PRODUCTION OF AMMONIA BY INDUSTRIAL

METHOD
Dissertation
Submitted
For
The partial fulfilment of the
Award of the degree of
MASTER OF SCIENCE TECHNOLOGY
IN
BIOTECHNOLOGY
to
Department of Biotechnology
Invertis University, Bareilly (U.P)

BY
ABRAR ALI KHAN
Roll no.1420806002

Candidates Declaration
I hereby certify that the dissertation entitled PRODUCTION OF AMMONIA BY
INDUSTRIAL METHOD which is being submitted for the partial fulfilment of the
requirement for the award of degree of Master of Technology in Biotechnology is a record
of my own work carried out under the Supervision of MR.RAJ KAPOOR RAHI, IFFCO
AONLA, and co guided by Er. Sachin Srivastava, Dep. Of Biotechnology, Invertis
University, Bareilly.
The matter presented in this dissertation has not been submitted elsewhere for the
award of any degree/diploma.
Date:

(Abrar Ali Khan)

Place:

This is to certify that the above statement made by the candidate is correct to be the best of
my knowledge and belief.

Guided By:
Mr. RAJ KAPOOR RAHI
IFFCO, AONLA

Approved by

Dr. Sanjeev Maurya

Head, Department of Biotechnology
Invertis University, Bareilly (U.P)
Forwarded by

Dr. R. K. Shukla
Dean, Invertis University
Bareilly (U.P)

Co-Guided By:
Er. Sachin Srivastava
Asst. Prof., Dep of
Biotechnology
Invertis University, Bareilly
(U.P)

Acknowledgement
We feel profound pleasure in bringing out this project report for which we have to go
form pillar to post to make it a reality. This project work reflects contribution of many people
with whom we had long discussion and without which it would not have been possible. We must
first of all, express our heartiest gratitude to respected DR.SAJEEV MOURYA(HOD),
DR.SHASHANK UPADHAYE,DR.RAVI DEVAL, ER.SACHIN SRIVASTAV and MR. RAJ
KAPOOR RAHI for providing us all guidance to complete the project.
It would be unfair if we do not mention the invaluable contribution and timely
cooperation extended to us by staff member our department, and especially we can never forget
the most worthy advices given by RAJ KAPOOR RAHI that would help us entire lifetime.
Last but not least we express our sincere thanks to the INVERTIS UNIVERSITY,
BAREILLY for implementing the ideas in our mind.

Thanking You
Abrar Ali Khan

Certificate
This is to certify that Report entitled PRODUCTION OF AMMONIA BY
INDUSTRIAL METHOD which is submitted by ABRAR ALI KHAN in partial fulfilment of
the requirement for the award of degree M.Sc. in Biotechnology to Invertis University, Bareilly
is a record of the candidate own work carried out by her under my/our supervision. The matter
embodied in this report is original and has not been submitted for the award of any other degree.

Date:

Supervisor Name
MR.RAJ KAPOOR RAHI
Signature:

Contents
Candidates Declaration............................................................................................. 2
Acknowledgement...................................................................................................... 3
Certificate................................................................................................................... 4
Ammonia plant......................................................................................................... 11
1. Desulphurization............................................................................................ 12
2. Steam reforming............................................................................................ 12
3. Shift conversion............................................................................................. 14
HTS CONVERTER................................................................................................ 14
4. CO2 removal selection (absorption & regeneration)......................................14
5. METHANATION................................................................................................ 14
DESIGN PROCESS GAS ANALYSIS.............................................................................. 15
Biochemical Oxygen Demand................................................................................... 17
Apparatus.............................................................................................................. 17
Reagents............................................................................................................... 17
Action Details........................................................................................................ 18
Calculation............................................................................................................ 19
Analysis of total phosphate (PO4) as P.....................................................................20
Chemical oxygen demand..................................................................................... 21
Calculation............................................................................................................ 22
Ammonia analysis.................................................................................................... 23
Calculation............................................................................................................ 23
SYNTHESIS OF UREA................................................................................................. 24
Physical and chemical properties..........................................................................24
Uses of urea.......................................................................................................... 25
Process Technology............................................................................................... 25
Striping process..................................................................................................... 26

Theory of Stripping................................................................................................ 27
Effect of process variables.................................................................................... 28
Effect of NH3/CO2................................................................................................... 28
Effect of Water/Carbon Dioxide ratio.....................................................................28
Effect of pressure and temperature.......................................................................28
Biuret in urea......................................................................................................... 29
7. DUCKWEED (HARASONA) ANALYSIS......................................................................31
7.1 Crude protein method.............................................................................................. 31
7.2 Calculation........................................................................................................... 32
7.3 Crude protein method (MAFF) (kjeldahl method)...........................................................33
7.5 Crude fat lipids...................................................................................................... 34
7.6 Reagents material and equipments.............................................................................. 34
7.6.1 Method............................................................................................................. 34
7.7 Calculation........................................................................................................... 35
7.8 Crude Fiber.......................................................................................................... 36
7.8.1 Reagents........................................................................................................... 36
7.8.2 Equipments........................................................................................................ 36
7.8.3 Method............................................................................................................. 37
7.8.4 Calculation........................................................................................................ 37
7.9 Ash content.......................................................................................................... 37
7.9.1 Moisture............................................................................................................ 38
7.9.2 Percentage nitrogen free extract (NFE)......................................................................38
8. Total available carbohydrates...............................................................................39
8.1 Reagents.............................................................................................................. 39
8.2 Method............................................................................................................... 39
8.3 Determination....................................................................................................... 40
8.4 Calculation........................................................................................................... 40
Result and
Discussion
.41
Conclusion
.42

Abstract
This reviews the history of the ammonia industry and its use as a nitrogen rich fertilizer. Current
ammonia industries were analyzed economically and environmentally, and the specifications
from current ammonia plants were compared with the patented process illustrated of the project.
The economic comparison shows a breakeven point for a current medium-scale ammonia plant
to be five years with a production cost of $600/ton, where the patented process plant can break
even in less than two years and has a relative production cost of $232/ton. It was found in the
environmental comparison that the patented process, if scaled globally, would address and
eliminate 7% of the total CO2 emissions on the planet. Lab works as well as calculations were
made to predict and recommend continuing research to further optimize the industrial production
of ammonia and related fertilizers.

