MANUFACTURING OF H3PO4

USING ASPEN PLUS

[PROCESS PLANT SIMULATION LABORATORY - 2]

Submitted by

SUBHASRITAM BEHERA

115CH0123

Under the supervision of

PROF. SOUMYA SANJEEB MOHAPATRA

NATIONAL INSTITUTE OF TECHNOLOGY, ROURKELA

Department of Chemical Engineering

 INDEX

CONTENTS PAGE NO

1. INTRODUCTION 01
2. MANUFACTURE 01
3. FLOWSHEET 02
4. PROCESS DESCRIPTION 02
5. INPUT 03
6. RESULTS 04
7. SENSITIVITY ANALYSIS 05
8. CONCLUSION 07
1. INTRODUCTION
Food security is among the challenges facing many countries in the world due to increasing
population growth and poor yield of the crops as a result of essential nutrients depletion. The
need to enhance agricultural output is imperative. Phosphorus is among the essential elements
for plants growth. Replenishing of agricultural farms is done via fertilizer application. The sole
raw materials for phosphate fertilizer production is apatite. The phosphate rock consumption
is on the increase from its discovery to date. The major producers of rock phosphate in the
world are Morocco, Western Sahara and United States. Rock phosphate have contributed to
economy of the producing countries, for instance, in 2011, United States earned about 2.8
billion US Dollars from phosphate allied products. Nigeria is not left out of those that have
substantial quantity of rock phosphate deposit. The portable form of products obtainable from
phosphate rock is the phosphoric acid. Eighty to ninety percent of phosphoric acid is used for
phosphate fertilizer production, while the remaining fraction is used for detergent and animal
feed preparation. The world’s consumption of phosphate fertilizer as at 2015 was 45 million
MT, with a forecast annual growth rate of 1.9%.

Production of phosphoric acid from apatite is a well-established technology. The two major
routes of converting rock phosphate to phosphoric acid using wet process are dehydrate and
hemihydrate processes. The selection of the appropriate process depends on the inherent
properties of the deposit, and product quality requirements. The dehydrate process involves
grinding, beneficiation, reaction of the rock with sulphuric acid, crystallization and filtration.
In hemihydrate process the first two stages in dehydrate process are eliminated thereby
reducing capital cost. Furthermore, the concentration of phosphoric acid from hemihydrate
process is about 42%, which may not require further concentration for application in fertilizer
production, therefore eliminates evaporator unit in the plant. Despite the advantages of
hemihydrate process outlined, the process cannot practically stand alone to achieve the required
phosphoric and calcium sulphate qualities. The selection of the optimum conditions of
operation is essential to realization of higher plant efficiency, yield and product quality.

2. MANUFACTURE
The modern manufacturing methods of phosphoric acid are following:

1. Using phosphate rock and blast furnace

2. Using phosphate rock and electric furnace

3. Oxidation and hydration of phosphorous

4. Wet process or from sulfuric acid and phosphate rock

The wet process is according to the acids (sulfuric acid, nitric acid or hydrochloric acid) used
to decompose the phosphate rock. The process using sulfuric acid is the most common among
all particularly for producing fertilizer grade phosphoric acid. The wet process phosphoric acid,
also called as green acid. Depending upon the hydrate forms of calcium sulfate produced during
the wet process, it is classified as anhydrate, hemi hydrate and dehydrate. The hydrate form is
controlled mainly by temperature and acid concentration. Anhydrite (n=0) process is not
commercially viable due to high temperatures requirement and the higher rate of corrosion.
The dehydrate process is the most popular due to simplicity and ability to use a wide variety of
phosphate rocks in the process. Hemihydrate processes produce phosphoric acid of a relatively
high concentration without the need of the concentration step. There is also some attentiveness
in the two-stage processes that involve crystallization in the hemi-hydrate form followed by
recrystallization in the dehydrate form, with or without filtration or centrifugation.

3. FLOWSHEET

Fig - ASPEN flowsheet for manufacturing H3PO4

4. PROCESS DESCRIPTION
There are two processes i.e. dehydrate and hemihydrates (CaSO4.2H2O and CaSO4.1/2H2O)
are used for production of phosphoric acid. Sulfuric acid on reaction with phosphate rock along
with precipitation of calcium sulfate results into the formation of phosphoric acid. The process
is simple and requires grinding of phosphate rock reacting with dilute phosphoric acid so that
melt is produced which in a reactor as mixed with concentrated sulfuric acid for 4 to 8hrs in
the temperature range of 75-800C. Lot of air is required to control the temperature. Resulting
gases includes HF and P2O5 which in the absorption tower is separated and finally treated to
give fluorosilicates and dilute phosphoric acid. The main product in the liquid form which is
phosphoric acid and calcium sulfate is filtered and washed. Thus, gypsum and phosphoric acid
are separated and after minor purification the phosphoric acid is concentrated into the
evaporator.

