In-Plant Training Report on

TSP Complex Limited (TSPCL)

TSP COMPLEX LTD

An Enterprise of BCIC
Norrth Patenga, Chattogram
 Department of Chemical Engineering and
Polymer Science
Shahjalal University of Science and Technology, Sylhet

Report on Industrial Attachment at TSP Complex Ltd.

Course Title: In-Plant Training I

Course Code: CEP-378

Submitted to

Dr Mohammad Rakib Uddin Dr Muhammad Abdus Salam

Professor Associate Professor

Department of Chemical Department of Chemical

Engineering and Polymer Science, Engineering and Polymer Science,

Shahjalal University of Science and Shahjalal University of Science and

Technology, Sylhet Technology, Sylhet

2
 Submitted By:

Name Registration No Contribution

Energy Balance, TSP Plant,

Akib Uddin 2019332017 Material Balance, Phosphoric
Acid Plantt

Phosphoric Acid Plant,

Md Ibrahim Ahmed 2019332036 Material Balance, Energy
Chowdhury Balance

Material Balance, Sulphuric

Ahmed Shakibul Islam 2019332045 Acid Plant, Energy Balance,
Phosphoric Acid Plant

TSP Plant, Water Treatment

Ripon Rudra Paul 2019332053 Plant

Water Treatment Plant

Md Kamrul Islam 2019332058

Water Treatment Plant

Shah MD. Sadid Rahman 2019332069

Energy Balance, Sulphuric

Mamunur Rashid 2019332073 Acid Plant

Energy Balance, TSP Plant

Sk Salman Alam 2019332074

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Acknowledgement
We, the 8 students from the Department of Chemical Engineering and Polymer Science
(CEP) at Shahjalal University of Science and Technology (SUST), from the 2019-2020
session, extend our heartfelt gratitude to the entire TSP Complex Limited family for granting us
the privilege of undergoing Inplant Training at your distinguished organization.

We wish to express our sincere appreciation to the management, staff, and employees of TSP
Complex Limited for their gracious hospitality, unwavering guidance, and generous support
throughout our training program. We were particularly impressed by the dedication, expertise,
and professionalism exhibited by the engineers at TSP. Their willingness to share their wealth of
knowledge and practical experiences with us greatly enriched our learning journey.

Furthermore, we would like to acknowledge and express our thanks to the esteemed faculty
members of the Department of Chemical Engineering and Polymer Science at SUST. Their
mentorship and rigorous academic guidance have provided us with a strong academic foundation,
which enabled us to actively engage and benefit from this invaluable training opportunity.
Special mention to Dr. Mohammad Rakib Uddin sir & Dr. Muhammad Abdus Salam sir for
their unwavering support and dedication.

The exposure and insights we gained during our time at TSP, coupled with the mentorship from
our faculty members, have undoubtedly broadened our horizons and deepened our understanding
of the intricate interplay between theoretical knowledge and real-world applications in the
domains of Chemical Engineering and Polymer Science.

This report is sincerely dedicated to the TSP Complex and the Department of Chemical
Engineering and Polymer Science at Shahjalal University of Science and Technology
(SUST).

-Authors

4
Table of Contents:
1. Introduction:...............................................................................................................................6
2. Main Plants:................................................................................................................................6
3. Main Raw Materials and Source:............................................................................................. 7
4. Sulphuric Acid Plant:.................................................................................................................7
4.1 Raw Materials.................................................................................................................... 7
4.2 Chemical Reactions........................................................................................................... 7
4.3 Sulfur Burning and Energy Capture................................................................................... 7
4.4 Sulfur Dioxide Conversion..................................................................................................7
5. Phosphoric Acid Plant:.............................................................................................................. 8
5.1 Basics:.................................................................................................................................. 8
5.2 Grinding:.............................................................................................................................. 9
5.3 Digester:............................................................................................................................... 9
5.4 Crystallization:..................................................................................................................... 9
5.5 Filter:.................................................................................................................................... 9
5.6 Concentration:...................................................................................................................... 9
6. TSP PLANT.............................................................................................................................. 10
6.1 Equipment:......................................................................................................................... 10
6.2 Reaction System:................................................................................................................10
6.3 Granulation & Bagging Process:........................................................................................ 11
7. Water Treatment Plant........................................................................................................... 12
7.1 AIM of the Plant:................................................................................................................12
7.2 Water Treatment Process Overview:.................................................................................. 12
8. Material Balance & Energy Balance...................................................................................... 13
8.1 Material Balance:............................................................................................................... 14
8.1.1 TSP Mass Balance:....................................................................................................14
8.1.2 Phosphoric Acid Plant Mass Balance:...................................................................... 14
8.1.3 Sulphuric Acid Plant Mass Balance:.........................................................................14
8.2 Energy Balance:................................................................................................................. 15
8.Conclusion:................................................................................................................................ 16
9. Reference:..................................................................................................................................17
Appendix:.......................................................................................................................18