Introduction:
In solid or liquid states, ammonia salts and solutions are the active components of most synthetic
fertilizers used in agriculture, which consume 83% of the worlds ammonia and warrant higher
demands for ammonia production. The primary industrial method for ammonia synthesis is the
Haber-Bosch process, created by Fritz Haber in 1905 and developed for industry by Carl Bosch
in 1910. The overall process synthesizes ammonia from molecular nitrogen and hydrogen by
feeding the reactants over iron catalysts at a high pressure and temperature, requiring bulky,
well-insulated reactors to house the process. The Haber process synthesizes approximately 150
million tons of ammonia each year and has allowed the earth to sustain a population nearly five
times larger than before the procedures invention. However, the use of natural gas as a source
of hydrogen and energy needed to derive nitrogen from atmospheric air have been the subjects of
environmental concern. The industrial use and geological extraction of natural gas are known to
contribute to carbon dioxide emissions and water pollution, respectively, and today an estimated
59% of natural gas produced in the United States is used in ammonia synthesis to meet the high
demand of gaseous hydrogen. Approximately 80% of ammonia synthesized today is eventually
converted into urea fertilizer, a dense nitrate that is more stable at room temperature, allowing
easier storage and transportation than ammonia.
To truly understand the significance of ammonia and urea as fertilizers, one should understand
the impact of treating soil with an effective fertilizer. Plants generally require soil containing
high amounts of available nitrogen, phosphorus and potassium, as well as other minor nutrients.
Synthetic and organic fertilizers can be used to successfully obtain this nutrient balance and
optimize plant growth, though synthetic fertilizers tend to work more consistently than organic
fertilizers, which are typically made from plant and animal wastes and tend to vary in
composition. Thus, the global demand for synthetic nitrogenous fertilizers has reached new
heights, with the 2012 global market generating over $98.6 billion and estimated to reach $114
billion by 2018.5 Considering that, in 2012, the industrial production of ammonia in the United
States alone was responsible for 9.4 million tons of carbon dioxide emissions, it is obvious that
the worldwide production of ammonia and urea must be monitored and reformed to handle the
expected increase in usage.However, in order to make necessary changes to these industries,
different options for ammonia and urea synthesis, as well as any potential environmental and
economic effects that may result from these options, should be assessed.

Due to their usage in the manufacturing of gunpowder and explosives, European chemists in the
late 1700s developed an interest in obtaining and synthesizing diverse nitrogenous compounds
such as nitric acid, sodium nitrate and ammonia, beginning research into the synthesis of these
compounds that would last for over a century. In the 1840s, German chemist Justus von Liebig
discovered nitrogen to be one of several nutrients essential to plant growth, leading to the
widespread use of nitrogenous compounds in fertilizers.7 Nitrogen was originally taken from
natural deposits in the earth, such as the Atacama Desert of Peru and Chile (rich in Chilean
saltpeter that could be converted to nitric acid). However, in the 1870s, ammonia was first
created industrially as a byproduct in the production of coke, though this method of ammonia
synthesis could yield only two-thirds of the nitrogen exported from South America.
In the late 1800s, chemists agreed that the demand for nitrogenous compounds would likely soon
exceed the natural supply, catalyzing the search for more effective industrial processes. The
creation of the Haber process in 1905, and its subsequent industrial scale-up by Carl Bosch in
1910, marked the first practical procedure for synthesizing anhydrous liquid ammonia from
hydrogen and atmospheric nitrogen. This process is still used industrially today. This procedure
has proven sufficient for meeting synthetic ammonia demands and the abundance of both
reactants suggests that the Haber process may be the most sustainable option possible, though
increased demands and a scarcity of resources may encourage the development of alternative
methods.
To increase the rate of ammonia synthesis to produce the necessary amount of product, the
temperature must be raised to the range of 400 - 500C, with pressure increased to 15 25 MPa
to compensate for the high temperature. The Haber process also relies on heated iron catalysts to
break the bonds of molecular nitrogen, and requires frequent cooling phases to maintain a
manageable equilibrium constant and repeated recycling of unreacted hydrogen and nitrogen to
achieve a higher overall conversion (approximately 18% of reactants are converted to ammonia
in each pass). These conditions can only be met with the protection of expensive reaction
vessels, that are strengthened and insulated to withstand the necessary pressures and
temperatures, and the high consumption of electricity, and in many cases, the reaction byproduct
carbon dioxide is released into the atmosphere where it is detrimental as a greenhouse gas.
Fritz Haber and Carl Bosch, the developers of the Haber-Bosch process were each awarded
Nobel prizes for their work, on the basis that they had overcame many difficulties associated
with reliable fertilizer manufacturing and high-pressure technology at an industrial scale. The
significance of their contribution became clear as agriculture improved across the world,
allowing the global population to increase from 1.6 billion people in 1900 to over 7 billion alive
today. However, many suspect that, if population increases at the same rate as it has over the past
century, the carrying capacity of earth will be tested and earths population could expand to the
point where food demand exceeds supply, ensuring death for many who will starve due to
insufficient food. Even today, the global population relies greatly on a consistent supply of food
being produced, and any large instability in crop yields is capable of leaving a noticeable
percentage of the population without food. Due to the dependence of crop prices on fertilizer
prices, it can be assumed that the first people to lose access to food will be those who can no
longer afford to feed themselves.
Modern agricultural yields are similar from season to season due to the consistent performance
of synthetic fertilizers and their unchanging composition, making nitrogenous fertilizers a more
reliable choice than organic fertilizers which vary in nutrient content. About 50% of nitrogen

applied to crops is absorbed while the remainder is lost to the soil and because this nitrogen is
easily manufactured, fertilizer is abundantly reapplied to assure that the minimum required
nitrogen will be available to all plants. However, nitrogenous compounds such as ammonia and
nitric acid can pollute soil and groundwater when used in excess, and the runoff is potentially
harmful to plants and animals depending on the nitrogen concentration. Humans, particularly
small children, have been known to suffer health complications from living in areas with heavy
use of synthetic fertilizer due to the excess nitrogen in the areas soil and water, or from eating
fish that were contaminated.
The environmental consequences of fertilizer manufacturing consist not only of ground
pollution, but include emissions into the atmosphere. The agricultural industry is responsible for
10% of total greenhouse gas emissions worldwide, according to the EPA, not including the
release of carbon dioxide as a by-product or any pollutants emitted due to ammonia synthesis.

