Arid Zone Journal of Engineering, Technology and Environment, June, 2018; Vol.

14(2):169-171
Copyright © Faculty of Engineering, University of Maiduguri, Maiduguri, Nigeria.
Print ISSN: 1596-2490, Electronic ISSN: 2545-5818, www.azojete.com.ng

MODELING AND SIMULATION OF HEMIHYDRATE PHOSPHORIC ACID PLANT

A. S. Grema*, Y. Y. Imam and H. I. Mohammed

(Department of Chemical Engineering, University of Maiduguri, P.M.B. 1069,
Maiduguri, Borno State.)
*Corresponding author’s e-mail: a.grema@unimaid.edu.ng

Abstract
In this paper, wet hemihydrate phosphoric acid process was modeled and simulated using ASPEN PLUS
using properties of Sokoto Phosphate Rock to characterise the basic raw material. The process consisted
of the reaction section, filtration section, and purification unit. Results of the simulation showed that the
model developed in this study described the behavior of a real plant. Sensitivity analyses for the
fundamental parameters were performed using the model. From the results of the sensitivity analyses, it
was found that the temperature and pressure of the flash separator are the main factors that affect the
purity of wet process phosphoric acid. At a temperature above 400°C, the purity of the phosphoric acid is
maintained at 100%. This value changes at temperatures below 80°C where the phosphoric acid purity is
maintained at 74%. This indicates that the purity of the acid increases with increase in flash separator
temperature. The purity of the phosphoric acid varies inversely with the pressure of the flash separator.
The purity of the phosphoric acid is about 84% at 0.5 bar. It decreases gradually with increase in pressure.

Keywords: phosphate rock, sensitivity analysis, gypsum, Gibbs free energy

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 (Jasinki, 2013). The major producers of rock phosphate in the
world are Morocco, Western Sahara and United States (Ridder et al., 2012). 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 (Jasinki, 2013). Nigeria is
not left out of those that have substantial quantity of rock phosphate deposit (RMRDC, 2010).
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 (Van Kerwenbergh, 2010). The
world’s consumption of phosphate fertilizer as at 2015 was 45 million MT, with a forecast
annual growth rate of 1.9% (FAO, 2011).
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 dihydrate and
hemihydrate processes (John, 2008). The selection of the appropriate process depends on the
inherent properties of the deposit, and product quality requirements. The dihydrate process
involves grinding, beneficiation, reaction of the rock with sulphuric acid, crystallization and
filtration (John, 2008). In hemihydrate process the first two stages in dihydrate process are
Arid Zone Journal of Engineering, Technology and Environment, June, 2018; Vol. 14(2):169-171.
ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng

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 (EFMA, 2000). Despite
the advantages of hemihydrate process outlined, the process cannot practically stand alone to
achieve the required phosphoric and calcium sulphate qualities (Technip, 2011). The selection of
the optimum conditions of operation is essential to realization of higher plant efficiency, yield
and product quality (Prayon, 2012). This development has led to combination of the two
processes (hemihydrate and dehydrate) in a single plant. However, a lot of works have been done
to develop models that simulate the production of phosphoric acid from apatite. Papadopoulos et
al. (2009) have developed generic modelling and optimization framework for industrial scale
dihydrate process using iterative modeling and optimization procedure. Theodosiadi et al. (2017)
have modelled dihydrate reactor crystallizer unit using modified Maxwell-Stefan’s equation,
discretized using Orthogonal Collocation on Finite Element, (OCFE) and solved using gPROMS.
Abu-Eisha and Abu-Jabal (2000) have developed computer programme to simulate three CSTR
for dihydrate process pilot plant. However, there is no established model that has considered
hemihydrate conditions, or combined process conditions. For instance, Abu-Eisha and Abu-Jabal
(2000) did not consider age distribution but only considered the simplified mass balance.
Theodosiadi et al. (2017) assumptions’ that the temperature within the reactor is uniform is
invalid. Experimental data have shown co-crystallization of hemihydrate and dihydrate of
calcium sulphate, due to temperature fluctuation. A robust model should account for temperature
variation due to exothermic nature of the reaction. The operating condition of the dihidrate and
hemihydrate nearly overlapped, at maximum yield of the former process. The operating
temperature of dihydrate process is between 90 to 110°C, while that of hemihydrate is 110-
120°C. There are losses observed in the processes, these are: losses as a result of hemihydrate
and dihydrate co-crystallization due to temperature build-up in the reactor; and incomplete
conversion of the apatite due to low acid concentration. It is therefore necessary to optimize the
operating condition with an appropriate algorithm that will achieve higher efficiency. The
objectives of this study is to model, simulate and optimize hemihydrate process for production of
phosphoric acid. Typical properties of Sokoto phosphate rock (RMDC, 2010) were used (see
Table A3 in the Appendix).

