrument air, plant air
and LP/MP steam.
3.4.1. PRENEUTRALIZER
Preneutralizer is a cylindrical reactor used for production of ammonium
phosphate / sulfate slurries. This PN may operate in combination with the pipe
reactor. It can be fed with phosphoric acid, sulfuric acid, phosacid liquor from
scrubbing system, process water and ammonium from chiller / evaporator. PN
level indicators should be carefully followed from DOS in the control room. PN
also keeps proportions between phosacid, sulfuric acid, scrubbing liquid and gas
ammonia. The temperature in PN should be 115 3000C. The slurry leaving the
PN reactor is transferred to the granulator by the variable speed slurry pumps.
3.4.2. GRANULATION
Granulator drum is another important point where the reactions take
place, after PN. The function is to transform the slurry into a granular fertilizer
product of required composition and size. Granulation is mainly accomplished by
a series of chemical and physical reactions. The main reaction is the ammonia
neutralization wit phosphoric acid, and in a lesser extent with sulfuric acid. PN
slurries are ammoniated with ammonia, fed through the ammonization system
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deeply into the solids

product N / P ratio.
important

that

the

performance in order to
granulated product are in
granulometry conditions.
Chemical

reaction

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H3PO4

bed to achieve the required final

During

the

operators

plant

observe

operation
the

it

is

granulators

ensure that the solids bed and the

the proper liquid / solid phase and

H2SO4 + 2 NH3 ------> (NH4)2SO4

+ NH3 ---------> NH4H2PO4

3.4.3. DRYING
The product leaving the granulator drum has a free humidity of between 2
to 3.5 % that should be reduced till the final product specification of 1 1.5 %.
The combustion chamber is natural gas fired. Air for combustion and dilution is
supplied by fans. The temperature of the hot gases entering the dryer is about
150 300 0C. Discharge air temperature will usually be between 80 -110 0C,
depending on NP / NPK grade. The gas flow at the dryer outlet passes through
the cyclones sucked by the dryer exhaust fan. After cyclones the gas flow goes
through the scrubbing steps before being released to the atmosphere.
3.4.4. SCREENING AND GRINDING
The product leaving the dryer, a mixture of fines, oversize and on-size
product, is discharged to belt conveyor. Later to elevator and conveyor, being
finally fed to the screening section. A screens splitter divides the flow into two
lines feeding the oversize screen feeders. Oversize screens are designed to
separate and send oversize material to be crushed and discharged by gravity to
the recycle hopper to granulator. Oversize screens feed the product of over 2
mm. For on-size product of below 2 mm from undersize process screens is
collected in th recycle regulator conveyor hopper.
3.4.5. POLISHING SCREEN

18

The product from

containing

some

fine

fines larger than 4 mm or

product elevator. There
be

separated

and

size product advances to

3.4.6. PRODUCT COOLING

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recycle

regulator

conveyor

still

product under 2 mm and few oversize

with irregular shape, feeds the final
the remaining fines and oversizes will
returned to the recycle, whereas onfluidized bed cooler.

The

on-size

product coming from the granulation

usually

has

temperature of 80 95 0C. In order to

keep the final product in

good physical state, it will be necessary

loop

to cool it down; otherwise its surface will soften up enhancing

its caking. To cool it down, a fluidized bed cooler is installed. This equipment
blows the air required for cooling. It is necessary to ensure that air blown is cold
and dry enough. To achieve that goal, air should pass through an air chiller and a
steam desaturator then come to the cooler. The temperature of outlet product will
be approximately 40 0C. Finally, the final product is ready to storage.
H2SO4