Ammonia plant

N6/Naphtha
Raw water

AMMONIA
PLANT

Atmospheric air

NH3
CO2

Electric power

NG Analysis
Methane
Ethane
Propane
Butane
Pentane
Hexane
CO2
N2
Lower heating value
Carbon No.
Specific gravity

Lean gas
95.075
2.699
0.68
0.21
00.00
0.016
1.23
0.08
8182
1.047
0.59

For production of NH3 from N6/ Naphtha involves following steps

1. Desulphurization
2. Steam reforming
3. Shift conversion
4. CO2 removal selection
5. Methanation
6. NH3 synthesis

Rich gas
80.42
9.86
3.47
1.20
0.22
0.07
4.64
0.08
9118
1.2158
0.70

7. Refrigeration
1. Desulphurization: N6/ Naphtha containing Sulphur compounds up to 10/70 ppm.

Sulphur is poisonous for Primary reformer and LTS converter catalyst so N6/ Naphtha must be
desulphurised.
1. Hydrogenation
2. H2S absorption
Hydrogenation: N6 preheat 380

in E3204, before entering HDS H2 required for

hydrogenation (from recycle gas synthesis gas compound) added steam.

RSH + H2

RH + H2S

COS + H2

CO + H2S

C4H4S + 4H

C4 H10 + H2S

Exit of HDS
H2S Absorption 39kg (cm2 g,390 ,

passed through ZnO

H2S is absorbed by ZnO

ZnO + H2S

ZnS +H2O

ZnO + COS

Sulphur is removed up to < 0.05

ZnS + CO2

2. Steam reforming

CnH2n +2 +H2O + heat

Cn-1H2n-2+3H2O+CO

2CH4+3H2O+ heat

CO+CO2+7H2

CO+H2O

CO2+H2+heat

*reformer feed gas from ZnO absorber is mixed with process steam at 380 , mixed feed is
preheated to temperature of 490 , in mixed feed coil located in WHS of primary reformer.
Adiabatic pre-reformer
Adiabatic pre-reformer required when naphtha is used as feed stock
NC based catalyst for low temperature operation.
All higher hydrocarbons are decomposed in H2, CO, CO2, and CH4.

 Temperature
For NG

490 , and 470 , for mixed feed.

endothermic reaction and for naphtha

exothermic.

Primary reformer
Preheated hydrocarbon and steam mixture (485-490 ) passed downwards
through vertical tubes containing Ni based catalyst.
MP steam from process condensate stripper also mixed to process steam line to
primary reformer
Primary reformer is a fired heater having 576 side fired burns supply heat is catalyst
filled tubes (288 tubes).
Fuel for primary reformer furnace is normally a mixture of NG and tail gas from
PCR plants.
Hydrocarbon feed to primary reformer is converted H2 and carbon oxides.
Exit gases contain 10-11% methane and leave the tubes at 800 .
Fuel gases from P.R at 990 are cooled to 150 and divert to fuel gas path.
Secondary reformer
Process gases are mixed with preheated (550 ) air.
Partial oxidation takes place in top secondary reformer which caused considerable
increase in temperature to extents of 1100-1200 .
Gas from combustion chamber passed through NG based catalyst bed.
Reforming takes place with simultaneous cooling of gas.
Process gas from exist secondary reformer temperature -990 .
Methane contained is approximately 0.3%.
Amount of year flow to secondary reformer adjust so as to get a H2/N2 of 3:1 is make up
synthesis gas.

3. Shift conversion
Process gas leaving reforming selection contains approximately 13% CO which is
converted in to CO2 and H2 means of shift reaction.
CO + H2O
CO2 + H2 + heat
Shift conversion takes place in two CO shit conversion HTS & LTS.
HTS CONVERTER
Contains copper promoted iron based catalyst where CO is reduced to about 2.74%.
Inlet temperature is 350 and 044 .
HTS GUARD REACTOR
Contains chloride guard and Cu-n based catalyst.
Co is reduced to about 67% in process gas.
Outlet temperature is 224 .
LTS CONVERTER
Cu-Zn based catalyst.
CO is further reduced to about 0.14% in process gas.
LTS catalyst is very sensitive to sulphur poisoning.
4. CO2 removal selection (absorption & regeneration)

CO2 removal selection comprises of vetrocoke absorber and two regenerators.

CO2 in process gas is absorbed in liquid phase in EV solution at high pressure in absorber
and is again transferred in gas phase in two regenerators operating at low pressure.
EV solution consist of 27% H2CO3, 1% DEA, 1% glycine and 0.5% V2O5.

