Project Report

Odda Process

1
1 Abstract

One of the toughest challenges the human race will be facing in near future is to
provide every individual with adequate food. According to an estimate by the Food
and Agriculture Organization (FAO) of the United Nations, food production must
increase by 70% by 2050. In order to achieve this, we need to come up with pro-
ductive fertilizers so as to enhance the crop yield. As 40 to 60% of the net global
crop yield is attributable to fertilizers, our purpose will definitely be satisfied.

The Odda process is an industrial method to produce nitrogenous fertilizers. It

was discovered by a chemical engineer named Erling Johnson in the municipal-
ity of Odda, Norway in 1927. The entire process mainly involves acidification of
phosphate rock with nitric acid in order to produce a mixture of calcium nitrate
and phosphoric acid.

In order to come up with a detailed flowchart of the Odda process, various sources
had been referred to. Similarly, values of heat capacities, heats of formations, &
heats of combustion of various compounds were obtained using reliable databases.
All these values made the energy calculations of all the intermediate streams pos-
sible.

Given the input feed rate, the mass & energy compositions of various streams have
been calculated. Concepts of material balance & energy balance, have been elu-
cidated & are extensively used for performing the calculations. All the computed
values for every stream of the process have been tabulated. However, for the ease
of calculations, various assumptions have been taken, which are also mentioned
further.

Reactive as well as non-reactive processes observed over each stream have been
described along with the mention of temperatures & pH value conditions, wherever
necessary. Also, the conclusions which are drawn from the analysis of the Odda
process & the importance of process has been explicitly mentioned. Through this
project, we were able to gain an insight of the real world chemical industries as
well as the job of a chemical engineer. Also, we’ve come to a consensus about
the significance of accurate data so as to refrain from the error observed in the
efficiency of the process.

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Contents
1 Abstract 2

2 Introduction 4

3 Material Balance 7
3.1 Dissolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2 Neutralisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3 CAN Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.4 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

4 Energy Balance 13
4.1 Dissolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.2 Neutralisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3 CAN Conversion . . . . . . . . . . . . . . . . . . . . . . . . . . 17
4.4 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

5 Conclusion 21

6 Roles And Responsibilities 22

7 Calculation Data 23

8 References 24

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2 Introduction
Odda process is an industrial method of the production of nitrogenous fertilizers.
Erling Johnson from Odda, Norway, brought light to this process. This process
involves the acidification of phosphate rock with nitric acid to produce calcium
nitrate and phosphoric acid, which undergoes CAN conversion reaction and neu-
tralization respectively to produce ammonium nitrate.

Nitrogenous fertilizers play a notable role in the growth of the plants by stimu-
lating chloroplasts, which are responsible for photosynthesis. The plants absorb
nitrogen in two forms: nitrate form and the ammoniacal form. The nitrate fertiliz-
ers dissolve easily in water and are quickly accessible to the plants. The ammonia-
cal fertilizers comprise of the positively charged ammonium ions that can interact
with the negatively charges clay or humus and hence are resistant to leaching. They
can also be used by the plants that require nitrogen in the nitrate form because of
its easy conversion into nitrate. The Odda process indulges in the production of
nitrogenous fertilizers by the production of ammonium nitrate. Ammonium nitrate
consists of both ammonia and nitrate; hence, its application lies in a wide range of
industries.

The production of ammonium nitrate involves 5 stages which are as mentioned

below:
The process begins by the dissolution of Calcium fluorapatite(phosphate rock) in
excess nitric acid(60 % w/w and 10% excess) and to produce calcium nitrate, phos-
phoric acid, and hydrofluoric acid.
Ca5 (P O4 )3 F(s) + 10HN O3(aq) −→ 5Ca(N O3 )2(aq) + 3H3 P O4(aq) + HF(g)
The calcium nitrate produced undergoes a crystallization process to produce cal-
cium nitrate tetrahydrate.
Ca(N O3 )2(aq) + 4H2 O −→ Ca(N O3 ).4H2 O(s)
The solution then undergoes a filtration process to separate calcium nitrate from
the mother liquor.
Further, the separated calcium nitrate reacts with ammonia in the presence of ex-
cess carbon dioxide to produce ammonium nitrate and calcium carbonate. This
process takes place in the CAN conversion reactor.
Ca(N O3 )2 + 2N H3 + CO2 + H2 O −→ 2N H4 N O3 + CaCO3

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On the other hand, the mother liquor is subjected to the neutralization reaction in
the presence of ammonia to form ammonium nitrate.

HN O3(aq) N H3(g) −→ N H4 N O3(aq)

Ammonium nitrate is collected from both the processes and is then subjected to
drying. The final product obtained can be used as a fertilizer.