2. Methodology
ASPEN PLUS software was used to model and simulate the production of phosphoric acid via
hemihydrate process. Main process units considered involved chemical reaction, filtration and
flash separation. Sensitivity analyses of some parameters were also carried out. A step-by-step
procedure followed in carrying out this task is explained below:

2.1 Components Specification

ASPEN PLUS stores physical property parameters for a large number of components in several
databanks. Components may be entered by either component name or chemical formula. ASPEN
PLUS also requires that a nickname, Component ID, which is used in all stream reports, be
provided for all components. Selecting the Components item on the Data Browser panel
produces Table 1. The components represent the chemical species present in the process.

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Table 1: ASPEN PLUS Component Specification

Component ID Type Component Name Alias
Rock Solid Ca10(PO4)6F2 Ca10P6O24F2
CAL-PHSP Solid Calcium-Phosphate Ca3(PO4)2
CaF2 Solid Calcium-Fluoride CAF2
Sulfuric Conventional Sulfuric-Acid H2SO4
Water Conventional Water H2O
Cal-Hemi Solid Calcium-Sulfate- CaSO4*1:2W:A
Hemihydrate
H3PO4 Conventional Orthophosphoric-Acid H3PO4
HF Conventional Hydrogen-Fluoride HF
Fe2O3 Solid Hematite Fe2O3
Al2O3 Solid Alumium-Oxide-Alpha- Al2O3
Coru
SiO2 Solid Silicon-Dioxide SiO2

2.2 Property Method

A property method is a collection of methods and models that ASPEN PLUS uses to calculate
the chemical and thermodynamic equilibrium, and the physical properties of all streams. The
SOLIDS and Electrolyte-NRTL options in ASPEN PLUS was used in this work to compute all
the physical properties required for the phosphoric-acid model. SOLIDS option was used in
modeling mechanical processes such as crushing, sieving and filtration. Solid filtration is
involved in the phosphoric acid plant and thus the choice of the solid property method.
ELECNRLT option provides an accurate description of the process chemistry in the phosphoric
acid process.

2.3 Process Flowsheet

The ASPEN PLUS simulation flowsheet for the process is given in Figure 1. The process
involves the addition of phosphate rock, sulfuric acid and water to the reaction system. The
product of this reaction system enters a filtration unit that separates gypsum crystals from the
phosphoric acid. The phosphoric acid is then fed to the purification section which purifies the
produced acid.

Figure 1: Process Flow Sheet of Hemihydrates Plant

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ISSN 1596-2490; e-ISSN 2545-5818; www.azojete.com.ng

2.4 Unit Operations

Unit operations in the process are represented by choosing from the library of ASPEN PLUS
"Blocks." The block chosen for a particular operation depends on the level of description of the
simulation (Tecnology, 1999). The RGibbs and RStoic are the two blocks selected to model the
first and second reactor, respectively. RGibbs uses Gibbs free energy minimization with phase
splitting to calculate equilibrium, thus the name RGibbs. RStoic is used when stoichiometry and
the molar extent or conversion is known for each reaction hence it is called RStoic. For the
filtration, SSplit which stands for solid split cyclone was used. Heater for pre-heating and
FLASH 2 for the liquid-liquid separation were also among the blocks selected for the model.