 Glycine is and DEA act as activators and V2O5 as corrosion inhibiter passed to absorber
having beds containing SS packing materials
In absorber, gas flows upwards against a descending stream of EV solution
The solution leaving the Absorber to loaded with CO2 and is known as rich solution.
The steam/CO2 mixture leaves from the top of regenerator and is cooled up to 67 .
The condensate form is separated and totally recycled co2 removal unit by gravity.
5. METHANATION

The final part of the gas purification is the methanation where residual oxides of carbon are
converted into methane as oxides of carbon are poisonous to ammonia synthesis catalyst.
Methane acts like as an inert gas in the ammonia synthesis loop .Methanation takes place in
methanation having Ni-based catalyst. The reaction involved are inverse of reforming.
CO+3H2

CH4+H2O+heat

CO2+4H2

CH4+2H2+heat

The process gas(38 & 27 kg/cm2) from methanator containing about 74% H2, and 25% N2
and some amount of methane and Ar. is called synthesis gas compression and ammonia synthesis

DESIGN PROCESS GAS ANALYSIS

S.NO.
1
2
3
4
5
6
7
8
9
10

POINTS
Exit prereformer
Exit primary
reformer
Exit seem
reformer
Exit HTS
Exit LTS
Inlet
methanator
Exit
methanator
Converter
inlet
Converter
out
S-50
converter
out

CO2
13.68

CO
0.23

H2
23.36

CH4
60.56

Ar+H2
2.17

12.29

10.23

66.12

10.26

0.95

8.70

13.76

54.59

0.30

22.65

17.44
19.55
00.03

2.87
0.14
00.30

58.93
59.17
74.52

0.27
0.57
0.33

20.49
20.53
24.82

74.25

0.67

25.08

5.59%NH3

64.25

5.85

24.31

19.56%NH
3
22.98%NH
3

49.85

9.96

20.63

46.49

10.24

19.79

3H2+N2

2NH3+ heat

Biochemical Oxygen Demand

Apparatus
B.O.D incubator
B.O.D bottles
Volumetric flask

Titration flask

Reagents
Sodium hydroxide solution-1N (App)
Hydrochloric acid-1N (App)
Dilution water-distilled water
Phosphate buffer solution-Dissolve 8.5 gm potassium di-hydrogen phosphate,21.75 di-potassium
hydrogen phosphate,33.4 gm of di-sodium hydrogen phosphate hepta-hydrate and 1.7 gm of
ammonium chloride in about 500 ml of water and dilute to 1 liter .The pH of the solution should
be 7.2.Dissolve 22.5 gm of magnesium sulphate in water and dilute to 1 liter. Calcium chloride
solution Dissolve 27.5 gm of calcium chloride in water and dilute to 1 litre. Ferric chloride
solution Dissolve 0.25 gm of ferric chloride in water and dilute to 1 liter. Seeding material
Supernatant liquor of domestic sewage stored for 24-36 hours at 20C.

Action Details
Store the dilution water at 20 C. For every 1 liter of water 1ml of each of phosphate buffer
solution magnesium sulphate solution calcium chloride solution and ferric chloride solution is
added. Seed the dilution with seeding material. The quantity of seeding material(0.1 1 % of
settled sewage)added should be such that oxygen depletion in the dilution water control is
between 0.2-0.8 mg/liter after incubation at 20 C for 5 days. Dilute the sample, if necessary so
as to obtain a depletion of at least 2mg/liter of dissolved oxygen after incubation for 5 days.
Usually 5-25% for treated effluent solution is taken. Fill the 2 glass BOD bottles with prepared
sample water and stopper on it. Similarly prepare succeeding dilution of lower concentration.
Determine the dissolved oxygen in 1 bottle as per method. Determine the dissolved oxygen in the
sample in blank or determine the dissolved oxygen by using dissolved oxygen analyzer OXI-323.
Water seals the other bottles and incubates at 20 C for 5 days. Also take the dilution water alone
into 2 glass stopper bottles and determine the blank in 1 and incubate the other at 20 C for 5
days, after incubation for 5 days.

Trial no.

Day

Volume of Initial
sample(ml)

final

Blank
3.
4.

0
0
0

200
200
200

8.2
7.9
7.9

0
0
0

Volume of Dissolved
titrent(ml)
oxygen(mg/l
)
8.2
8.2
7.9
7.9
7.9
7.9

Blank
1.
2.

5
5
5

200
200
200

0
0
0

8.0
3.2
3.2

8.0
3.2
3.2

8.0
3.2
3.2

Result:
Initial DO of the dilution sample, Do

= 7.9 ml

DO at the end of 5 days for the dilution sample = 3.2 ml

Blank correction = C0-C5,BC

= 0.2 ml

Initial DO of the blank,C0

= 8.2 ml

DO at the end of 5 days for the blank, C5

= 8.0 ml

Biological oxygen demand = (D1 - D2) - ((C1 - C2) * F)

P
Biological oxygen demand = (7.9-3.2-.0.2) 200/10
= 4.5200/10
= 90 mg/L

Calculation
Biological oxygen demand = (D1 - D2) - ((C1 - C2) * F)
P
Where,
D1= Initial dissolved oxygen content of diluted sample.
D2=Dissolved oxygen content of diluted sample after incubation
C1=Initial dissolved oxygen content of seeded dilution water after incubation
C2=Dissolved oxygen content of seeded dilution water after incubation
F=Ratio of the seed in the sample to that in the control that is percent seed in D 1/percent seed in
C1
P=decimal fraction of the sample used

Analysis of total phosphate (PO4) as P

Take 250 ml beakers

Blank

100ml DM Water
+
5ml 37% H2SO4
+
5 ml ammonium molebdate

Sample

Sample 100ml
5ml 37% H2SO4
5 ml ammonium molebdate

+
5 ml amino solution for PO4

5 ml amino solution for PO4

Shake properly to each beaker after each step

Appearance of blue colour
See absorbance at = 650 nm by U.V Spectrophotometer.
PO4 (ppm) = Concentration * 1000* 0.326
Sample Volume

Chemical oxygen demand

Oxygen in drinking water is 8 ppm. Sample collect in glass bottle for analysis of COD.
For preservation of sample we add some concentrated H 2SO4 in sample (5-10ml). Take
250 ml flat bottom round flask.

Blank
Sample
Take 5ml Distilled water
Take sample according to COD concentration
2 ml
5 ml / 2 ml
+
+
Add 1 gm mercuric sulphate
Add 1 gm mercuric sulphate, shake
+
+
Add 5ml concentrated H2SO4
Add 5ml concentrated H2SO4, shake
+
+
Add 0.5 gm silver sulphate
Add 0.5 gm silver sulphate, shake
Add 50 ml 0.1 N K2Cr2O7
Add 50 ml 0.1 N K2Cr2O7, shake
Add 70 ml concentrated H2SO4
Add 70 ml concentrated H2SO4
from condenser slowly and carefully
from condenser slowly and carefully
Arrange distillation unit and put on the flask in distillation unit

Fig1. Distillation Unit

Raise the temperature of distillation unit and given the water flow to condenser.
Digest up to 3-4 hours. After digestion, let to cool the flask. Titrate against 0.1N FAS with
ferroien indicator(2-3 drops). End point brick like red.