PRENEUTRALIZ
ER

H3PO4

FILLER
AIR HEATER

FUEL

AIR

GRANULATOR
solution

SCRUBBER LIQUOR
RECYCLED

SCRUBBIN
G SYSTEM

NH3
DRYER

SCREENING
AND GRINDING

19
POLISHING
SCREEN
COOLER

CYCLONES

oversizes

CRUSHER

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Oversizes / irregular shape

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AMBIENT AIR

COATING AGENT

COATING DRUM

STORAGE

Fig. 5 NPK Process Diagram

3.5. DAP FERTILIZER PLANT

TOROS TARIM has the DAP (Diammonium phosphate) fertilizer production
capacity of 300.000 tons / year. This chemical fertilizer is a fertilizer that can be
produced when ammonia reacts with phosphoric acid.
The process production of DAP is like as NPK production. There is mole ratio
between nitrogen and phosphorus which is 1.5. Phosphoric acid, ammonia gas and
pre-scrubber liquor enter to the preneutralizer maintained a mole ratio to guarantee the
solubility of the slurry. The ammonium phosphate slurry is fed to the granulator. In the
granulator, there are pipes flowed by phosphoric acid and ammonia gases in order to
increase the mole ratio of DAP up to the desired value. Then the product leaving
granulator is fed to the rotary dryer where the product is dried by hot gases from the
combustion chamber to lower the humidity to 1.0 -1.5%. After that the product is
distributed over the screens. The screens are double check screens where the
oversize product is sent to the chain mills and the on-size product is transferred to the
product screen elevator for distribution on the product screens. The aim of the product
screens is to remove the oversize and irregular shapes which are not removed by the
oversize screens. The filtered fines fall onto the recycle belt and the product size is fed
to the fluidized bed cooler. After that the product comes to the coating drum then
conveyed to the storage.
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PRENEUTRALIZ
ER

H3PO4

FILLER
AIR HEATER

FUEL

AIR

GRANULATOR
solution

SCRUBBER LIQUOR
RECYCLED

NH3
DRYER

SCREENING

CYCLONES

oversizes

CRUSHER

AND GRINDING

POLISHING
SCREEN

AMBIENT AIR

SCRUBBIN
G SYSTEM

COOLER

21
COATING DRUM

Oversizes / irregular shape

GAS

COATING AGENT

Fig. 6 Flow Diagram of DAP

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STORAGE

Plant

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3.6. SOME AUXILIARY PLANTS

a. START-UP BOILER
The aim is to keep the start-up boiler ready to operate and to use / activate it when
the sulfuric acid facility needs steam.
b. AIR COMPRESSOR and DRYER
The aim to fulfill the need of the units instrument and service air.
c. RMS-C NATURAL GAS STATION
The aim is to deliver the natural gas to the point of usage at the RMS-C natural gas
pressure reducing station and activating / deactivating the pressure reducing
station.
d. STEAM BOILER
The aim is to keep the steam boiler ready to operate when it is needed to enter the
circuit and SAP facility stop working, to use / activate it when it needs steam, and
to send steam to the units.
e. DEMINERALIZED WATER SYSTEM
The aim is to satisfy the need of the unit production from raw water passing
through Bernoulli unit, ultrafiltration unit, reverse osmosis unit, MBDI unit and
neutralization unit.

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4. WORK DONE IN THE PLANT

I

did

my

second

summer

A.S., Samsun, Turkey from 24th of

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practice in TOROS TARIM SAN. VE TIC.

august to 27th of September, 2016.

This company produces fertilizers

with variety of compositions. Fertilizers

produced

Furthermore,

are

DAP

and

NPK.

