Amity Institute of Nanotechnology

NANO-AGROCHEMICALS IN CROP MANAGEMENT

1
 Amity Institute of Nanotechnology

• Agriculture also known as “farming”

• Climate change, energy and resource
constraints, and rapidly growing global
population
• Necessity of modern technologies such as
nanotechnology

2
 Amity Institute of Nanotechnology

• Nanoformulations of agrochemicals
• Application of nanosensors/nanobiosensors
• Nanodevices for the genetic manipulation
of plants
• Plant disease diagnostics
• Animal health, animal breeding, poultry
production; and
• Postharvest management.

3
 Some successful ventures of nanotechnology in agriculture

Product Application Amity Institute of Institution*

Nanotechnology
Nanocides pesticides encapsulated in nanoparticles for controlled release BASF

nanoemulsions for greater efficiency Syngenta

Bucky ball ammonia from buckyballs Kyoto Univ, Japan
fertilizer
Nanoparticles Adhesion-specific nanoparticles for removal of Campylobacter Clemson Univ.
jejuni from poultry

Food packaging airtight plastic packaging with silicate nanoparticles Bayer

Use of agri- nanofibres from cotton waste for improved strength of clothing Cornell univ
cultural waste

Nano-sensors contamination of packaged food Nestle, Kraft

pathogen detection Cornell Univ
Precision nanosensors linked to GPS for real-time monitoring of soil USDA
agriculture conditions and crop growth
Live stock and nano-veterinary medicine (nanoparticles, buckyballs, dendrimers, nanocapsules for Cornell Univ,
drug delivery, nanovaccines; smart herds, cleaning fish ponds (Nanocheck); feed
fisheries (iron nanoparticles) Nanovic, Australia
 Amity Institute of Nanotechnology

• Nanotechnology in agriculture – a
castle in the air
• It works, If scientists working on
basic sciences put foundation beneath
 Amity Institute of Nanotechnology

Manure: organic, bulky, no definite composition

Classification of Manures: Bulky and concentrated

Fertilizer: inorganic , Non bulky , definite chemical

composition

6
 Amity Institute of Nanotechnology

• A commercial fertilizer : a material

containing at least one of the primary
nutrients in assemble or available form to
plants in known amounts
• Elements essential for plant growth:
Macronutrients: N, P, K, Ca, Mg and S
Micronutrients : Fe , Zn ,Cu ,Mn , Mo, B
,Cl, etc.,
Primary nutrients: N, P and K
Secondary nutrients: Ca, Mg and S
7
 FERTILIZERS

Fertilizer is any material of natural or synthetic origin added to the soil

to supply one or more plant nutrients.

CLASSIFICATION OF FERTILIZERS

Fertilizer
 Category of Fertilizer

1. Straight fertilizers 2. Complex fertilizers 3. Mixed fertilizers:

Straight Complex Physical

fertilizers are those fertilizers contain two or mixtures are straight

which supply only one three primary plant fertilizers. They

nutrients of which two contain two or three
primary plant nutrient,
primary nutrients are in primary plant nutrients.
namely nitrogen or
chemical combination. Mixed fertilizers are
phosphorus or
These fertilizers made by thoroughly
potassium. E.g. Urea,
are usually produced in
ammonium sulphate, mixing the ingredients
granular form e.g.
potassium chloride either mechanically or
Diammonium phosphate,
and potassium manually.
nitrophosphates and
sulphate.
ammonium phosphate.
Fertilizers can also be classified based on physical form

Liquid fertilizers
Solid fertilizers
Solid fertilizers are in several forms:
• Powder (single superphosphate)
• Crystals (ammonium sulphate)
•Prills (urea, diammonium phosphate,
superphosphate),
• Granules (Holland granules)
• Supergranules (urea supergranules)
• Briquettes (urea briquettes).

Urea prills Ammonium sulphate Granulated urea

Liquid fertilizers
Liquid form fertilizers are applied with irrigation water or for application.
Ease of handling, less labour requirement and possibility of mixing with
herbicides has made the liquid fertilizers more acceptable to farmers.

TYPES OF FERTILIZERS

Fertilizer
Nitrogenous fertilizers
More than 80 per cent of the fertilizers used in this country are made up
of nitrogenous fertilizers, particularly urea.