2.4.1 Reaction System

The attack tank which is the first reactor was modeled using RGibbs. The RGibbs block can be
used to establish the chemical equilibrium composition between reactants and products. This
model does not require reaction stoichiometry. RGibbs can determine phase equilibrium without
chemical reaction, particularly for multiple liquid phases.
The product of the RGbbs in stream S1 enters the second reactor where phosphoric acid reaction
takes place (see Figure 1). This reactor was modeled using RStoic. The RStoic block is the
simplest of ASPEN PLUS’s reactor blocks. It permits the use of several reactions with the molar
extent of conversion or fractional conversion of a component, specified for each reaction. RStoic
models a reactor when: Reaction kinetics is unknown or unimportant, Stoichiometry is known, or
you can specify the extent of reaction or conversion. There are two reactions taking place in the
RStoic. These are:
Ca3(PO4)2 + 3H2SO4 + H2O → 3CaSO4. H2O + 2H3PO4 (1)
CaF2 +H2SO4+ H2O → CaSO4. H2O + 2HF (2)
Both reactions were assumed to attend 100% conversion.

2.4.2 Filtration
The product of the phosphoric acid reactor is fed to a filter which separates the phosphoric acid
from the calcium sulphate (Gypsum). This was modeled using SSplit from ASPEN PLUS library
which is used to model solid-liquid separator based on splits specified for each sub-stream.

2.4.3 Flash Separation

The phosphoric acid stream from the filter is further purified by first pre heating (to set it to an
adequate temperature for separation) it using a heat exchanger before it is fed to a flash which
separates the acid from other impurities. The flash was modeled using FLASH 2 from the
ASPEN PLUS library. The Flash2 block is designed to produce a single vapor phase and a single
liquid phase that are in equilibrium when the flash conditions are specified such that a multi
component mixture’s state is in the two-phase region. Modeling the flash involves simple steps
of specifying the temperature and pressure condition of the flash.
2.5 Sensitivity Analyses
Sensitivity analyses were conducted on the developed model with a view to finding out those
model parameters that are more sensitive. This was done by first specifying the manipulated

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variables, which in this case are temperature, pressure and mass flow. The upper and lower limits
of the manipulated variables were also specified. The measured variables on which impacts of
the manipulated variables are sought to be established were then defined. The measured variables
selected are phosphoric acid mass flow rate and mass fraction in stream 7. The mass fraction
gives an indication of the phosphoric acids purity while the mass flow rate indicates the yield.

3 Results and Discussion

3.1 Model Simulation
Table A1 and Table A2 give a summary of all streams’ properties. It can be seen that the model
produces 73, 623.53 kg/h of phosphoric acid and 181, 750.4 kg/hr of gypsum (over two times the
amount of phosphoric acid produced). This value is almost same for most phosphoric acid plants,
which produce more gypsum than they do phosphoric acid.
3.2 Sensitivity Analyses
Sensitivity analyses were conducted using the developed model to determine the influence of
operation parameters on plant performance, yield and purity of the acid. Figure 2, Figure 3 and
Figure 4 show how phosphoric acid yield responds to changes in the reactor temperature, flash
separator temperature and pressure, respectively.
80000
Mass flow kg/hr

75000
70000
65000
60000
55000
50000
0 20 40 60 80 100
Temperature °C

Figure 2: Phosphoric Acid Mass Flow Rate against Rector (R2) Temperature

80000
Mass flow kg/h

60000

40000

20000

0
0 200 400 600
Temperature °C
Figure 3: Phosphoric Acid Mass Flow Rate against Flash Separator Temperature