fertilizer is supported by their raw

the

production

of

material plants which are sulfuric acid,

phosphoric acid and ammonia plant. During my summer practice work, I was introduced by
the supervisor about the production as well as the development done in the company for
about twenty work days.
In the first 4 days of the practice, I was given a brief orientation regarding the whole
company, such as SE (Salk Emnyet evre), maintenance, technical services and
process and plan department. After the first 4 days, for the rest of the days I was shown the
whole production from the raw materials storage until the packaging of the product in the
plant. Inside the plant, some workers, technicians and chemical engineers also introduced
certain production in which each of the worker work at. Besides that, I also was shown the
laboratory work within the plant. I also conducted a literature research regarding the
materials used by the plant as well as the unit operations run the plant. Having introduced
the general production, I was also explained the human resources information given by the
human resources department. This information includes total employees work in the plant.
Besides getting information from the staffs, I also had a chance to ask the workers that
responsible for the production in the plant. Some information related to the source of the
raw materials, selling distribution of the company and certain processes were explained by
the workers.
In the 5th day I was shown the whole production plants existed in the factory. In the 6 th
and 7th day I was having brief information about the ammonia plant with the detail
process and some auxiliary plants such as start-up boiler, air compressor, natural gas
station, demi water system and steam boiler. In the 8th 10th day I did work in the sulfuric

23

acid plant. I was introduced the

rocks to the sulfuric acid product.
in this plant was explained to me
melting, filtration, combustion of
absorption

and

collecting

the

produced by the factory itself from

me so that the company has its own
th

plant, In the 11

13

th

day I did

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whole process in details from sulfur

Some chemical reactions occurred
such

as

feeding

sulfur

rocks,

sulfur, conversion of SO2 to SO3, SO3

product of sulfuric acid. Electric
steam turbine was also explained to
electricity. Likely in the sulfuric acid
work in the phosphoric acid plant. I

also was

having brief about the whole process in details from phosphor rocks to the phosphoric
acid product. I was In the 14th- 17th day I was shown how the NPK and DAP fertilizer unit
produce.
In every plants all professional chemical engineers working on their each
responsibilities was introduced to me. I was also explained by them about all unit
operations used in the plants with their functions which I have learnt at METU such as
heat exchanger, turbine, boiler, condenser, packed column absorption, etc. Beside them,
all processes related with chemical engineers are introduced to me such as, combustion,
filtration, neutralization, conversion, recycle, etc.
In the 18th- 19th day I was focusing on the calculation that was going to be done within
the plant. After several observations and also asking the internship supervisor and some
chemical engineers, then my problem got approved to work and focus on the drying tower,
melter and furnace existing in the sulfuric acid plant. I prepared the calculation of material
and energy balance that I learnt in CHE 204, CHE 222 and CHE 327. I got some data
required for calculation by asking my supervisor and a chemical engineer from process
and plan department. I took some properties required in the calculation from literatures. I
also always consulted with my internship in order to be controlled whether there exists
mistakes in the calculation part.

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5. MATERIAL AND ENERGY BALANCE CALCULATION

Properties:
Species
Mw (g/mol)
Entahlpy of formation (KJ / mol)
S
32
0
SO2
64.063
-296.8
SO3
80.058
-394.93
H2SO4
98
-810.40
H2O
18.015
-285.84
O2
31.99
0
N2
28.013
0
(Perry, 1999)
(Sinnott, Coulson, and Richardsons chemical engineering volume 6, chemical engineering
Species
Latent heat (KJ / mol)
design,
1999)
S
Fusion, 1254.4
Vaporization, 48320
SO3
Vaporization, 40679
Cp = a + bT + cT 2 + dT3
H2SO4
Vaporization, 56000
H2O
Vaporization, 56000
where T in 0C
Species

a x 103

B x 105

C x 108

D x 12

Range

of
0

S
29.00
0.2199
O2
29.10
1.158
SO2
38.91
3.904
(Rousseau and Felder, 2005)
Specie
s
25

Temperature range (0C)

0.5723
-0.6076
-3.104

-2.871
1.311
8.606

temperature ( C
0 1500
0 1500
0 1500

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298 368
368 388
115 - 445

(Perry, 1999)
Dry Air in

DRYING
TOWER

-0.53376 + 0.17792T 4.992x10-4T2

0.104352 + 0.16592T 4.142 x 10-4T2
-4540.97 + 26.065T - 5.552 x 10-2 T2 +
4.201 x 105 T3 + 5.4588 x 107 T-2