Ammoniacal Nitrate Ammoniacal and Amide fertilizer

[NH4+] [NO3-] Nitrate [-NH2]
Ammoniumm Sodium Nitrate Ammonium Nitrate Urea
Sulphate Calcium Nitrate Calcium Ammonium Nitrate Calcium Cynamide
Ammonium chloride Potassium Nitrate Ammonium Sulphate Nitrate
Anhydrous
ammonia
 Amity Institute of Nanotechnology

Ammonical fertilizers

• Ammoniacal fertilizers contain the nutrient nitrogen in the form of

ammonium or ammonia.
• These fertilizers are resistant to leaching loss, as the ammonium ions
get readily absorbed on the colloidal complex of the soil.

14
 Amity Institute of Nanotechnology

AMMONIA: 1913 by FRITZ HABER and CARP

BOSCH , Germany

- By passing N2 and H2 mixture (1:3 mole ratio)

over an activated iron oxide catalyst.
- This process is carried out in a typical NH3
synthesis reactor . It is a steel cylinder of 80-140
cm diameter and 10-18 meters height, provided
with a catalyst container which helps for
dissipating the heat expelled.
15
Amity Institute of Nanotechnology

16
 Amity Institute of Nanotechnology

Raw materials:
I) Water
II) Natural gas :Natural gas is a mixture of gases viz.,
methane ,ethane ,butane , propane ,pentane and CO2 etc.,
About 64 % of ammonia produced in the world is from natural
gas .
III) Naphtha :The light distillate fraction of petroleum with a
maximum boiling point (B.P.) of 215 oC is called Naphtha,
which is produced during the refining of crude oil .Naphtha
contains hydrocarbons such as a) paraffin (79%) b) Olefins
(1.0%) c) Naththanes(14 %) d) aromatics (6%) .It has C:H
ratio by weight around 5.48 .About 75% of nitrogen produced
in India utilizes NAPHTHA.

17
 Amity Institute of Nanotechnology

IV) Fuel oil ( or) Heavy petroleum products:

products obtain from primary distillation and
cracking of crude oil .Example : low sulphur
heavy stock (LS HS) and heavy sulphur heavy
stock (HS HS)
v) Coal : contains hydrogen gas varying from 4.5
to 6.0 % by weight
Vi) Coke oven gas : Coke oven gas consists of
gases (%) H2 (52.6), CH4 (28.9), CO(7.5) CO2
(3.5) and produced during coal carbonization in
steel industry
18
a) Ammonium sulphate [(NH4)2 S04]
• It is a white salt completely soluble in water containing
20.6 per cent of nitrogen and 24.0 per cent of sulphur.

• It is used advantageously in rice and jute cultivation.

• It is easy to handle and it stores well under dry conditions.

But during rainy season, it sometimes forms lumps.

• It can be applied before sowing, at the time of sowing or as

a top-dressing to the growing crop.
 Amity Institute of Nanotechnology

• AMMONIUM SULPHATE [(NH4)2 SO4 ] :

By product process : [Raw materials Coal and Sulphuric acid ]

2-3 kg of ammonia

20
 Amity Institute of Nanotechnology

• Neutralization process: [Raw materials: NH3 and H2SO4]

2NH3 (g)+H2SO4(liquid ) = (NH4)2SO4 (salt) +67.710 k.cal
/gram mole

21
 Amity Institute of Nanotechnology

• Gypsum process or leuna

process: (Raw materials :
NH3 ,CO2 and Gypsum )
NH3 +H2O= NH4OH +
8.32K.Cal/g.mole
2 NH4OH +CO2 = (NH4)CO3 +
H2O +22.08 K Cal /g.mole
(NH 4)CO3 + CaSO4 2H2O
=(NH4)2SO4 + CaCO3 +2
H2O+ 3.9K Cal/g.mole

22
Amide fertilizers
Amide fertilizers are readily soluble in water and easily
decomposable in the soil.

Urea [CO (NH2)2]

It is the most concentrated solid nitrogenous fertilizer, containing 46
per cent nitrogen.

It is a white crystalline substance readily soluble in water.

 Amity Institute of Nanotechnology

UREA [Carbamide (NH2CO NH2)]

- nearly 91 per cent of the total production
of nitrogen in India
- Raw materials : Ammonia and Carbon
dioxide
- F. Wholer (German chemist ),first
prepared urea in the year 1828
[Commercial production started in 1922]
- by dehydration of ammonia carbamate
24
 Amity Institute of Nanotechnology

-reactor
-a carbamate strippers

25
Amity Institute of Nanotechnology

26
Amity Institute of Nanotechnology

27
 Amity Institute of Nanotechnology

Chemical properties:
• Synthetic protein, organic compound,
richest source of N (46%) in amide form
among solid N fertilizers
• Soluble in water and solubility is 100 g
/100 g of water at 20oC
• Biuret content is about 1.5 per cent by
weight
• identical to urea found in animal urine.
28
 Amity Institute of Nanotechnology

What happens when urea is applied to soil?