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1. Introduction:
Triple Super Phosphate Complex Limited (TSPCL) operates as a unique entity, being a Public
Sector enterprise with the legal status of a Private Limited Company. Located in Patenga,
Chittagong, its official address is at BCIC Bhaban, 30-31, Dilkusha C/Area, Dhaka-1000. It falls
under the administrative oversight of Bangladesh Chemical Industries Corporation (BCIC), a
renowned public-sector conglomerate interested in industries like Nitrogenous and phosphate
Fertilizers, Paper, Cement, Chemicals, and Sanitary Ware.

TSPCL was established with the goal of producing Triple Super Phosphate (TSP) Fertilizer. This
initiative included setting up two production units, named TSP-I and TSP-II, each with a
substantial capacity of 120,000 metric tons. TSP-II became operational before TSP-I, with TSP-I
starting in April 1977 and TSP-II in September 1974. TSP Complex is the sole Phosphatic
Fertilizer Factory in the country.

Due to technical challenges, the Phosphoric Acid (PA) Plant associated with TSP-I had to be
closed. In response to the growing demand for Single Super Phosphate (SSP) Fertilizer in
Bangladesh, TSP-I's facilities were adapted for SSP production. Additionally, TSP-I and TSP-II
units within the TSP-II Unit were renamed Unit-I and Unit-II, respectively. Over time, the
factory's production increased significantly, reaching a total output of 200,528 metric tons of
Phosphatic Fertilizer in the fiscal year 2002-2003.

The manufacturing process primarily relies on essential raw materials, namely Phosphate Rock
(PR) and Elemental Sulphur (S), which are sourced internationally and serve as the fundamental
components for producing high-quality fertilizers.

In summary, Triple Super Phosphate Complex Limited (TSPCL) is a distinctive entity with a dual
public-private status, situated in Patenga, Chittagong, and overseen by Bangladesh Chemical
Industries Corporation (BCIC). Its journey in Phosphatic Fertilizer production, adaptability, and
commitment to quality raw materials make it a significant player in the national landscape.

2. Main Plants:
1. Sulphuric Acid Plant
2. Phosphoric Acid Plant
3. TSP Plant
4. Water Treatment Plant

6
3. Main Raw Materials and Source:
a) Rock Sulphur from Iraq, Iran, Canada, Morocco, Saudi Arabia and Poland
b) Rock Phosphate from Jordan, Morocco, Egypt, China, Algeria and Syria
c) Phosphoric Acid from Tunisia, Poland, Iran, Morocco and India

4. Sulphuric Acid Plant:

The Sulphuric Acid Plant plays a critical role in the production of sulfuric acid, an essential
component in the manufacturing of phosphoric acid. The plant employs the Monsanto Contact
Process in both of its operational units.

4.1 Raw Materials

The primary raw materials required for the production of sulfuric acid in this facility include rock
sulphur, air (O2), and demineralized water (H2O).

4.2 Chemical Reactions

The synthesis of sulfuric acid involves a series of chemical reactions as outlined below:

1. Sulfur + Oxygen (O2) → Sulfur Dioxide (SO2)

2. Sulfur Dioxide (SO2) + Half Oxygen (O2) → Sulfur Trioxide (SO3)
3. Sulfur Trioxide (SO3) + Sulfuric Acid (H2SO4) → Pyrosulphuric Acid (H2S2O7)
4. Pyrosulphuric Acid (H2S2O7) + Water (H2O) → Sulfuric Acid (H2S2O4)

These sequential reactions are pivotal in the conversion of sulfur into sulfuric acid.