Step 1:
Dissolution of phosphate rock in excess nitric acid Phosphate rock is pulverized to
increase its surface area and therefore the rate of the reaction. It is then dissolved
in excess nitric acid(60%w/w and 10% excess) in a cascade reactor to produce
calcium nitrate, phosphoric acid, and hydrofluoric acid. The temperature of the
reaction increases to about 70 degrees celcius because of the heat of the reaction,
which results in the evaporation of hydrofluoric acid. The reaction can be repre-
sented by:

Ca5 (P O4 )3 F(s) + 10HN O3(aq) −→ 5Ca(N O3 )2(aq) + 3H3 P O4(aq) + HF(g)

Step 2
Crystallization of Calcium Nitrate The solution undergoes a slow cooling process
at -5 degrees Celcius to separate 80-85 % of calcium nitrate in the form of crystals
of calcium nitrate tetrahydrate.

Ca(N O3 )2(aq) + 4H2 O −→ Ca(N O3 ).4H2 O(s)

The calcium nitrate is filtered out of the solution and is then processed in the CAN
conversion reactor. The left mother liquor is subjected to the neutralization pro-
cess.

Step 3
Neutralization of mother liquor The mother liquor comprising phosphoric acid, ni-
tric acid, hydrofluoric acid, and other impurities like calcium, magnesium nitrates,
and dissolved cations like iron, aluminum is contacted with ammonia gas. The am-
monia gas initiates the neutralization process under strict ph control. Nitric acid is
the first substance to react during the process because of its high acidic strength.

HN O3(aq) + N H3(g) −→ N H4 N O3(aq)

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There is an increase in the ph of the solution due to the addition of ammonia gas
that results in the precipitation of the dihydrogen phosphate salts of several metals.
The amount of ammonia gas added is regulated so as to avoid the precipitation of
metal fluorides.

Step 4
CAN Conversion reactor The separated calcium nitrate reacts with ammonia in
the presence of excess carbon dioxide to produce ammonium nitrate and calcium
carbonate. The produced calcium carbonate can be further processed in the con-
struction industries.

Ca(N O3 )2 + 2N H3 + CO2 + H2 O −→ 2N H4 N O3 + CaCO3

Step 5
The ammonium nitrate produced in step 3 and 4 finally undergoes the drying pro-
cess. The water present in the solution is evaporated to form a slurry of ammonium
hydrogen phosphate. It is then granulated and ultimately processed to form prills
of the final product, which can be used as nitrogenous fertilizer in the agriculture
industry. The addition of potassium chloride in the final product also results in the
formation of NPK fertilizers.

H2 O(l) −→ H2 O(g)

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3 Material Balance
The most important process to understand the basics of the a chemical process
is to perform the material balance. Material Balance is the application of law of
conservation of mass to the chemical process.Material balance for a stream is an
equation which assures that conservation of mass/moles holds true.

MInput + MGenerated = MOutput + MConsumed + MAccumulated

MInput is the mass of the substance in the input stream

MGenerated is the mass of the substance generated during the process
MOutput is the mass of the substance in the output stream
MConsumed is the mass of the substance consumed during the process
MAccumulated is the mass of the substance accumulated throughout the

Note:- Material Balance cannot be applied to Nuclear Reactions because the prin-
ciple of mass conservation is violated in these reactions.

3.1 Dissolution
Ca5 (P O4 )3 F(s) + 10HN O3(aq) 5Ca(N O3 )2(aq) + 3H3 P O4(aq) + HF(g)

Figure 1: Dissolution reaction streams

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 Compound 1A 2A Generated Consumed A3B O1
Ca5 (P O4 )3 F F 0 0 F 0 0
HN O3 0 A 0 B A−B 0
Ca(N O3 )2 0 0 C 0 C 0
H3 P O4 0 0 D 0 D 0
HF 0 0 E 0 0 E
N H3 0 0 0 0 0 0
N H4 N O3 0 0 0 0 0 0
CO2 0 0 0 0 0 0
CaCO3 0 0 0 0 0 0
H2 O 0 0 0 0 0 0

Compound 1A 2A Generated Consumed A3B O1

Ca5 (P O4 )3 F 90.9 0 0 90.9 0 0
HN O3 0 100 0 90.9 9.09 0
Ca(N O3 )2 0 0 45.45 0 45.45 0
H3 P O4 0 0 27.27 0 27.27 0
HF 0 0 9.09 0 0 9.09
N H3 0 0 0 0 0 0
N H4 N O3 0 0 0 0 0 0
CO2 0 0 0 0 0 0
CaCO3 0 0 0 0 0 0
H2 O 0 0 0 0 0 0