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H2SO4 In

H2SO4 out

Dry Air out

FURNACE

MELTER
Liquid Sulfur

SO3 gas
Solid Sulfur

N2
O2

(Fig. 6 Process Flow Diagram Problem)

26

Aim

: To design 2200 tons /

Assumptions :

1. The process is
2. The process

Material Balances

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day of H2SO4
an open system
occurs at a steady-state condition

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Product of acid=2200
-

tons
day 1000 kg
x1
x
=9166.67 kg/hr
day
24 hr
1 ton

Assume the strength of the product acid is 98%

0.98 x 9166.7 kg / hr = 89833.35 kg / hr
In Kmoles,

1 Kmoles
kg
x 89833.35 =916.67 Kmol/hr
98 Kg
hr

Assume that overall absorption of the acid is 100%

Than SO3 required = 916.67 Kmoles / hr

Assume that there is 100% combustion of sulfur

Then

amount of sulfur required=916.67

Kmol
Kg
Kg
x 32
=29333.44
hr
Kmoles
hr

The amount of oxygen required to convert 1 Kmoles of S to SO3 is 1.5 Kmol

Then

the amount of oxygen required=916.67

Kmol sulfur 1.5 Kmol O2

KmolO 2
x
=1375.005
hr
1 Kmol sulfur
hr

There is some amount of excess oxygen that has to be used.

40% excess of oxygen,

Oxygenrequired=1375.005

27

KmolO 2
KmolO 2
x 1.4=1925.007
hr
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Then total dry air coming from drying

calculated

tower or fed to the furnace can be

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Dry Air dryingtower =1925.007

In Kg,

9166.7

Kmol O 2 100 Kmol Dry air

Kmol Dry air
x
=9166.7
hr
21 Kmol O 2
hr

Kmol Dry air 29 Kg Dry air

Kg
x
=265834.3
hr
1 Kmol dry air
hr

At 30 0C there exists 65% relative humidity.

From the psychometric chart (perry, 1999). Humidity = 0.0165 Kg water / 1 Kg Dry air
Then,

water entering with dry air=9166.7

Kmol Dry air 29 Kg Dry air 0.0165 Kg water

x
x
=4386.2
hr
1 Kmol dry air
1 Kg Dry air

7 Kg/hr

Moles of water entering with dry air=4386.27

Kg water 1 Kmol
Kmol water
x
=243.7
hr
18 Kg
hr

Finally, total weight of dry air entering

Dry Air inlet=9166.7

28

Kmol dry air 29 Kg dry air

Kmol water 18 Kg water
Kg
x
+243.7
x
=270220.5
hr
1kmol dry air
hr
1 kmol water
hr

Dry air in

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H2SO4 In

H2SO4 out
DRYING TOWER

Dry air out

(Fig. 7 Drying Tower)

dry air

Given :
m

m
( dry air out )=265834.2 Kg/hr
As water is being removed from the incoming air to make it dry, the 98.5% acid that is being
recycled to the tower, decreases in concentration and let this concentration be assumed as
98%, then,

Equation (1)

29

acid

0.015 x m

Equation (2), H2SO4 balance

acid

Solve both equations,

m

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acid

0.985 x m

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m
( acid out ) =864095.20

kg
hr

ENERGY BALANCES

MELTER
Solid Sulfur

Liquid Sulfur

m=29333.44

kg
hr

(Fig. 8 Melter)
Assumptions : 1. All solid sulfur are melted 100%
2.
3.
4.
5.

Sulfur procured is in its rhombic form which is the most stable

Open system
No accumulation of material and energy
Work done against pressure is neglected, any redual energy input from shaft
work is also assumed to be negligible.