Calculation
COD(ppm) = burette reading N of K2Cr2O7 factor of K2Cr2O7 8 1000
Sample Volume

Ammonia analysis

Take two 50 ml volumetric flask.

Blank
Take some DM water

Sample
Take some DM water

Take sample according to ammonia

concentration such as 5 or 10 ml
2 or 3 drops of sodium potassium titrate

2 or 3 drops of sodium potassium titrate

Make up mark with DM water

Make up mark with DM water

Add 1 ml Nesslers reagent

Add 1 ml Nesslers reagent

Shake and wait 5minutes and see absorbance at =460nm

Calculation
Ammonia (ppm) = Concentration from spectrophotometer 1000
Sample Volume

SYNTHESIS OF UREA

Urea synthesis isof historical importance, it being the first organic compound to be synthesized
from inorganic compounds in a laboratory Wholer in 1828, obtained urea from ammonium
cyanate. Previous to this, urea had been separated from urine and the experiment by Wholer
showed that organic material could be prepared from an inorganic chemical. Commercial
production of urea was started in 1920, by I .Farben in Germany based on ammonium carbamate
process, since then, considerable ingenuity was used to overcome process difficulties such as
corrosion problems recovery of off-gases and economics process roots which resulted in present

day development. Ammonia and CO2 are usually available from same site, as CO 2 is a bi=product
of ammonia plant using hydrocarbons as feed stock.

Physical and chemical properties

Molecular weight 60.05
Boiling point decomposes at atmospheric pressure before boiling
Density (Crystal at 20 C) 1.335
Heat of combustion (Solid, Cal/gm) 2531
Heat of solution in water, Cal/gm 57.8
Critical humidity 70.1
Viscosity at 150 C 2.16CPS
Crystallization heat 47.0 Kcal/Kg
Fusion heat 59.95 Kcal/Kg
Thermal conductivity 0.191Kcal/sec
Solubility in water by weight % Temperature C
120
Urea in gm/100gm of water
2244

20

40

60

80

100

67

105

163

246

396

725

Urea is a white crystalline chemical compound with a melting point of 132.6 C. It is readily
soluble in water. On heating beyond its melting point, it decomposes giving CO 2, NH3 and other
complex compounds of carbon, nitrogen, oxygen .At 160 C it decomposes to yield ammonia,
Biuret and higher condensation products, the longer the urea is held above its melting point,
further the reaction proceeds .Urea is in fact the diamide of carbonic acid with a chemical
formula NH2CONH2

Uses of urea
Its main application area) As fertilizer in agriculture
b) As cattle feed
c) As an important raw material for a number of industrial/household products like- urea
formaldehyde melamine and urea furfural
Due to high nitrogen content of urea the demand for fertilizer grade urea is rising rapidly. Urea
today accounts for a large percentage of nitrogenous fertilizer. Urea is used as cattle feed in
western countries. Sheep and cattle are capable of digesting urea up to about 40%. Urea also

finds extensive use in preparation of adhesives, textile, anti-shrink compounds and in the
exchange of resins and as in intermediate in the preparation of pigments

Process Technology
Urea is produced by synthesis from liquid ammonia and gaseous carbon-dioxide. Ammonia and
CO2 react to form ammonium carbamate,a portion of which dehydrates to form urea and water.
The fraction of ammonium carbamate that dehydratesis determined by ratio of various reactants,
the operating pressures temperature and the residence time in rector. The reactionof ammonia
and CO2 to produce urea takes place in two stages at elevated pressure and temperature.
2NH3 +

CO2

Liquid
Ammonia

Gaseous

NH2COONH4

======>

38.1Kcal/gm.mol

H2O

Ammonium
Carbamate

======>

Ammonium
Carbamate

NH2COONH4

NH2CONH2
Urea

Water
-7.1Kcal/gm.mol

The first reaction is strongly exothermic and therefore heat is liberated as this reaction occurs.
With excess NH3 and CO2 conversion to carbamate is almost 100%, provided solution pressure is
greater than decomposition pressure.The decomposition pressure is the pressure at which
carbamate will decompose back into CO2 and NH3, i.e.
NH2COONH4
=====>
2 NH3 +
CO2
Decomposition pressure is a function of NH3 concentration in the feed and the solution
temperature and increases if either temperature or NH 3 recycle is increased. It is desirable to
operate at higher pressure and the high mole ratio of NH 3 to CO2 provided reactor operating
pressure is quite highenough to prevent carbamate from decomposition into NH 3 and CO2.This
will maximize CO2 conversion to urea and towards the reaction.The second reaction is
endothermic therefore heat is required for this reaction to start. The heat for this reaction comes
from the formation of carbamate. This reaction is a function of temperature and ammonia
concentration in the feed. The solution effluent from the reactor being a mixture of urea solution,
ammonium carbamate, unreacted ammonia water and CO 2 is extremely corrosive in nature. The
subsequent stages of process consist of decomposition of unconverted carbamate, recovery of
resulting ammonia and carbon dioxide for recycle, concentration and prilling of urea solution.

