INTRODUCTION TO THE WORLD OF UREA

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CONTENTS
• WHAT ARE FERTILIZERS

• WHY FERTILIZERS ARE USED

• NITROGEN CYCLE

• FERTILIZER BUSINESS

• PRODUCTION SCHEME

• PLANT LAYOUT
WHAT ARE FERTILIZERS?
Fertilizers are simply plant food with all the essential nutrients that plants
need to grow, in a form that they can easily use:
Primary nutrients:
• Nitrogen (N)
• Phosphorus (P)
• Potassium (K)
Secondary nutrients:
• Sulfur (S)
• Calcium (Ca)
• Magnesium (Mg)
Balancing nutrients:
• Finding the right balance is essential.
• Plants need more nitrogen than phosphorous or potassium. That's why
nitrogen is the major component of most fertilizers
• Phosphorous provides the energy that plants need to thrive
• potassium helps them to fight disease and grow strong stalks
WHY FERTILIZERS ARE USED?

• As plants grow, nutrients are absorbed from the soil

• To maintain a rich and fertile growing environment, these nutrients must

be returned to the soil after they have been depleted

• Plants need 1kg of nitrogen to produce 10-15kg of grain

• Most tropical soils can fix nitrogen by drawing it from our nitrogen-rich
atmosphere - enough to yield around 1 ton of grain per hectare

• However, to produce more grain it is essential that the plants boost their
source of nitrogen (as well as phosphorous, potassium and trace
elements) from fertilizers.
Nitrogen Cycle
INTRODUCTION TO UREA PRODUCT
• Urea indentified 1773
• First organic compound prepared by inorganic synthesis in 1828 (Wöhler)

• Commercial production started in Germany 1922

• Urea considered as a slow-release fertilizer as it must undergo two
transportations:
1. Hydrolysis:
2. Nitrification: => Nitrite or Nitrate (microbes, moist, warm soil)
• Biuret is the impurity of urea
• More than 160 Million tons is produced annually
• Over 80% of urea is used to fertilize crops
• Demand for urea fertilizer is growing at over 3%
- even faster than the global rise in population.
PROPERTIES OF UREA
USES OF UREA

• Main N₂ fertilizer, specially for the flooded regions

• Cattle feed supplement (where it is cheap)
• Feedstock for melamine plastics
• Feedstock for various glues
• Reduction of NOₓ emissions in diesel motor exhaust gases (AdBlue)
• Deicing agent for airport runaways
• Raw material in:
- Pharmaceutical industry
- Fermenting and brewing industries
AMMONIA-UREA PLANTS; started-up 1995-2015 (1/3)
AMMONIA-UREA PLANTS; started-up 1995-2015 (2/3)
AMMONIA-UREA PLANTS; started-up 1995-2015 (3/3)
World Urea Production
Urea price, (Black Sea), bulk, spot, f.o.b. Black Sea

Month Price Change

Apr 2015 259.00 -
May 2015 253.00 -2.32 %
Jun 2015 292.00 15.42 %
Jul 2015 273.00 -6.51 %
Aug 2015 273.00 0.00 %
Sep 2015 259.00 -5.13 %
Oct 2015 255.00 -1.54 %
Nov 2015 257.00 0.78 %
Dec 2015 239.83 -6.68 %
Jan 2016 214.00 -10.77 %
Feb 2016 209.00 -2.34 %
Mar 2016 203.00 -2.87 %
Apr 2016 204.00
 Schematic Diagram
Of
Ammonia production
 Schematic Diagram of Urea Production

NH₃ :CO₂ = 3.1 - 4.1

T: 170 – 210 C
P: 130 – 240 bar
Rt: 20 – 30 mins

P₁: 17 bar
P₂: 2 bar
Urea (68%)
P₃: -0,35 bar
H20

Urea (99%)
Urea granules going to the bulk storage on the belt convayor
Additional material
Simplified ammonia process flowdiagram
 Simplified urea process flow diagram

atm

U-C-804

H₂SO₄
U-C-201

U-C-501 U-C-662

Steam condensate
NH3

U-P-501
U-V-101
U-R-201
U-V-801 U-C-801
U-A-101 A/B

U-P-102 A/B
U-C-803
U-C-305

CW U-E-804
U-V-102 U-R-101
stm
CO2 stm
U-P-802 A/B
U-T-703
U-P-309 A/B
U-P-705 A/B
U-E-803
AIR U-X-102
U-E-201 U-E-802
U-J-702 U-P-703 A/B
U-J-704
U-E-702
U-V-301 U-E-703
U-P-801 A/B
To Granulation unit
U-C-303 U-E-801

U-E-303
To Polishing unit
U-V-304 U-V-401
U-V-402 U-P-807 A/B CW
U-E-302
U-E-401 U-E-402

U-P-302 A/B U-T-302 UREA MELT

Formaldehyde
TO GRANULATION
U-P-303 A/B U-P-401 A/B
 UREA UNIT - GRANULATION

DUST SCRUBBER

H₂SO₄
steam

RECYCLE EVAPORATION
SEPARATOR
steam

UREA DISSOLVING
VESSEL
HYDROCARBONS – Organic chemistry, chemistry of carbon and hydrogen

Carbon atom C
Hydrogen atom H

Molecyle: - 2 or more atoms

- same or different atoms
- atoms joins together by bonds
- single bond, double bond, triple bond

Simplest hydrocarbon: Methane CH4 (four hydrogen atoms joinded in one carbon atom)

Alkanes: - only single bonds, C – C (ethane)

Alkenes: - at least one double bond, C = C (ethene) (= olefines)
Alkynes: - at least one triple bond, (ethyne)

Forms of hydrocarbons molecules:

1. Straight chain; C – C – C – C - C – C (N-hexane)

2. Branched chain; C – C – C – C - C (Isohexane)
C
3. Ring form; (cyclo) (Cyclohexane)

Functional group gives the name for hydrocarbon:

Aromatics
Alcohols -OH
Ethers -O-
Aldehydes >C=O (Carbonyle)
Amines -NH2
CHEMICAL REACTIONS IN AMMONIUM PRODUCTION:
Catalyst
Sulphur removal:
Hydrogenation RSH + H2 RH + H2S Co/Mo/Al2O3
H2S absorption H2S + ZnO ZnS + H20 ZnO

Steam reforming CH4 + H2O CO + 3 H2 Ni/Al2O3

Shift conversion CO + H2O CO2 + H2 HT: Cu Promoted

Fe/Cr oxide
LT: Zn/Co/Al oxide

CO2 removal MDEA

Methanation CO + 3 H2 CH4 + H2O Ni/Al2O3

CO2 + 4 H2 CH4 + 2 H2O

Ammonia 3 H2 + N2 2 NH3 Fe
synthesis
CHEMICAL REACTIONS IN UREA SYNTHESIS

• Urea is produced by two stage reaction: (1)

• Ammonia and gaseous carbon dioxide react at about

170 – 185 °C and 137 – 147 kg/cm2A

• First reaction is fast and exothermic => Heat recovery

• Second reaction is slow and endothermic

• Overall conversion of NH3 and CO2 is about 78 – 79 %

Unwanted reaction => Biuret formation

• Biuret is injourious to germinating seed

• Also to pine apple and citrus trees when sprayed on the leaf => wither
• Biuret forms almost everywhere in urea production steps
• In fertilizer urea grade biuret content < 1%

• Conditions favourable for biuret formation:

- High residence time
- High temperature
- Low amount of water