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80000

Mass flow kg/h

60000

40000

20000

0
0 10 20 30
Pressure (Bar)
Figure 4: Phosphoric Acid Mass Flow Rate against Flash Separator Pressure
From the above results, it can be seen that the phosphoric acid yield is independent of the reactor
temperature, flash separator temperature and pressure respectively. A change in any of these
variables will leave the flow rate of phosphoric acid unchanged.
In Figure 5, Figure 6 and Figure 7, changes in phosphoric acid purity with changes in flash
separator temperature, pressure and reactor temperature are shown respectively.
1
0.9
Mass Fraction

0.8
0.7
0.6
0.5
0.4
0 100 200 300 400 500
Temperature °C
Figure 5: Phosphoric Acid Mass Fraction against Flash Separator Temperature
0.88
Mass fraction

0.84

0.8

0.76

0.72
0 5 10
Pressure (Bar)
Figure 6: Phosphoric Acid Mass Fraction against Flash Separator Pressure
1
Mass fraction

0.8
0.6
0.4
0.2
0
0 100 200 300 400
Temerature °C
Figure 7: Phosphoric Acid Mass Fraction against Reactor (R2) Temperature

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It can be observed that the purity of phosphoric acid can be increased to 100% with increase in
flash separator temperature (Figure 5). The purity of most wet phosphoric acid plant is usually
around 60-70% while those of thermal process are above 80%. The figure indicates that heating
to a temperature above 400 °C results in a phosphoric acid with higher purity. This however will
incur additional cost of heating and is limited by operational constraint and feasibility. The
pressure of flash separator also plays a significant role in the purity of wet process phosphoric
acid as can be seen from Figure 6; increase in pressure occasions a decrease in the phosphoric
acid purity. Furthermore, operating the flash at a pressure of about 0.5 bar will yield the highest
purity of the phosphoric acid. However, the purity of phosphoric acid is shown to be independent
of reactor temperature as evidenced from Figure 7.

4 Conclusion and Recommendations

Modeling and simulation of a wet process hemihydrate phosphoric acid plant was carried out
using ASPEN PLUS V8.4 software. Typical properties of Sokoto Phosphate Rock were
considered to characterize the basic raw material for the plant. To achieve accurate results,
ASPEN PLUS block models were carefully selected to best describe each unit operation in the
phosphoric acid plant. After the model was developed and simulated, sensitivity analyses were
conducted to investigate the effects of various process conditions on yield and purity of produced
phosphoric acid. It was found out that the yield of the acid is independent on the reactor
temperature as well as flash separator pressure and temperature. On the other hand, the purity is
affected by both separator pressure and temperature but remained unchanged with reactor
temperature.
Thermal process produces phosphoric acid of higher purity than wet process plants but with a
very high cost of production. Based on the findings from these research work, operating the
purification unit of a wet, hemihydrates process phosphoric acid plant at a temperature above
400 °C and atmospheric pressure will ensure a product of higher purity just as that of thermal
process. It is therefore recommended that further studies be conducted to see if it is economically
viable to operate at that condition. Furthermore, future study should investigate systematic
optimization of the entire process plant with a view to finding out optimal process conditions.

References
Abu-Eishah, SI. and Abu-Jabal, NM. 2000. Parametric study on the production of phosphoric
acid by the dihydrate process. Chemical Engineering Journal, 231-250.
EFMA. 2000. Best Available Techniques for Pollution Prevention and Control in the European
Fertilizer Industry. Brussels: European Fertilizer Manufacturers’ Association (EFMA).
FAO. 2011. Food and Agriculture Organization of the United Nations. Rome: Current World
Fertilizer Trends and Outlook to 2015.
Jasinki SM. 2013. 2011 Minerals Yearbookk [Phosphate Rock]. U.S. Geological Survey.
John Wing PE. 2008. Selecting a Phosphoric Acid Process. ClearWater Beach, Florida:
American Institue of Chemical Engineers.