Striping process
Efforts to find some additional driving force beyond the usual addition of heat and reductions in
pressure to decompose carbamate from urea reactor effluents have met with great success. In this
process decomposition of ammonium cabamate is done at the synthesis pressure by using either

CO2 (Stamicarbon CO2 striping process) or NH 3 vapors (SNAM PROGETTI NH3 STRIPING
PROCESS) in a falling film type decomposer, normally called striper. The reactor effluents are
allowed to fall through the striper tubes in the form of liquid film from the top while the striping
agent is introduced from the bottom which travels upwards. Medium pressure steam condensing
on the shell side of the striper supplies heat for decomposition of ammonium carbamate.
Currently, Snamprogetti process does not require in ejection of ammonia vapors at stripper
bottom, only higher molal ratio of NH3/CO2 is maintained in the reactor .At higher molal
NH3/CO2 ratio,ammonia liberated in stripper is adequate to carry out stripping effectively .Since
the reactor stripper condense system operates at nearly same pressure it is possible to feed
recycle carbamate either by gravity flow which however recessiates the installation of carbamate
condenser at a much higher elevation so as to give the required heat or to use a recycle ejector
using a part of the feed reactants as a motive fluid.Snamprogetti was the first to develop use of
such recycle ejector and locate condensers at ground level. Since a major portion of unconverted
carbamate is decomposed and recycled to reaction at synthetic pressure,load on downstream
decomposition and recovery section is comparatively much less resulting in lower utility
consumption. Further since the synthesis pressure in the stripping process is lower,it is possible
to employ steam driven centrifugal CO2 compressor which has lower maintenance and operating
cost.In both stamicarbon and Snamprogetti stripping process low pressure steam is generated in
carbamate condenser which has resulted in lower consumption of steam and cooling water.

Theory of Stripping
The theory of stripping is based on Henrys Law. The concentration of components insolution
while in equilibrium with vapour phase is directly proportional to partial pressure of the
components in the vapour phase. By changing partial pressure of a component concentration of
solution can be changed. This can be illustrated as follows
Let us assume that A and B are two components.
CA=Concentration of component A in solution
CB=Concentration of component B in solution
PA and PB=Partial pressures of components A and B in vapour phase
P=Total pressure; PA+PB
In stripper we introduce excess NH3alongwith reactor effluent .This NH3 is released as vapour by
heating in stripper. This NH3 vapour increases partial pressure of ammonia over the solution as
the total pressure remains same partial pressure of CO 2 reduces to a lower value. In accordance
with Henrys law ammonia carbamate decomposes to increase partial pressure of CO 2 in vapour
phase to approach equilibrium concentration. This NH 3 is released as vapour by heating in
stripper. Stripping action is thus carried out and heat of decomposition is supplied from an
external source by condensation of medium pressure steam. Partial pressure of either of the
components can be charged and this will result in the decomposition of carbamate. .

Effect of process variables

Carbamate formation takes place with liberation of heat and urea formation takes place with
absorption of heat. The former reaction is rapid and the latter is slow. The equilibrium conversion
to urea will be favored under the following conditions:i.
Higher NH3 concentration
ii.
Less H2O concentration
iii.
Higher temperature
iv. Increased residence time

Effect of NH3/CO2
Theoretical ratio of NH3/CO2 is 2. But in this condition urea yield is only 43.44% at 170 atm
and 155C. This low yield can be improved by changing NH 3 /CO2 ratio. When the excess ratio
of NH3 is increased to 280% urea yield will change from 43.5% to 85.2%. On the other hand
when excess ratio of CO2 is changed from 0 to 300% urea yield will increase only from 43.5% to
46%. The effect of excess CO2 is very small. Moreover, in the CO2 rich conditions the solution
becomes very corrosive. In general almost all the urea plants are operated under NH 3/CO2 ratio
around 2.5 to 5.

Effect of Water/Carbon Dioxide ratio

Water is a product of urea formation. One mole of water is formed when 1 mole of urea is
produced by the presence of excess water, equilibrium reaction shifts in reverse direction and
yield of urea is poor. However water has to be added for recycling unconverted NH 3 and CO2
back to reactor. Lower the amount of water in reactor higher is the yield of urea. Too low water
concentration in low pressure recovery section results in higher carbamate concentration and this
causes pumping problem and clogging in piping system. Excess water in reactor also reduces
effective volume for urea formation and additional energy is required to get rid of this water.
Study show that presence of 1 mole of excess water per mole of carbamate reduces equilibrium
yield of urea to half.

Effect of pressure and temperature

As per Le Chatliers principle higher pressure favors carbamate formation. At the operating
condition carbamate formation is almost instantaneous and reaction tends to completion,
provided reaction heat is removed simultaneously. Lower temperature favors carbamate
formation, being an exothermic reaction. In case of urea formation, higher temperature is
favorable because the reaction is endothermic. The relation is such that when temperature
increases the conversion increases proportionally. Maximum equilibrium conversion is achieved
at around 190 to 200 C. Reactants are highly corrosive at higher temperature. Operating
pressure is totally dependent on temperature at which conversion takes place. Urea conversion
takes place in liquid phase. So equilibrium pressure becomes increasingly higher when the
temperature rises.

Urea conversion reaction is slow and takes 20 minutes to attain equilibrium. Considering the
slowness of the reaction, urea rector is so designed that residence time should be more than 20
minutes. Higher residence time favors equilibrium conversion and normally reactors are
designed for residence time of 30 minutes to 1 hour depending upon operating parameters. 68%
urea conversion takes place with residence time of 30 minutes at a mole ratio of 4:1 and
temperature of 188 C whereas to achieve 60 % conversion with a mole ratio of 2:8:1 at 181 C
almost a residence time of 55 minutes is required. Residence time in urea reactor plays an
important part on equilibrium conversion, where operating parameters including mole ratio are
not favorable for a good yield higher residence time compensates to some extent to achieve a
better yield. But this is done by providing higher reactor volume which increases capital
investment.

Biuret in urea
A problem is faced by every urea manufacturer in the formation of biuret during theproduction
process. It is not a desirable substance as it is toxic to the plants. It should not exceed more than

1.5% in urea as per fertilizer control order. When urea solution is heated in the absence of free
ammonia and objectionable ingredient called Biuret is formed according to following reaction:2NH2CONH2
Urea

<======>

NH2CO.NH.CONH2
Biuret

NH3

The formation of biuret is favored by higher temperature, higher concentration of urea solution,
lower ammonia content and higher residence time.