29
Phosphatic fertilizers
• chemical substances that contain the nutrient
phosphorus in absorbable form (Phosphate
anions,PO43−) or that yield after conversion in the soil.
• raw material of P-fertilizers are essentially rock
phosphates

• In India phosphate rock deposits have been found in

Udaipur in Rajasthan and Mussoorie in Uttaranchal .
Some deposits occur in Singbhum district (Bihar)
,Jhabhua district (M.P) , Visakhapatnam district (AP)
,Tiruchanapalli (TN)
 Amity Institute of Nanotechnology

- Classification of phosphatic fertilizers based on

relative solubility of phosphate
a)Water soluble-P in form of mono calcium
phosphate , Ca(H2PO4)2
1. Single super phosphate (16-18% P2O5)
2. Double super phosphate (32 % P2O5)
3. Triple super phosphate (46-48% P2O5)

31
 Amity Institute of Nanotechnology

b) Citrate soluble –
- P in soluble in 2% citric acid or neutral normal
ammonium acetate solution.
- P is present as dicalcium phosphate
Ca2H2(PO4)2
- Examples
1.Basic slag (14 to 18% P2O5)
2.Dicalcium phosphate (34-39 % P2O5)
- suitable for the acidic soils, because with low pH
citrate soluble phosphoric acid gets converted

32
 Amity Institute of Nanotechnology

C) Water and citrate insoluble phosphorus

fertilizers :
Phosphorus present in the fertilizer is not
soluble both in water and citrate solution
containing insoluble phosphoric acid or tri
calcium Phosphate (Ca3(PO4)2
1)Rock phosphate (20 to 40 % P2O5)
2)Raw bone meal (20 to 25% P2O5)
3)Steamed bone meal (22% P2O5)
33
 Amity Institute of Nanotechnology

Production of phosphate fertilizers:

1)Thermal methods
2)Chemical methods using H2SO4 or other
acids
3)Combination of above two methods

34
Single Super phosphate [Ca (H2PO4)2)
This is the most important phosphatic fertilizer in use.

It contains 16 % P2O5 in available form.

It is a grey ash like powder with good keeping or storage qualities.

Phosphatic fertilizer hardly moves in the soil and hence they are
placed in the root zone.
Ground Rock Phosphate
 Amity Institute of Nanotechnology

SINGLE SUPER PHOSPHATE

• J.B. LAWES from ENGLAND prepared first time
in 1842
- Raw materials: Phosphate rock and Sulphuric
acid
- Continuous rock acidulation with sulphuric acid
is done continuously in mixer provided with
indigenous metering (H2SO4) and weighing (RP)
devices

37
There are two methods of preparation of SSP viz.,
i. Den process
ii. Continuous rock phosphate acidulation process

Den Process:
• Weighed quantities of Rock phosphate(0.14mm) and sulphuric acid
(75% ) are mixed in a mixer (capable of handling 40-50 tonnes per
hour)
• Mix is allowed to react for about a minute and the resultant slurry is
dumped into a compartment known as DEN (100-300 tonnes
capacity)
• In a few hours the reaction goes to completion .
• Water ,carbon dioxide ,fluorine ,volatilize away resulting in the
reduction in the bulk of the material
• By retaining the material in the Den becomes a hard block and
removal is accomplished by means of mechanical excavators
equipped with revolving knifes which cut into the block and the
disintegrated SSP is stored for 2 to 6 weeks to cure and attain the
desired physical condition .
 Amity Institute of Nanotechnology

Continuous rock phosphate acidulation process

39
Triple super phosphate:

• It contains 46 per cent P2O5.

• This fertilizer is suitable for all crops and all soils.
• In acid soils, it should be used in conjunction with organic manure.
• It can be applied before or at sowing or transplanting.
 Amity Institute of Nanotechnology

• Raw materials : Rock phosphate and

Phosphoric acid
• CONE MIXER PROCESS:
Ca 10 [PO4]6 F2 +14 H3 PO4 +10H2O = 10
CaH4(PO4)2 H2O +2HF

41
 Amity Institute of Nanotechnology

CONE MIXER PROCESS 42

Potassic fertilizers
There are a limited number of fertilizer materials that can be used to
supply K when needed.