4.3 Sulfur Burning and Energy Capture

The combustion of sulfur in the plant generates a substantial amount of heat. This heat is
efficiently harnessed to produce steam, which serves as a vital source of energy for various
processes. This is achieved by passing the hot gases resulting from sulfur combustion through
pipes containing water, consequently generating steam. This process bears resemblance to the
operation of water tube boilers, where hot gases flow externally to tubes containing water, as
opposed to fire tube boilers in which water is situated internally, surrounded by hot gases.

4.4 Sulfur Dioxide Conversion

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To facilitate the conversion of sulfur dioxide (SO2) into sulfur trioxide (SO3), the plant employs a
crucial catalyst known as Vanadium pentaoxide (V2O5). The hot gases produced during sulfur
combustion are mixed with cooler gases derived from the boiler to achieve the necessary
temperature for this conversion process. The catalytic action of Vanadium pentaoxide is
instrumental in this chemical transformation.

In summary, the Sulphuric Acid Plant employs a well-defined process, encompassing the
utilization of raw materials, controlled chemical reactions, and efficient energy capture, to
produce sulfuric acid essential for phosphoric acid production.

5. Phosphoric Acid Plant:

5.1 Basics:

Chemical formula: H3PO4

Raw Materials: Rock phosphate, Sulphuric Acid, Return Acid(dilute Phosphoric Acid 17-19%)

Plant process: Nissan (Hemihydrate-Dihydrate)

Use & application: It is an intermediate product used for the manufacture of TSP.Entire quantity
of phosphoric acid produced is used in the process.

By-product: Gypsum

Process Description:

Reaction: Ca3(PO4)2 + 3H2SO4 + 6H2O = 2H3PO4+ 3CaSO4.2H2O

In this process, phosphoric acid is produced by reacting sulfuric acid with naturally occurring
phosphate rock. The reaction also forms calcium sulfate, commonly referred to as gypsum. The
insoluble gypsum is separated from the reaction solution by filtration. Phosphoric acid is an
intermediate product in the production of TSP fertilizer. The main reaction of this plant is,
Са3(PO4)2 + 3H2SO4 + 6H2O = 2H3PO4 + 3CaSO4. 2H2O In the PA-2 plant the rock phosphate is
mixed with acid in a tank to acidulate. The reacted slurry is passed into a series of tanks
successfully to complete the decomposition of rock and the reaction. Then the gypsum slurry is
separated from the acid and the acid is concentrated for the production of TSP. PA-2 plant can
produce 270MT of 48.5% P2O5 in a day. For the optimum condition of the reaction, there are
some requirements of the raw materials. Rock phosphate needs to be 80% passing through 200
Tyler mesh. This requirement comes from the concept that the smaller the particles the more will
be the surface area for reaction. This will speed up the reaction process. Sulfuric acid
concentration has to be 70-75% as it is a wet process and water is required to complete the
reaction.[3]

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5.2 Grinding:

Phosphoric acid production begins with the grinding of rock phosphate to mesh it into smaller
particles. Rock phosphate is fed into the ball mill. In the ball mill, the phosphate rocks are passed
through the gaps between the balls which crush them into small particles like dust.

5.2 Pre-mixer:

Then ground rock phosphate is fed with a bucket conveyor and screw conveyor to the pre-mixer
where rock phosphate comes in contact with the sulphuric and the return acid. Return acid is
19-21% phosphoric acid that is later collected from the process. In the pre-mixer, an agitator
circulates the mixer to decompose the rocks in the acid.

5.3 Digester:

From the pre-mixer, the mixture of rock phosphate, Sulphuric acid and return acid goes into the
digester where the reaction is completed. There is also an agitator to properly decompose the
rock into acids and to prevent the gypsum from settling down. There are two digesters, but only
one keeps running at a time and the other one stays in the standby mode.

5.4 Crystallization:

The recrystallization process separates the acids from the gypsum. There are three crystallizers.
The first one completes almost 80-85% crystallization in 60-65°C temperature. After the third
crystallizer, almost 98% of crystallization is completed. From the first crystallizer to the third
crystallizer it takes almost 6 hours to complete the recrystallization process.

5.5 Filter:

Then the mixer is pumped into a vacuum filter using a centrifugal pump to separate the acid from
the gypsum slurry. The mixer first falls into a tray where slurry gets stuck in the tray and the acid
passes through the nets below the tray into a cylindrical chamber. The first filter is 30% P2O5.
Again some water is mixed in the slurry and a second filtered acid is separated which is used as
the return acid. The 30 remaining filter cake or gypsum is sent to the gypsum yard after final
washing with hot water.