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3.2 Neutralisation
HN O3(aq) + N H3(g) −→ N H4 N O3(aq)

Figure 2: Neutralisation reaction streams

Compound 9E C6E Generated Consumed E10F

Ca5 (P O4 )3 F 0 0 0 0 0
HN O3 0 A 0 0 0
Ca(N O3 )2 0 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 B 0 0 0 0
N H4 N O3 0 0 0 0 C
CO2 0 0 0 0 0
CaCO3 0 0 0 0 0
H2 O 0 0 0 0 0

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 Compound 9E C6E Generated Consumed E10F
Ca5 (P O4 )3 F 0 0 0 F 0
HN O3 0 9.09 0 0 0
Ca(N O3 )2 0 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 9.09 0 0 0 0
N H4 N O3 0 0 0 0 9.09
CO2 0 0 0 0 0
CaCO3 0 0 0 0 0
H2 O 0 0 0 0 0

3.3 CAN Conversion

Ca(N O3 )2 + 2N H3 + CO2 + H2 O −→ 2N H4 N O3 + CaCO3

Figure 3: CAN Conversion reaction streams

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 Compound C5D 7D 8D O2 D11F
Ca5 (P O4 )3 F 0 0 0 0 0
HN O3 0 0 0 0 0
Ca(N O3 )2 C 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 0 D 0 0 0
N H4 N O3 0 0 0 0 F
CO2 0 0 E 0 0
CaCO3 0 0 0 B 0
H2 O 0 0 0 0 0

Compound C5D 7D 8D O2 D11F

Ca5 (P O4 )3 F 0 0 0 0 0
HN O3 0 0 0 0 0
Ca(N O3 )2 45.45 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 0 90.9 0 0 0
N H4 N O3 0 0 0 0 45.45
CO2 0 0 45.45 0 0
CaCO3 0 0 0 90.9 0
H2 O 0 0 0 0 0

3.4 Drying
H2 O(l) −→ H2 O(g)

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 Figure 4: Dissolution Streams

Compound E10F D11F F12 F13

Ca5 (P O4 )3 F 0 0 0 0
HN O3 0 0 0 0
Ca(N O3 )2 0 0 0 0
H3 P O4 0 0 0 0
HF 0 0 0 0
N H3 0 0 0 0
N H4 N O3 A B C 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 D E

Compound E10F D11F F12 F13

HN O3 0 0 0 0
Ca(N O3 )2 0 0 0 0
H3 P O4 0 0 0 0
HF 0 0 0 0
N H3 0 0 0 0
N H4 N O3 9.1 90.9 100 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 2.23 145.99

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4 Energy Balance
Energy balance for a reaction is an equation which assures that the conservation
of energy holds true. The general equation of energy balance is as given below

Einput + Egenerated = Eoutput + Econsumed + Eaccumulated

where,
Einput is the total energy of the input stream
Egenerated is the energy generated during the process
Eoutput is the total energy of the output stream.
Econsumed is the energy consumed during the process.
Eaccumulated is the energy accumulated during the process.

While doing the energy balance calculations, we made the following assumptions:

1. Steady state operations of the process

2. The changes in Kinetic Energy and Potential Energy of reactants is negligi-

ble

3. All reactions are taking place at atmospheric Pressure, i.e. P = 1atm

4. The cp values of all compounds are constant for a given reaction.

⇒ Enthalpy Calculation:
Z T2
h= ∆Hfo + cp dT
T1

where, ∆Hfo denotes the standard enthalpy of formation

4.1 Dissolution
⇒ Reaction

Ca5 (P O4 )3 F(s) + 10HN O3(aq) −→ 5Ca(N O3 )2(aq) + 3H3 P O4(aq) + HF(g)

⇒ Reaction Conditions

• Tinitial =25 degrees celcius

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 • Tf inal =70 degrees celcius

• P =1 atm

⇒ Reference : Ca5 (P O4 )3 F(s) , HN O3(aq) , Ca(N O3 )2(aq) , H3 P O4(aq) , HF(g) at

298K and 1 atm Pressure

Figure 5: Dissolution Streams

Compound 1A (MJ) 2A (MJ) A3B (MJ) O1 (MJ)

Ca5 (P O4 )3 F h1 0 0 0
HN O3 0 h2 h3 0
Ca(N O3 )2 0 0 h4 0
H3 P O4 0 0 h5 0
HF 0 0 0 h6
N H3 0 0 0 0
N H4 N O3 0 0 0 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 0 0