Common fertilizer sources of K

Material Chemical Formula K2O Contend(%)

Potassium chloride KCl 60

Potassium-magnesium sulfate K2SO4-2MgSO4 20

Potassium nitrate KNO3 44

Potassium sulfate K2SO4 50

 Amity Institute of Nanotechnology

• Taken up by the plant as K+

• Does not form organic compounds in the
plant
• Is vital to photosynthesis and protein
synthesis
• Is associated with many metabolic
functions
• Essential role for regulating leaf stomata
and controlling water use

44
a)Potassium chloride (KCl)
• Potassium chloride or muriate of potash is a white or red, crystal
containing 60.0 per cent K2O.

• It is completely soluble in water and therefore readily available to

the crops.

• It is not lost from the soil, as it is absorbed on the colloidal

surfaces.

• It can be applied at sowing or before or after sowing.

 Amity Institute of Nanotechnology

• Where Does Potash Come From?

All commercial potash deposits come from
marine sources:
1. Ancient seas that are now buried
2. Salt water brines
Sylvinite is a sedimentary
rock made of a mechanical
mixture of the
minerals sylvite (KCl, or
potassium chloride)
and halite(NaCl, or sodium
chloride)

46
Amity Institute of Nanotechnology

47
 Amity Institute of Nanotechnology

Crystallization
• The process to make pure and totally
soluble KCl
• Hot-process: KCl.NaCl is dissolved in
boiling water to dissolve NaCl and KCl.
As the hot brine cools, salts differentially
crystallize and are removed from solution.
• Cold process: KCl solubility is lower in cold
temperatures than Na and Mg salts,
allowing crystallization and separation
48
 Amity Institute of Nanotechnology

1.starch or mannogalactan gums

49
Amity Institute of Nanotechnology

50
Micronutrient Fertilizers
• The importance of fertilization of crops with micro-nutrients is
increasing mainly because of greater removal from the soil, intensive
liming of soil, intensive drainage of soil, higher use of nitrogenous,
phosphatic and potassic fertilizers etc.
• There are seven essential micronutrients required by plants - iron,
manganese, zinc, copper, chlorine, boron and molybdenum.
lron fertilizers
• These are generally water-soluble substances, predominantly
sprayed as foliar nutrients on the crops.
• Plants absorb iron in the form of Fe2+
• Ferrous sulphate (FeSO4 7H2O) : water-soluble fertilizer containing
20 % Fe
• Fe Chelates ( Fe-EDTA and Fe-EDDPA) : Suitable for application
as foliar nutrients
 Manganese fertilizers

ManganousSulphate It is the well-known water-soluble Mn fertilizer.

( MnSO4 7H2O) It is pink salt containing 24 % Mn.
It dissolves in water and is suitable for foliar
application.
Mn – chelates (Mn – DTA) It contains 13 % Mn.
It plays an important role in the crop fertilization.
 Zinc fertilizers: play an important role in Zn deficient soil

Zincsulphate • water soluble whitish salt containing 23

(ZnSO4 7H2O) % Zn.
• applied as foliar nutrient
• acidic action causes corrosion damage
to plants
Zinc-oxide(ZnO) • contains 70 % Zn.
• slightly soluble in water
• used as slow acting foliar nutrient
Copper Fertilizers
Copper fertilizers have been used to correct copper (Cu),deficiencies.
Copper sulphate (CuSO4 5H2O) – 25 % Cu
Copper sulphate (CuSO4 H2O) – 36 % Cu

Boron Fertilizers
Borax • contains 11 % B
(Na2B4O 10H2O) • water soluble white salt
• can be applied as a soil dressing or foliar
application
Boric acid (H3BO3) • contains 18 % B
• a white crystalline powder
• applied as a foliar nutrient
Molybdenum Fertilizers

Sodium It contains 40 % Mo
molybdate
(Na2MoO 42H2O)
Ammonium It contains 54 % Mo
molybdate
(NH4)6Mo7O2 44H2O)
 Sources and Forms of Fertilizer

To Sum up

• Fertilizers are available in both organic as well as inorganic forms.

• They are classified as straight, complex and mixed fertilizers.
• They can also be classified into solid and liquid fertilizers.
• Fertilizers are applied to supply nutrients required by the crop that
are taken up from the soil.