5.6 Concentration:

The required concentration of P2O5 is 48.5% for the production of TSP. The product acid of the
PA-2 plant is 30% P2O5 which is then concentrated to 50% P2O5 in a concentrator. There the
acid is heated with steam under a forced vacuum circulation system. The product concentrated
phosphoric acid is then supplied to the reaction plant for the production of TSP. All the vessels
and pipelines in the PA-2 plant are rubberized inside as this plant produces dilute phosphoric acid
which is highly corrosive. This plant is also very dusty for the grounded rock phosphate.[2]

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6. TSP PLANT
This is the plant where Triple Super Phosphate (TSP) is manufactured. The plant has a capacity
to produce 150,000 metric tons per year. The TSP produced here contains 50% of P2O5 and is
made from rock phosphate ground to 80% fineness passing through a 200 Tyler mesh in an
air-swept Ball Mill.

6.1 Equipment:

1. Ground Rock Bin: Stores the ground rock phosphate.

2. Bucket Conveyor: Transports the ground rock to the next process.

3. Screw Conveyor: Used for conveying materials.

4. Sensor Plate: Likely for monitoring levels.

5. Sliding Plate: Possibly part of the conveying system.

6.2 Reaction System:

6. Phosphoric Acid Heater: Heats phosphoric acid to a designated temperature.

7. Cone Mixer: Mixes ground rock and phosphoric acid.

8. Belt Conveyor: Transports the mixed materials.

9. Scrubber: Removes gases and impurities.

10. Exhaust Fan: Assists in gas removal.

The process begins with grinding the phosphate rock and heating it to the desired temperature.
The ground phosphate is stored in the Ground Rock Bin. Phosphoric acid is pumped to a holding
tank and then supplied to the Phosphoric Acid Heater, where it's heated to a high temperature
using steam. The heated phosphoric acid is then sent to the premixer.

In the premiere, the ground rock and phosphoric acid are thoroughly mixed. The mixer can adjust
its rotating speed to control mixing time. The mixture becomes increasingly solid as it progresses
through the continuous den to prevent clogging. The temperature in the den reaches around
100°C.

The reaction product is cut into pieces at the den outlet, and its retention time in the den is
approximately 20 minutes. The product is then sent to a slicer and subsequently to a curing
house, where it's stored for further curing. During curing, moisture content decreases.

Gases generated during the process, including carbon dioxide and silicon tetrafluoride, are
removed by an exhaust fan and passed through a scrubber to remove impurities before being
released into the atmosphere.

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This process results in the production of TSP fertilizer.[2]

6.3 Granulation & Bagging Process:

TSP obtained from the reaction plant is initially in powder form, which is inconvenient for
farmers. Granulation is done for three reasons:

1. Prevents powder from caking or clumping, making it easier for farmers to use.

2. Reduces environmental pollution caused by dry powder.

3. Makes it easier to apply as granules don't fly away.

Here's a brief overview of the process:

1. Crushing: Green TSP is first crushed to regain a powdered form, as it may accumulate.

2. Granulation: Crushed TSP, steam, and process water are fed into a rotating granulator,
forming granules through agglomeration. Finer TSP from a fine screen acts as seed for granule
formation. The granulated TSP has 12% moisture and a temperature of 80°C.

3. Drying: The granulated TSP is sent to a dryer, which is heated with natural gas. The dryer
reduces moisture content from 12% to about 5% and increases the temperature to 85°C.
Oversized granules are separated by a coarse screen and sent for crushing.

4. Screening: Granules are screened through a fine screen (16 mesh) to obtain the desired size.
Undersized granules are recycled back into the granulator.

5. Cyclone Separator: Undersized TSP separated in the exhaust is collected using a cyclone
separator and then dropped into the recycle line.

6. Scrubber: The stack is sent to a scrubber where the remaining dust is separated by water and
settled in a drain. It is collected and ground along with rock phosphate.

7. Bagging: Standard-sized (6-16 mesh) TSP granules are conveyed to the bagging plant. TSP is
bagged in polyethene plastic bags with two layers: a white outer layer and a transparent inner
layer. These bags are manually arranged. A sensor controls the filling of 50 kg TSP into each
bag, which is then semi-automatically sewn and stored for distribution.