Energy balance equation for open system (Rousseau & Felder, 2005)

H + Ek + Ep=Q+
30

With assumptions that we have,

Specific enthalpy of sulfur at 30 0C (303

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H=Q
K)

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303

KJ
H= (0.53376+ 0.17792T 4.992 x 104 T 2 ) dT =39.2614
Kmol
298

Specific enthalpy of sulfur at 150 0C (403 K)

303

388

42

H= (0.53376+ 0.17792T 4.992 x 104 T 2 ) dT + ( 0.104352+ 0.16592T 4.142 x 104 T 2 ) dT + 1254.4+

298

368

For calculation of specific enthalpy of sulfur at 150 0C, The changing phase of sulfur was
accounted. The phase of sulfur changes at 95 0C and then melts at 115 0C.

H=Q
^
H=n x ( H OUT H )

^
H=916.67 Kmol x ( 266939.26 ) KJ =2410603 KJ

hr
Kmol
hr

Or

2410603

KJ
1 hr
x
=669.61 KW
hr 3600 s

Thus, the energy of melter should be supplied with 669.61 KW

31

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Dry Air out 25 0C

FURNACE

Liquid Sulfur

SO3 gas 1100 0C

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150 0C
N2

(Fig. 9 Furnace)
O2

Moles of liquid sulfur

Moles oxygen with dry air
Mass rate of dry air

= 916.67 Kmol / hr
= 1925.007 Kmol hr
= 265834.3 Kg / hr

As we mentioned before, 100% combustion of sulfur

Then,

SO 2 formed =moles of liquid sulfur =916.67

Kmol
hr

Oxygenleaving=moles of oxygen comingmoles of SO 2 formed

1925.007

Or

1008.337

Kmol
Kmol
Kmol
916.67
=1008.327
hr
hr
hr

Kmol 31.99 Kg
Kg
x
=32266.78
hr
Kmol
hr

Nitrogen gas leaving=Dry air outoxygen leaving

265834.3

Kg
Kg
32266.78
hr
hr

233567.52

Kg
hr

Energy balance equation for open system (Rousseau & Felder, 2005)

H + Ek + Ep=Q+

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By assumptions that I made then,

H + Ek + Ep=
Q+

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Heat of reaction from the heat of

formation
T

H= H 0f + Cp ( T ) dT
25

Inlet

KJ
^
H sulfur =2669
Kmol
n sulfur
=2933.44

Kg 1 Kmol
x
=916.67 Kmol/hr
hr 32 Kg

^
^ x T =1005
H sulfur =Cp

KJ
Kj
x 25 =25125
Kg.
Kg

DA =265834.3 Kg
m
hr

Outlet
1100

KJ
^
H SO 2= ( 38.91 x 103+3.904 x 105 T3.104 x 108 T 2 +8.606 x 1012 T 3 ) dT =54.814
mol
25
n SO2
=2933.44

33

Kg 1 Kmol
x
=458335 mol /hr
hr 64 Kg

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1100

KJ
^
H O 2= ( 29.10 x 103+ 1.158 x 105 T 0.6076 x 108 T 2 +1.311 x 1012 T 3 ) dT =36.069
mol
25
nO 2=3266.78

Kg 1 Kmol
x
=1008340 mol / hr
hr 32 Kg

1100

KJ
^
H N 2= ( 29.00 x 103 +0.1299 x 105 T 0.5723 x 108 T 2+2.871 x 1012 T 3 ) dT =33.99
mol
25
nN 2=233567.52

Kg 1 Kmol
x
=8335743 mol/ hr
hr 28.02 Kg

n OUT . ^
H=Q=
H
. ^
H

OUT n

[ ( 8335743 X 33.99 ) + ( 1008340 X 36.069 )+ ( 458335 X 54.814 ) ] OUT [ ( 916.67 X 2669 )+(25125 X 265834
H=Q=

6336708485 KJ /hr
Or

6336708485

KJ
1 hr
6
x
=1.76 x 10 KW
hr 3600 s

Minus sign indicates exothermic

34

The value is valid since in the literature

furnace.