7. DUCKWEED (HARASONA) ANALYSIS

7.1 Crude protein method

1 gm dry sample in kjeldhal flask
+
10 gm of potassium sulphate
+
0.7 gm of mercuric oxide
+
20 ml conc. H2SO4
Place the flask for digestion (flask must be tilted)

Heat up to B.P & maintain

Until solution is clear

Extra heat 30min more.

If foaming is present add paraffin wax.

After digestion leave to cool (adding then 90 ml DMW.)

+
25ml 4% sodium sulphate solution

Stir and add glass beads

+
80ml of NaOH(40% solution) keeping the flask tiled.

2 layers will form

Connect the flask to distillation unit.

Collect 50ml distillate containing ammonia in 50ml of boric acid (1%) with mixed indicator

Titrate the collect distillate with std. 0.1 N HCl

7.2 Calculation
% nitrogen in sample = 100 ( BR N F 0.014 ) /sample weight (g)
% crude protein =% N2 in sample 625.

7.3 Crude protein method (MAFF) (kjeldahl method)

Weight 1gm of sample (dry)

+
16gm potassium sulphate
+
0.6 to 0.7gm of mercuric oxide
+
25ml conc. H2SO4 & a few grains of pumice stone .

Heat flask moderately at first, shaking occasionally until the material is carbonized and the
bubbles have disappeared. Then rise the temperature and bring to gentle boil. Do not allow the
flask walls to overheat so that organic particles do not adhere to them.

When the solution looks clear and colorless, continue to boil for 2 hours longer, than cool. If
after digestion and cooling the solution crystallizes, repeat the analysis of crystallization continue
to occur. Repeat the analysis using more sulphuric acid.

Add 250-350 ml DMW in flask ,stirring the contents at the same time. Let cool and add a few
zinc pellets.

Transfer 25ml 0.1 N H2SO4 in a beaker for collect distillate with methyl red indicator
+
100ml NaOH solution (40%)
+
10ml sodium sulphate solution

Mixed an connect to kjeldahl for distillation

Heat
Collect the 150ml distillate liquid in 30 minutes

Titrate the distillate of collecting beaker by 0.1 N NaOH

7.4 Calculation
Determined the H2SO4 consumed.
1ml H2SO4= 1.4mg nitrogen
Or
Calculate the % of N2 in sample and multiply by 6.25 for getting % of protein (MAFF)

7.5 Crude fat lipids

In this method the fats are extracted from the sample with petroleum either and evaluated as a %
(percentage) of the weight before the solvent is evaporated .

7.6 Reagents material and equipments

Petroleum either, B.P 40 -60

Soxhlet extraction apparatus.

Laboratory kiln set at 100 .

Dryer and extraction thimbles.

7.6.1 Method

1. Remove extraction flasks from kiln without touching them with fingers, coal in a dryer
and weight to within milligrams
2. Weight 3 to 5 gms of sample to within mgs in an extraction thimbles, handling it with
longs and place in the extraction unit. Connect the flask containing petroleum either at
2/3 of total volume to the extractor.
3. Bring to boil and adjust heat to obtain 10 refluxes/hours the length of extraction will
depend on the quality of liquids in samples ,very fatty materials will take 6 hours.
4.When finished evaporate the either by distillation or in a rotoevaporater . cool the flask
in a dryer and weight them to within milligrams. The defalled sample can be used in
determining crude fibre analysis.

7.7 Calculation
Crude lipid content (%) = 100
A = wt of clean by dry flask (gms
B = wt of flask with fats (gms)
C = wt of the sample (gms)

3-5 gm sample

Sokhlet extraction 6 hours

With petroleum eather

Calculate

Weight
flask

7.8 Crude Fiber

7.8.1 Reagents

H2SO4 0.255 N
NaOH 0.313 N
Anti foam
Ethyl alcohol (95% V/v)
Petroleum ether
1% HCL solution (V/v)

7.8.2 Equipments

600 ml flat bottomed balloon fly

Condensation unit
11 kitazate flask
Buchner funnel
Filtration crucible
Rubber cones
Whatmann filter paper
500 ml retort dryer
Laboratory kiln
Crucible furnace

Eliminate
solvent in
evaporator or

Cool in dryer

7.8.3 Method

Weight 2-3 gm defatted ,dry sample in flask, add 200 ml hot H2SO4(0.255 ml)
Attach the condenser and bring to boiling points in 1 minute, of necessary, add antifoam.
Boil for exactly 30 minutes, maintaining the volume of distilled water constant and
swirling the flask periodically to remove particles adhering to the side.
Line the Buchner funnel with the filter paper and pre-heat with boiling water. At the same
time ,at the end of the boiling period remove the flask, let rest one minute filter the
contents carefully, using suction , filtration should be carried out in less than 10 minutes.
Wash the filter paper with boiling water.
Transfer the residue to flask using a retort containing 200 ml of boiling NaOH solution
and boil for 30 minutes as in step 2
Pre-heat the filtration crucible with boiling water and carefully filter the hydrolyzed
mixture after letting it rest for 1 minutes.
Waslv the residue with boiling water, with the HCL solution and then again with the
boiling water, finishing with three washes with petroleum ether place the crucible in a
kiln set at 105 for 12 hours then cool in dryer.
Quickly weight the crucible with the residue inside and place in the crucible furnace at
550 for 3 hous. Leave to cool in a dryer and weight them again.

7.8.4 Calculation
Crude fibre content (%) = 100 (A-B)
C
A = wt of crucible with dry residue (gm)
B = wt of crucible with ash (gm)
C = wt of sample (gm)

7.9 Ash content

2.5 to 5.0 gm sample in crucible (previously calcined and brought to constant wt.)

Place the crucible in a furnace and heat at 550 for a 12 hours.

Leave to cool and transfer to a dryer

Carefully weigh the crucible with ash

% Ash content = 100 (A-B)
C
A = wt of crucible with sample (gm)
B = wt of crucible with ash (gm)
C = wt of sample=100 (B-A)-(C-A)
B-A

7.9.1 Moisture

Weight out approx 5-10 gm of previously ground sample

Place sample in drying own at 105 for at least 12 hrs.