This process transforms the powdered TSP into granules for ease of handling and application by
farmers.[1]

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7. Water Treatment Plant
7.1 AIM of the Plant:

This plant has been planned to supply process water to the chemical complex of Chittagong
(Bangladesh Chemical Industries Corporation.)

Characteristics of Raw Water:

The water to be treated is river water.
Its main characteristics are as follows:

Physical-chemical analysis (contractual analysis)

● Turbidity =1500 kaolin

● pH = 7.4
● Total hardness (ppm CaCO3)=128.41
● Calcium hardness (ppm CaCO3) = 38.52
● Magnesium hardness (ppm CaCO3) =89.89
● m-alkalinity (ppm CaCO3)=43.66
● Chloride (ppm CaCO3) =39.18
● Iron =0.25 mg/l
● Silica = 40 mg/l
● Nitrite = None
● Nitrate =traces

Water Source:

● Karnaphuli River ( Main Source)

● WASA (Water Supply and Sewerage Authority)

● Deep Tubewell

● Water Brought by Barges from the Halda River

The Karnafuli River serves as the primary source of sweet water, collected when the chloride
level is below 250 ppm. However, during the dry season, when chloride levels are higher,
alternative sources like deep tubewells and WASA are utilized. In crisis situations, water is
transported by barges from the upstream area. This section delves into the significance of each
source and the challenges associated with them.

7.2 Water Treatment Process Overview:

1. Screening: Removes wood chips, leaves, aquatic plants, and floating debris. Prevents solid
garbage from entering the treatment plant.

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2. Sedimentation: In this stage, particles with a specific gravity higher than water settle down.
The average time in the sedimentation tank is the detention period. Clarified water is then
drained.

3. Clarifiers: Waste is purified in three steps:

- Coagulation: Chemicals are added to encourage particles to join together into flocs.

- Flocculation: Gentle mixing helps flocs grow for easier settling.

- Clarification: Large flocs sink to the tank bottom, clear water overflows to a reserve tank.

4. Filtration: Water passes through filters to remove impurities like turbidity, taste, colour, iron,
and odour. Filters can be of different types.

5. Demineralization: Removes dissolved salts (bicarbonates, sulphates, chloride, silica) from the
raw water using cation and anion exchangers. This process yields highly pure deionized water,
continuously monitored for pH.

Cation Exchanger:

- Contains acid, and sulphonic radicals in its molecules.

- Swaps cations with liquid ions, a reversible process.

- Regenerated with acid when saturated.

- Can remove all cations, even those in equilibrium with strong anions like sulphates, chlorides,
and nitrates.

Anion Exchanger:

- Has basic functional radicals in its molecules.

- Exchanges anions with liquid ions, a reversible process.

- Regenerated with an alkaline solution.

- Weak base types only take up anions from strong acids like HCl, and HNO3.

After passing through both exchangers, all cations become H ions, and all anions become OH
ions. The resulting deionized water is highly pure, with continuous pH monitoring.[2][3]

8. Material Balance & Energy Balance

As we want to scale up to 450 M/T per day, We are going to find out the amount needed to reach
the value.

13
8.1 Material Balance:

According to TSP Complex to get 1 Metric Ton of TSP Per day, Rock Phosphate and Phosphoric
Acid should be mixed with a ratio of 0.55:0.64.

8.1.1 TSP Mass Balance:

Material Input(MT/day) Output(MT/day)

Rock Phosphate (Ca3(PO4)2) 297 59.4

Phosphoric Acid(H3PO4) 288 28.8

8.1.2 Phosphoric Acid Plant Mass Balance:

Material Input (MT/day) Output (MT/day)

Rock Phosphate (Ca3(PO4)2) 445.5 111.375

Phosphoric Acid(H3PO4) 297 44.55

Sulphuric Acid(H2SO4) 445.5 44.55

8.1.3 Sulphuric Acid Plant Mass Balance:

Material Input(MT/Day) Output(MT/Day)

Rock Sulphur(S) 222.75 55.6875

Oxygen(O2) 334.125 83.53125

Sulpher Di-Oxide (SO2) 222.75 22.275

Sulpher Tri-Oxide (SO2) 222.75 22.275

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H2S2O7 222.75 55.6875

Air 1501.07 375.2675

8.2 Energy Balance:

Melter:

S(s)→S(l) 300c 115.210 c 2.20*1012

Reaction Input Temperature(C) Output Heat evolved(kJ)

temperature(C)

Furnace:

Reaction Input Temperature(C) Output Heat evolved(kJ)

temperature(C)

S+O2 =SO2 115.210 C 10000C 2.06*1012

Converter:

Reaction Input Temperature(C) Output Heat evolved(kJ)

temperature(C)

SO2+½ O2=SO3 4300C 4250C

-197.76 kJ

PA PLANT:

Dilution Heat:

Input Temperature(C) Output temperature(C) Heat evolved(kJ)

15
 900C 830C 4.30*1010

Premixer and Digester:

Reaction Input Output Heat evolved(kJ)

Temperature(C) temperature(C)

750C 500C
Ca3(PO4)2 + 3H2SO4 + 6H2O = 1.0142 × 10^12
2H3PO4+ 3CaSO4.2H2O

TSP PLANT:

Cone Mixer:

Reaction Input Temperature(C) Output Heat evolved(kJ)

temperature(C)

Ca3(PO4)2+H3PO4→3 700C 400C

CaH4(PO4)2.2H2O 5.85 × 10^15

8.Conclusion:

In brief, our recent visit to the TSP industry was an enlightening experience that allowed us to
gain in-depth knowledge of industrial operations. We delved into the intricate workings of
various plants and gained practical insights into the management of particulate matter emissions.

During our visit, we made every effort to compile a comprehensive report that included material
balance and energy balance calculations. However, we encountered several challenges along the
way. The foremost issue was the lack of complete information, which hindered our ability to
perform accurate calculations and fully understand the intricacies of the industrial processes.

16
Additionally, the complexity of these processes made it susceptible to potential calculation errors,
which could impact the reliability of our scaling-up recommendations.

Despite these challenges, our industry visit was invaluable in terms of the insights gained. We
had the privilege of witnessing the entire production cycle, from raw material intake to emissions
control, and gained practical experience that is invaluable for our education.

Looking forward, we recognize the importance of ongoing collaboration with industry experts
and professionals to refine our understanding and improve our calculations. Addressing
information gaps and ensuring the accuracy of our material and energy balance calculations are
top priorities.

In conclusion, our TSP industry visit was a rich learning experience, although it presented
challenges in information gathering and calculation accuracy. We remain committed to continued
learning and engagement with industry experts to further enhance our knowledge and contribute
meaningfully to the field of industrial processes and emissions control.

9. Reference:

[1] Industrial Chemistry. (1991). GOEL Publishing House.

[2] TSP Complex Ltd.

[3]. (Fertilizer Production: TSP COMPLEX LIMITED, CHITTAGONG (AN ENTERPRISE OF

BCIC).) -Fertilizer Production: TSP COMPLEX LIMITED, CHITTAGONG (AN ENTERPRISE

OF BCIC) | The Lawyers & Jurists (lawyersnjurists.com)

[4] Huvard, G. S., Felder, R. M., & Rousseau, R. W. (2005). Elementary Principles of Chemical

Processes, Student Workbook. Wiley.

[5] Perry, R. H., & Green, D. W. (2008). Perry's Chemical Engineers' Handbook, Eighth Edition

(R. H. Perry & D. W. Green, Eds.). McGraw-Hill Education.

17
Appendix:

Fig.1: Process Diagram of Sulphuric Acid Plant

18
 Fig.2: Process Diagram of Phosphoric Acid Plant

19
 Fig.3: Process Diagram of Water Treatment Plant

20
Data:

● Specific heat capacity of solid sulfur = 0.21 J/g°C

● Specific heat capacity of liquid sulfur = 0.50 J/g°C
● Heat of fusion (ΔH_fusion) = 9.84 kJ/mol = 9840 J/g
● ΔHf for Sulfur Dioxide (SO2) = -296.83 kJ/mol
● The specific heat capacity of SO3 is approximately 0.897 J/g°C.
● The specific heat capacity of concentrated sulfuric acid is approximately 1.38 J/g°C.

Heat of Formation -

the heat of formation values:

1. Ca3(PO4)2 (Calcium Phosphate):

- ΔHf = -4188.0 kJ/mol

2. H2SO4 (Sulfuric Acid):

- ΔHf = -814.0 kJ/mol

3. H3PO4 (Phosphoric Acid):

- ΔHf = -1273.0 kJ/mol

4. CaSO4·2H2O (Calcium Sulfate Dihydrate):

- ΔHf = -1435.1 kJ/mol

[5]

Scale-Up Calculation:

As we want to scale up to 450 M/T per day, We are going to find out the amount needed to reach
the value.