With the following design of

material balances I have found the

and out in the drying tower are

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exothermic process occurs in the

2200 tons per day of H2SO4, from

mass rate of the concentrated acid in

85708.92

kg
hr

and

864095.20

kg
hr ,

respectively, with assumption that I

made are the strength of the product

acid of 98%, the overall absorption of

the acid is 100%, 100% combustion of

sulfur, steady state condition and open

system.

Moreover, from energy balance I found the energy transferred to the melter and furnace
6

are 669.61 KW and 1.76 x 10 KW , respectively. Those values are valid since endothermic
process occurs in the melter and exothermic process occurs in the furnace. Assumptions that I
made are open system and steady state conditions.

6. CONCLUSIONS
According to the calculation that I have made, heat transferred by furnace and melter are

1.76 x 106 KW and 669.61 KW, respectively. Furthermore, from material balance
calculation that I have made in the drying tower are the concentrated acid in and out of
35

85708.92

kg
hr

and

calculations are based on designing

production which is done in the
For the process calculation, I
advisor

and

needed

in

plan

some
calculation

with

TORO
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864095.20

kg
hr , respectively. Those

2200 ton per day of sulfuric acid

sulfuric acid plant.
have consulted with my internship
engineers. I also discussed for the data
chemical engineer from process and

Finally,

my

focused

on

material balance in the drying tower

and energy balance in the melter

As the personal effect, this

and furnace.
second summer practice that I did at

sulfuric

department.

chemical

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acid

plant

problem approved to work on the

TOROS TARIM SAN. VE TIC. A.S., Samsun, Turkey, under TEKFEN HOLDING really boost
my experience of actual application related to what I have learnt in the chemical engineering
department, METU. Although I may not learn in details for every process, I still can get the
insight of the process in factory. Furthermore, like my internship supervisor said, almost all
unit operations that I learnt in theory are found in the factory such fan, absorber, heat
exchanger, compressors, filters, condenser, reactor, etc. Also my internship supervisor said
that fertilizer factory is like a school for chemical engineer, working in 5 years in here is like
finishing the 2nd university. Without having summer practice in the factory, I will not be able
to enter the industrial world in the future if I only rely on my theoretical knowledge from the
college. So, I gained lots of practical thing that I may not get from the class in college.
Finally, as the innovation in the company goes on, I hope that TOROS TARIM SAN. VE
TIC. A.S. keep being the lead of Fertilizer Company in Turkey and in the world as its vision
and still provide the best quality of fertilizer for better agriculture of Turkey in the future.

7. REFERENCES
- Sinnott, R.K. (1999). Coulson and Richardsons Chemical Engineering Design, Vol.
6, Third Edition, pp. 407, 435.
-

Perry Robert H., Green Don W., (1999), Perrys Chemical Engineers Handbook, 7
Edition, McGraw-Hill Companies Inc., pp. section 18-2 to 18-12.

36

th

Felder, R.M. & Rousseau, R.W.

Chemical Processes,

3rd Ed. USA: John Wiley &

TOROS TARIM SAN. VE TIC.

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(2005). Elementary Principles of

Sons, Inc.
A.S. from www.toros.com.tr

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8. APPENDICES
APPENDIX A
SULFURIC ACID DOUBLE CONTACT DOUBLE ABSORPTION FLOW PROCESS

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APPENDIX B
SIMFLIFIED FLOW CHART OF
DIHYDRATE PROCESS

39

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PHOSPHORIC ACID PLANT WITH

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ME
R
PR
AC
TIC
E II
(C
HE
40
0)
TORO
S
AGRI

APPENDIX C
NPK-DAP FERTILIZER FLOW PROCESS DIAGRAM WITH PIPE REACTOR
SYSTEM

40

S
UM
ME
R
PR
AC
TIC
E II
(C
HE
40
0)

APPENDIX D
NPK FERTILIZER FLOW PROCESS

41

TORO
S
AGRI

DIAGRAM WITH PRENEUTRALIZER