Throughout the plant, corrosion resistant materials of construction must be used. The most
common ones are structural carbon or nickel alloy for evaporator heat exchangers; rubber or
carbon-brick for reactor linings; polyester-fiber glass in pipes, ducts, and small vessels. Yield
of phosphoric acid based on phosphorus content of raw material is 95%.

5. REACTIONS
Ca3(PO4)2 + 3H2SO4 + H2O → 3CaSO4. H2O + 2H3PO4

CaF2 +H2SO4+ H2O → CaSO4. H2O + 2HF

6. INPUT
Components Value (kg / hr)

Rock (Ca10(PO4)6F2) 136077

H2SO4 136077

Water 18143
7. RESULT

Units GYPSUM P-ACID S1 S2 S3 S4 S5

From CYCLONE FLASH2 RGIBBS RSTOIC CYCLONE HEATER FLASH2
To RSTOIC CYCLONE HEATER FLASH2
Substream: MIXED
Phase: All All Vapor All All Mixed Vapor
Component Mass Flow
CA10 KG/HR 0 0 0 0 0 0 0
CA3PO42 KG/HR 0 0 116517 0 0 0 0
CAF2 KG/HR 0 0 9776.177 0 0 0 0
H2SO4 KG/HR 8706.196 4560.062 0 13266.26 4560.068 4560.068 0.006512
WATER KG/HR 5174.024 2545.579 19163 7884.036 2710.013 2710.013 164.4339
CASO4 KG/HR 119276 62473.47 0 181749 62473.47 62473.47 0
H3PO4 KG/HR 48316.33 25306.78 4.53E-08 73623.11 25306.78 25306.78 4.80E-11
HF KG/HR 3288.029 991.8188 0 5010.209 1722.18 1722.18 730.3611
FE2O3 KG/HR 1339.439 701.5615 2041 2041 701.5615 701.5615 0
AL2O3 KG/HR 1339.439 701.5615 2041 2041 701.5615 701.5615 0
SIO2 KG/HR 3072.637 1609.363 4682 4682 1609.363 1609.363 0
Mole Flow KMOL/HR 1927.776 964.0825 1675.292 2937.492 1009.717 1009.717 45.63402
Mass Flow KG/HR 190512 98890.2 154220 290297 99785 99785 894.8015
Volume Flow L/MIN 1753.31 928.0351 692152 2671.646 918.3359 23892.21 22964.17
Temperature C 25 90 25 25 25 90 90
Pressure BAR 1 1 1 1 1 1 1
Vapor Fraction 0 0 1 0 0 0.045195 1
Liquid Fraction 0.536041 0.514079 0 0.536041 0.536041 0.490846 0
Solid Fraction 0.463959 0.485921 0 0.463959 0.463959 0.463959 0
Molar CAL/MOL -276010 -284050 -242310 -276010 -276010 -274080 -63306.1
Enthalpy
Mass CAL/GM -2792.93 -2769.25 -2632.19 -2792.93 -2792.93 -2773.37 -3228.55
Enthalpy
Enthalpy CAL/SEC -1.5E+08 -7.6E+07 -1.1E+08 -2.3E+08 -7.7E+07 -7.7E+07 -802480
Flow
Molar CAL/MOL- -87.9022 -83.4104 -26.8837 -87.9022 -87.9022 -79.5657 1.659196
Entropy K
Mass CAL/GM- -0.88948 -0.81317 -0.29204 -0.88948 -0.88948 -0.80512 0.084617
Entropy K
Molar MOL/CC 0.018325 0.017314 4.03E-05 0.018325 0.018325 0.000704 3.31E-05
Density
Mass GM/CC 1.810975 1.775978 0.003714 1.810975 1.810975 0.069608 0.000649
Density
Average Molecular 98.82477 102.5744 92.05558 98.82477 98.82477 98.82477 19.60821
Weight
8. SENSITIVITY ANALYSIS