Weight again

% Moisture content = 100 (B-A)-(C-A)

B-A
A = wt of the clean dry scale pan (gm)
B = wt of the clean dry scale pan (gm) + wt sample (gm)
C = wt of the clean dry scale pan (gm) + dry sample

7.9.2 Percentage nitrogen free extract (NFE)

NFC (%) = 1OO(A + B+C+ D+ E)
A = Humidity content (%)
B = Crude protein content (%)
C = Crude lipid content (%)
D = Crude fibre content (%)
E = Ash content (%)

8. Total available carbohydrates

Based on hydrolyzed starch and soluble content.

8.1 Reagents

52% perchloric acid solution (297 ml perchloric acid + 100 ml DMW)

H2SO4 Solution (760 ml of H2SO4 ( sp.6r 1.84) in 330 ml DMW) let cool
Anthrone reagent (0.1% anthrone in H2SO4 solution)

Standard glucose solution(100 mg in 100 ml DMW or 10 mg glucose in 100 ml DMW

0.1mg)

1 ml=

8.2 Method
Weight out 1 gm of dry sample ( 0.001 gm sample containing approx 60 to 300 mg of TAC
( Total available carbohydydrates)
Or
2.5 gm of wet sample

Transfer to gradualated cylinder (100 ml cylinder)

Add 10 ml water and stirr with glass rod .

Add 13 ml of perchloric acid solution (20 minutes starring with glass rod)

Transfer, filter & make up the volume to 250 ml in V.F (DMW)(make up mask)

8.3 Determination

Dilute (above prepared sample) 10 ml to 100 ml in V.F, shake and transfer 1 ml of this
sample in a test tube and 1 ml DMW for blank.
Take two 1 ml duplicate blanks using the dilute glucose solution.(glucose standard)
Quickly add freshly prepared anthrone reagents in all the tubes. Cap the tube and mix
vigorously.
Place in water both and heat for 12 minutes.
Cool rapidly to room temperature ( The green colour occurred and stable for 2 hours)
See absorbance at = 630 nm against blank.

8.4 Calculation
Total available carbohydrates ( % of glucose) = 25. B
A.W
W = wt of sample in gm
a= Absorbance of diluted standard
b= Absorbance of samples

RESULT & DISCUSSION

In the interest of developing future options for ammonia production, this project presents the
current industrial process alongside the patented process designed for this project and discussed
in Chapter 3, comparing the two methods in terms of their environmental impact and economic
feasibility, as well as their effect on the cost of ammonia production and sales. Because the
patented process in Chapter 3 has not yet been built, results concluding the production, cost and
efficiency of a plant are based on simplified calculations, while results concerning the price and
environmental impact of current ammonia production are found empirically.
According to the project advisor, additional factors must be taken into consideration to predict
more accurate capital costs for the patented process: All capital costs recorded in Chapter 3 of
this paper were calculated by the software Cap cost based on the input of several variables.
However,according to industry experts: Cap cost is known to overvalue, and it is expected that
the software consistently overestimates the cost of equipment by up to 30%. Software like Cap
cost is designed to predict the cost needed to build a plant and, because of the variety of
equipment that displays a large price range, the software gives the highest estimated price to
assure that this value could afford all capital costs. If the software calculated only average or
lower prices, users would risk calculating a capital cost less than the actual cost, putting the
plants budget and expected profit in jeopardy. As a result, the $702 million fixed capital cost of
the plant could in reality account for as little as $491.4 million. This reduction in capital costs
would result in a break-even point at approximately 1.6 years of operation. According to the
project advisor, commercial process designs estimated to reach a break-even point within two
years are typically approved for implementation by commercial manufacturers with minimum
review, due to optimization standards having already been achieved. Such processes are also
highly profitable in commercial production compared to processes that require more time to
break-even, paying off capital costs soon after the start of operation and turning a larger profit for
each year that the process is used.

Conclusion
1. Advantages
The technological advantage of ammonia is that it requires only small-dimensioned
piping and throttle cross sections. At the same time, assembling copper piping is
part of the daily routine of technicians. But due to ammonias incompatibility with
copper, different technologies have tobe used for building ammonia systems a
job which so far can only be mastered by a few specialized companies. In general,
ammonia is a natural refrigerant with only minor risk potential.

In nature, ammonia is produced by biological processes, is naturally

decomposed, and does not add to the global greenhouse effect.
Only 3% of the ammonia existing on this planet results from human activity,
even though it is produced in large quantities for fertilizers. Ammonia is
readily soluble in water; the solution is called sal ammoniac, which is wellknown in households.
The odor of ammonia has a highly alerting effect. Even the slightest traces of
ammonia in the air can be perceived easily. Refrigerant leaks are therefore
detected at once

2. Disadvantages
When in gaseous form, ammonia has a short atmospheric lifetime of about 24 hours and usually
deposits near its source (the majority of gaseous ammonia is depositied within 700 -1000 m of
feedlot parimeters; 29). In particulate form ammonia can travel much further impacting a larger
area. Both gaseous and particulate ammonia contribute to eutrophication of surface waters, soil
acidification, fertilization of vegetation, changes in ecosystems and smog and decreased
visibility in cities and pristine areas. Since ammonia is one of the only basic species in the
atmosphere, it readily reacts with strong acidic species in the atmosphere such as nitric and
sulphuric acids, which are by products of combustion process including vehicle and industrial
sources, to form ammonium salts, also known as fine particulate matter or PM2.5. Due to their
small diameter (less than 2.5 microns (m) )and increased atmospheric lifetime of 15 days, these
particulates are able to travel long distances before being dry or wet deposited to the ground
surface. This allows them to travel from rural areas to urban locations where they mix and build
up in the atmosphere leading to smog or transportation to other areas. In Colorado transport of
these particulates from urban areas to pristine mountain regions, such as Rocky Mountain

National Park, has been documented. Deposition of these N rich particulates in the Park has
caused changes in the Park's vegetation, lakes, and natural ecosystems

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