Z T2
h= ∆Hfo + cp dT
T1

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 where, ∆Hfo denotes the standard enthalpy of formation
Z T2
oCa (P O ) F
h1 = ∆Hf 5 4 3 + cpCa5 (P O4 )3 F dT
T1
Z T2
h2 = ∆HfoHN O3 + cpHN O3 dT
T1
Z T2
oCa(N O3 )2
h4 = ∆Hf + cpCa(N O3 )2 dT
T1
Z T2
h5 = ∆HfoH3 P O4 + cpH3 P O4 dT
T1
Z T2
h6 = ∆HfoHF + cpHF dT
T1

h1 + h2 = h3 + h4 + h5 + +h6 + Q

Compound 1A (MJ) 2A (MJ) A3B (MJ) O1 (MJ)

Ca5 (P O4 )3 F -616.074 0 0 0
HN O3 0 -1.6812 -1.867 0
Ca(N O3 )2 0 0 -42.404 0
H3 P O4 0 0 -34.528 0
HF 0 0 0 -2.474
N H3 0 0 0 0
N H4 N O3 0 0 0 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 0 0

4.2 Neutralisation
⇒ Reaction
HN O3(aq) + N H3(g) −→ N H4 N O3(aq)
⇒ Reaction Conditions

• Tinitial =25 degrees celcius

15
 • Tf inal = degrees celcius

• P =1 atm
⇒ Reference: HN O3(aq) , N H3(g) , N H4 N O3( aq) at 298K and 1 atm Pressure

Figure 6: Neutralization Streams

Compound 9E (MJ) C6E (MJ) E10F (MJ)

Ca5 (P O4 )3 F 0 0 0
HN O3 0 h1 0
Ca(N O3 )2 0 0 0
H3 P O4 0 0 0
HF 0 0 0
N H3 h2 0 0
N H4 N O3 0 0 h3
CO2 0 0 0
CaCO3 0 0 0
H2 O 0 0 0

Z T2
h= ∆Hfo + cp dT
T1

where, ∆Hfo denotes the standard enthalpy of formation

Z T2
h1 = ∆HfoHN O3 + cpHN O3 dT
T1

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 Z T2
h2 = ∆HfoN H3 + cpN H3 dT
T1
Z T2
h3 = ∆HfoN H4 N O3 + cpN H4 N O3 dT
T1

h1 + h2 = h3 + Q

Compound 9E (MJ) C6E (MJ) E10F (MJ)

Ca5 (P O4 )3 F 0 0 0
HN O3 0 -1.712 0
Ca(N O3 )2 0 0 0
H3 P O4 0 0 0
HF 0 0 0
N H3 -0.432 0 0
N H4 N O3 0 0 -3.086
CO2 0 0 0
CaCO3 0 0 0
H2 O 0 0 0

4.3 CAN Conversion

⇒ Reaction

Ca(N O3 )2 + 2N H3 + CO2 + H2 O −→ 2N H4 N O3 + CaCO3

⇒ Reaction Conditions

• Tinitial = 70o C

• Tf inal = 25o C

• P =1 atm

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 Figure 7: CAN Conversion Stream

Compound C5D (MJ) 7D (MJ) 8D (MJ) O2 (MJ) D11F (MJ)

Ca5 (P O4 )3 F 0 0 0 0 0
HN O3 0 0 0 0 0
Ca(N O3 )2 h1 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 0 h2 0 0 0
N H4 N O3 0 0 0 0 h3
CO2 0 0 h4 0 0
CaCO3 0 0 0 h5 0
H2 O 0 0 0 0 0

Z T2
h= ∆Hfo + cp dT
T1

where, ∆Hfo denotes the standard enthalpy of formation

Z T2
oCa(N O3 )2 )3 F
h1 = ∆Hf + cpCa(N O3 )2 dT
T1
Z T2
h2 = ∆HfoN H3 + cpN H3 dT
T1
Z T2
h3 = ∆HfoN H4 N O3 + cpN H4 N O3 dT
T1

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 Z T2
h4 = ∆HfoCO2 + cpCO2 dT
T1
Z T2
h5 = ∆HfoCaCO3 + cpCaCO3 dT
T1

h1 + h2 + h4 = h5 + h3 + Q

Compound C5D (MJ) 7D (MJ) 8D (MJ) O2 (MJ) D11F (MJ)

Ca5 (P O4 )3 F 0 0 0 0 0
HN O3 0 0 0 0 0
Ca(N O3 )2 -42.4 0 0 0 0
H3 P O4 0 0 0 0 0
HF 0 0 0 0 0
N H3 0 -4.14 0 0 0
N H4 N O3 0 0 0 0 -30.9
CO2 0 0 -17.9 0 0
CaCO3 0 0 0 -54.88 0
H2 O 0 0 0 0 0