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Papadopoulos AI., Theodosiadi K., Seferlis P. 2009. Generic modelling, design and optimization
of industrial phosphoric acid production processes. Chemical Engineering and Process: Process
Intensification, 48(1), 493-506.
Prayon. 2012. Prayon Process for Phosphoric Acid Production. Belgium: Prayon Technologies
Ltd.
Ridder M., Jong S., Polchar J. and Lingemann S. 2012. Risks and Opportunities in the Global
phosphate Market. Hague: The Hague Centre for Strategic Studies (HCSS).
RMRDC. 2010. Non – Metallic Mineral Endowments in Nigeria. Abuja: Raw Materials
Research and Development Council (Federal Ministry of Science and Technology).
Technip. 2011. Technip Process for Production of Wet Phosphoric Acid. Paris: Technip Group
communications.
Tecnology, A. 1999. Introduction to Aspen plus. Aspen Tech.inc.
Theodosiadi K., Papadopoulos AI., and Seferlis P. 2007. Modeling of the Reactor-Crystallizer
Unit in a Phosphoric Acid Production Plant. Thermi-Thessaloniki, Greece: aChemical Process
Engineering Research Institute,.
Van Kerwenbergh SJ. 2010. World Phosphate Rock Reserves and Resources. Alabama:
International Fertilizer Development Center (IFDC).

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Appendix
Table A1: Summary of Stream Properties for Simulated Hemihydrate Plant
H2O H2SO4 ROCK S1 S2
Temperature C 25 25 25 25 90
Pressure bar 1 1 1 1 1
Mass Vapor Fraction 0 0 0 0.183 0.009
Mass Solid Fraction 0 0 0.993 0.057 0.656
*** ALL PHASES ***
Mass Flow kg/hr 18143.7 136077.7 136077.7 154221.4 290299.1
Volume Flow cum/hr 18.24 74.417 7.084 38788.91 4190.197
Enthalpy Gcal/hr -68.749 -262.903 -442.39 -427.733 -793.619
Density kg/cum 994.694 1828.572 19208.04 3.976 69.281
Mass Flow kg/hr
ROCK 0 0 126293.7 0 0
CAL-PHSP 0 0 0 116517.5 0
CAF2 0 0 0 9776.233 0
SULFURIC 0 136077.7 0 0 13266.27
WATER 18143.7 0 1020.583 19164.28 7885.249
CAL-HEMI 0 0 0 0 181750.4
H3PO4 0 0 0 0 73623.53
HF 0 0 0 0 5010.237
Fe2O3 0 0 2041.166 2041.166 2041.166
Al2O3 0 0 2041.166 2041.166 2041.166
SiO2 0 0 4681.073 4681.073 4681.073

Table A2: Summary of Stream Properties for Simulated Hemihydrate Plant

S3 S4 S5 S6 S7
Temperature C 90 90 150 150 150
Pressure bar 1 1 1 1 1
Mass Vapor Fraction 0.026 0 0.104 1 0
Mass Solid Fraction 0 1 0 0 0
*** ALL PHASES ***
Mass Flow kg/hr 99785.29 190513.8 99785.29 10411.97 89373.32
Volume Flow cum/hr 4149.931 40.266 19522.15 19383.05 139.1
Enthalpy Gcal/hr -297.008 -496.611 -291.416 -33.095 -258.321
Density kg/cum 24.045 4731.392 5.111 0.537 642.51
Mass Flow kg/hr
ROCK 0 0 0 0 0
CAL-PHSP 0 0 0 0 0
CAF2 0 0 0 0 0
Sulfuric 13266.27 0 13266.27 20.391 13245.88
Water 7885.249 0 7885.249 5668.238 2217.012
CAL-HEMI 0 181750.4 0 0 0
H3PO4 73623.53 0 73623.53 0 73623.53
HF 5010.237 0 5010.237 4723.34 286.897
Fe2O3 0 2041.166 0 0 0
Al2O3 0 2041.166 0 0 0
SiO2 0 4681.073 0 0 0

Table A3: Properties of Sokoto Phosphate Rock (RMDC, 2010)

Property P2O5 CaO F SiO2 Al2O3 Fe2O3 H2O
Weight % 36.25 52.30 3.84 3.44 1.50 1.50 0.75

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