Material Balance:

According to TSP Complex to get 1 Metric Ton of TSP Per day , Rock Phosphate and Phosphoric
Acid should be mixed with a ratio of 0.55:0.64.

TSP Mass Balance:

To synthesize Triple Superphosphate (TSP), it is essential to combine Phosphoric Acid and rock
phosphate in the specified proportion, as indicated below:

21
Rock Phosphate is Needed:

For producing 1 MTD TSP 0.55 Rock Phosphate is needed

So, for 450 MTD TSP (450 × 0. 64) = 288 𝑀𝑇 𝑅𝑜𝑐𝑘 𝑃ℎ𝑜𝑠𝑝ℎ𝑎𝑡𝑒 is needed

MRock Phosphate = 288 MTD

Phosphoric Acid Needed:

For producing 1 MTD TSP 0.64 Phosphoric Acid is needed

So, for 450 MTD TSP 4500 × 0. 64 = 297 𝑀𝑇 𝑃ℎ𝑜𝑠𝑝ℎ𝑜𝑟𝑖𝑐 𝐴𝑐𝑖𝑑 is needed

MPhosphoric Acid = 297 MTD

According to TSP Complex the reaction occurs with 75% Conversion, So when we mix 288
MTD Rock Phosphate and 297 MTD Phosphoric Acid 75% will be converted to to create 450
MTD TSP

Phosphoric Acid Plant Mass Balance:

Reaction:

Ca3(PO4)2 + 3H2SO4 + 6H2O = 2H3PO4+ 3CaSO4.2H2O

(3 moles H2SO4 / 2 moles H3PO4) = (x MTD H2SO4 / 297 MTD H3PO4)

Now, solve for x:

x = (3/2) × (297 MTD) = 445.5 MTD

So, MSulphuric Acid=445.5 MTD

Rock Phosphate Needed= (½)297=148.5 MTD

MRockPhosphate For PA= 148.5 MTD

Mass Balance:

To produce 445.5 metric tons (MTD) of H2SO4 using the given chemical reactions, it is necessary
to work in a reverse manner through the reactions to ascertain the requisite quantity of starting
materials. This process can be methodically broken down into the following steps:

22
1. First, let's look at the final reaction:

H2S2O7 + H2O → 2H2SO4

This reaction tells us that 1 mole of H2S2O7 produces 2 moles of H2SO4

To produce 445.5 MTD of H2SO4, half that amount of H2S2O7 is needed

Moles of H2S2O7 needed = 445.5 MTD / 2 = 222.75 MTD

2. Now, let's move backwards to the third reaction:

SO3 + H2SO4 → H2S2O7

From this reaction, you can see that 1 mole of SO3 produces 1 mole of H2S2O7.

So, to produce 222.75 MTD of H2S2O7, the same amount of SO3 is needed

Moles of SO3 needed = 222.75 MTD

H2SO4 Needed- 222.75 MTD

3. Next, let's move backward to the second reaction:

SO2 + 1/2 O2 → SO3

From this reaction, you can see that 1 mole of SO2 produces 1 mole of SO3.

So, to produce 222.75 MTD of SO3, the same amount of SO2 is needed

Moles of SO2 needed = 222.75 MTD

4. Finally, let's move backwards to the first reaction:

S + O2 → SO2

This reaction tells us that 1 mole of S produces 1 mole of SO2.

So, to produce 222.75 MTD of SO2, same amount of S is needed:

Moles of S needed = 222.75 MTD

23
Therefore, to produce 445.5 MTD of H2SO4, 222.75 MTD of S is needed as the starting
material.

MSulphur = 222.75 MTD

Oxygen Needed:

SO2 + 1/2 O2 → SO3;

For this reaction: O2 Needed = 0.5 *222.75=111.375 MTD for another reaction ,1:1 Reaction so
O2 Needed = 222.75 MTD

Total Oxygen Needed = 222.75MTD +111.375 MTD= 334.125 MTD

Total Air Needed: 334.125/0.21 = 1501.07 MTD

Energy Balance Calculation:

Melter:

1. Heat Needed to melt Sulfur:

mS=222.75 MTD =222,750,000 grams

Q1 = m * 0.21 J/g°C * (115.21°C - 30°C)