4.4 Drying
⇒ Reaction
H2 O(l) −→ H2 O(g)
⇒ Reaction Conditions

• T = 25o C

• P =1 atm

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 Figure 8: Drying Streams

Compound E10F (MJ) D11F (MJ) F12 (MJ) F13 (MJ)

Ca5 (P O4 )3 F 0 0 0 0
HN O3 0 0 0 0
Ca(N O3 )2 0 0 0 0
H3 P O4 0 0 0 0
HF 0 0 0 0
N H3 0 0 0 0
N H4 N O3 h! h2 h3 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 h4 h5

Z T2
h= ∆Hfo + cp dT
T1

where, ∆Hfo denotes the standard enthalpy of formation

20
 Compound E10F (MJ) D11F (MJ) F12 (MJ) F13 (MJ)
Ca5 (P O4 )3 F 0 0 0 0
HN O3 0 0 0 0
Ca(N O3 )2 0 0 0 0
H3 P O4 0 0 0 0
HF 0 0 0 0
N H3 0 0 0 0
N H4 N O3 9.1 90.9 100 0
CO2 0 0 0 0
CaCO3 0 0 0 0
H2 O 0 0 2.23 145.99

5 Conclusion
Having learned about the Odda process, we came to know about the importance
of nitrogenous fertilizers in food and agriculture. They are necessary to enhance
crop yield. The byproducts formed in the reaction are also very useful in industries.

We came to know about the reactions that took place in the process and the con-
ditions that were applied to get a particular product. We came to know about how
plants are exactly operated. While going through the process, we understood the
real complexity involved in the production at the industry level. It really helped us
understand the importance of the material balance and energy balance which we
learned the entire course. We came to know about the actual application part.

The application of calculating the degree of freedom and solving the equation
through the table method was also clearly visible as in a big process as odda pro-
cess it almost becomes impossible to judge whether the equation are solvable or
not.

Due to a lack of information, we took many assumptions like steady-state oper-

ation of the process and 100 conversion undergoing in reaction but the outcome of
the Odda process clearly told a lot about the conditions of fertilizers in different
areas.

21
So we can conclude that the Nitrophosphate route provides an interesting avenue
for producing an agronomically balanced complex fertilizer.
Summing it up the project helped us understand the basic operations and calcula-
tions taking place in a real industry and gave us real insights about how chemical
engineers operate.

6 Roles And Responsibilities

1. Aditi Gera:
Involved in the material and energy balance manual calculations of the Odda
process. Involved in the discussion to decide the assumptions and approxi-
mations taken in the calculations. Helped in preparing the presentation and
report.

2. Maitreya Thakur:
Prepared the flow-chart for the overall Odda process. Also, prepared a table
with variables and assumptions for the degree of freedom analysis of the
entire process. Prepared and edited content for the report.

3. Pratyush Bhatt:
Worked on preparing the presentation. Prepared the content for the report.
Helped in material and energy balance calculations. Helped in the manual
energy balance of certain units.

4. Sakshi Baheti:
Involved in preparing the latex report for certain units. Played a crucial role
in the energy section of the latex report, along with the material balances.
Also, helped in creating the individual data tables for the report.

5. Sakshi Kabra:
Assisted in preparing the flow chart. Prepared the material balance tables,
results and other details in the report in latex. Was also involved in sorting,
proof-reading and organization of the content.

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7 Calculation Data
Compound Cp ∆Hof
Ca5 (P O4 )3 F 730 -13558
HN O3 53.29 -173.2
Ca(N O3 )2 149.4 -938.2
H3 P O4 150 -1271.66
HF 29.14 -268.6
N H3 35.564 -46.2
N H4 N O3 139.27 -365.5
CO2 37.12 -393.5
CaCO3 83.5 -1207.0
H2 O 75.348 -241.8

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8 References
• https://webbook.nist.gov/chemistry/

• http://nshs-science.net/chemistry/common/pdf/R-standard_enthalpy_of_formation.pdf

• http://www.matweb.com/search/datasheet.aspx?matguid=c4b97bcd7053495087c25611ce1d1d78ck

• https://en.wikipedia.org/wiki/Nitrophosphate_process

• https://chemicalprojects.wordpress.com/projects/production-of-nitrophosphate/detailed-
process-description/

• Theisis by Havard Kristiansen

• https://drive.google.com/drive/folders/0ABqLvXvrpU3sUk9PVA

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