Q2 = m * ΔHfusion=2.198 × 10^9 kJ

2. The heat involved in Furnace:

Heat of Reaction:

Number of moles of S = 222,750,000 g / 32.07 g/mol Number of moles of S ≈ 6,946,013.99

moles

3.Heat involved Converter:

ΔHreaction = [2 * ΔHf(SO3)] - [2 * ΔHf(SO2)]

ΔHreaction = [2 * (-395.71 kJ/mol)] - [2 * (-296.83 kJ/mol)]

ΔHreaction = (-791.42 kJ/mol) - (-593.66 kJ/mol)

ΔHreaction = -197.76 kJ/mol

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Total heat ≈ (-197.76 kJ/mol) * 6,946,013.99 moles= -1.375 × 10^12 kJ

4. Heat Removed from SO3 :

Q = m * Cp * ΔT ; Q = 222,750,000 grams * 0.897 J/g°C * (-205°C)=-40,413,322,500

8.2.2 PA Plant:

1. Dilution Heat:

ΔT = 90°C - 83°C = 7°C ,

Q = m * Cp * ΔT= 445,500,000 grams * 1.38 J/g°C * 7°C = 4.30*1010

2.Pre Mixture & Digester:

ΔHreaction = ΣΔHf(products) - ΣΔHf(reactants)

ΔHreaction = [2 * ΔHf(H3PO4) + 3 * ΔHf(CaSO·2H2O)] - [1 * ΔHf(Ca3(PO4)2) + 3 * ΔHff(H2SO4) +

6 * ΔHf(H2O)]

ΔHreaction = [2 * (-1273.0 kJ/mol) + 3 * (-1435.1 kJ/mol)] - [1 * (-4188.0 kJ/mol) + 3 * (-814.0

kJ/mol) + 6 * (0 kJ/mol)]

ΔHreaction = [-2546.0 kJ/mol - 4305.3 kJ/mol] - [-4188.0 kJ/mol - 2442.0 kJ/mol]

ΔHreaction = (-6851.3 kJ/mol) - (-6630.0 kJ/mol)

ΔHreaction = -221.3 kJ/mol

Moles of Ca3(PO4)2 = (148.5 * 1,000,000 g) / 310.10 g/mol Moles of Ca3(PO4)2 ≈ 479,134.82

moles

Moles of H2SO4 = (445.5 * 1,000,000 g) / 98.08 g/mol Moles of H2SO4 ≈ 4,543,359.92 moles

Total Heat = -221.3 kJ/mol * (479,134.82 moles + 4,543,359.92 moles)

Total Heat ≈ -1.0142 × 10^12 kJ

8.2.3 TSP Plant:

Cone Mixture: ΔHreaction = ΣΔHf(products) - ΣΔHf(reactants)

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ΔHreaction = [ΔHf(Ca(H2PO4)2·2H2O)] - [ΔHf(Ca3(PO4)2) + ΔHf(H3PO4) + ΔHf(H2O)]

ΔHreaction = [-2768.0 kJ/mol] - [-4188.0 kJ/mol - 1273.0 kJ/mol - 285.83 kJ/mol]

ΔHreaction = -2768.0 kJ/mol + 5546.83 kJ/mol

ΔHreaction = 2778.83 kJ/mol

Molar mass of Ca3(PO4)2 = 3 * (40.08 g/mol) + 2 * (31.97 g/mol) + 8 * (16.00 g/mol) = 310.10
g/mol

Molar mass of H3PO4 = 3 * (1.01 g/mol) + 31.97 g/mol + 4 * (16.00 g/mol) = 98.08 g/mol

Molar mass of H2O = 2 * (1.01 g/mol) + 16.00 g/mol = 18.02 g/mol

Now, calculate the moles of each reactant:

Moles of Ca3(PO4)2 = (288,000,000 g) / 310.10 g/mol ≈ 928,570.59 moles

Moles of H3PO4 = (297,000,000 g) / 98.08 g/mol ≈ 3,028,600.66 moles

Moles of H2O = (200,670,000 g) / 18.02 g/mol ≈ 11,130,966.70 moles

Total Heat = ΔHreaction * (moles of Ca3(PO4)2 + moles of H3PO4 + moles of H2O)

Total Heat ≈ 2778.83 kJ/mol * (928,570.59 moles + 3,028,600.66 moles + 11,130,966.70 moles)

Total Heat ≈ 5.85 × 10^15 kJ

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