CFE 4715: FERTILIZERS, PULP AND PAPER

TECHNOLOGY

Course Instructor:

Md. Shihabuzzaman

Lecturer

Chemical and Food Engineering Department,

DUET
WELCOME
To My Class
Any Idea
????
 FERTILIZER

A chemical or natural substance added to soil or land to increase its fertility (nutrient content)

Primary Nutrients Secondary Nutrients Mircro Nutrients

N Ca B Cu Cl

Zn Mn Mo
P K Mg S

Fe

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Why Fertilizer ??

Nitrogen, phosphorus and potassium are the most important nutrients need to supply because
these are basic building blocks of amino acids, cell membranes and ATP.

 Every amino acid contains nitrogen.

 Every cell's membrane contains phosphorous (the membrane molecules are called
phospholipids), and so does every molecule of ATP.
 Potassium makes up 1 % to 2 % of the weight of any plant and as an ion in cells, is essential
to metabolism

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Specific Function of N, P, K

Nitrogen

Nitrogen is primarily responsible for vegetative growth. Nitrogen assimilation into amino acids is
the building block for protein in the plant. It is a component of chlorophyll and is required for
several enzyme reactions.

Phosphorus

Phosphorus is a major component in plant DNA and RNA. Phosphorus is also critical in root
development, crop maturity and seed production.

Potassium

The role of potassium in the plant is indirect, meaning that it does not make up any plant part.
Potassium is required for the activation of over 80 enzymes throughout the plant. It's important for
a plant's ability to withstand extreme cold and hot temperatures, drought and pests. Potassium
increases water use efficiency and transforms sugars to starch in the grain-filling process.

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 How Minerals Affect Our Health

• Ammonium Nitrate exposure cause other health problems such as eye and skin irritation,
producing a burning sensation. Inhalation exposure can result in irritation of the nose,
throat, and lungs. Also experience with nausea, vomiting, flushing of the face and neck,
headache, nervousness, uncontrolled muscle movements, faintness and collapse.

• Potassium Chloride interferes with nerve impulses, and interrupts with virtually all bodily
functions and mainly affects heart functioning. It can cause all kinds of gastric and
stomach pains, dizziness, bloody diarrhea, convulsions, headaches, mental impairments,
redness or itching of the skin or eyes.

• Cadmium ultimately enters the human tissues resulting in diseases such as tracheo-
bronchitis, pneumonitis, pulmonary edema, renal failure, osteoporosis, and many others.

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Organic Vs Mineral Fertilizer

Characteristics Organic fertilizer Mineral fertilizer

Nitrogen from the air

Crop residues and
Nutrient source and minerals from the
animal manures
soil
Nutrient
Low concentration High concentration
concentration

Immediately available
Nutrient availability Variable
for the crop

Traceable and
Quality Often inconsistent
consistent

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Ammonia Manufacturing Process

Ammonia is under pressure, a liquefied gas, which is recognizable at the smell. It is lighter than air,
and be explosive and flammable under certain circumstances. Ammonia is soluble in water in an
exothermic reaction.

Ammonia has the following physical properties

Density (liquid,20kg/cm2,250C): 603kg/m3

Melting point:-780 °C
Boiling point:-330 °C
Ignition temperature: 6300 °C
Lower explosion limit(in air): 15 vol% ammonia
Upper explosion limit(in air): 29 vol% ammonia
Molecular weight: 17.03

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

Process Block Diagram

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Desulphurization

The Natural gas received at Ammonia plant is divided into two streams namely process natural
gas which is used for producing H2 & CO2 and fuel natural gas that generates heat for primary
steam reforming.

The process natural gas is passed at temperature 3800 °C through Hydrogenator containing
Co-Mo catalyst where organic Sulphur in natural gas is converted into inorganic Sulphur (H2S).

The process gas is then introduced to Sulphur Adsorber containing two beds of ZnO catalyst
where ZnO reacts with H2S producing ZnS & H2O that ensures Sulphur content less than 0.1 ppm
on dry volume basis at the PRF inlet process gas at all times. Generally it is considered that the
natural gas may contain maximum 10 ppm Sulphur by volume.

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Primary Reformer

The treated process gas after mixing with process steam receives heat from process gas &
steam preheater is then passed at temperature 5200 °C through Haldor Topsoe side fired box
type heater catalyst tubes containing NiO catalyst arranged in chambers. The steam reforming
of hydrocarbons is highly endothermic reactions and the necessary heat of reaction for primary
steam reforming is supplied as indirect heat by firing in the PRF furnace. Fuel natural gas & off
gas/flash gas are the heat sources for primary steam reforming. The methane slippage at the
exit of primary reformer (1RF) is about 14.3 mol.% (dry basis) at temperature 778° C.

The steam reforming of Natural gas can be described by the following reactions:
CH4 + H2O = CO + 3H2 - Heat
CO + H2O = CO2 + H2 + Heat

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Catalyst Deactivation/Poisoning

• Sulphur poisoning:
Catalyst poisons act by blocking active surface sites. In addition, poisons may change the atomic surface structure
in a way that reduces the catalytic activity.

• Sintering:
Sintering is the process of agglomeration of the crystallites of the active phase, which leads to loss of active
surface and, consequently, a decrease in activity.

• Oxidation:
Oxidation of the metal particles may occur at a high steam-to-carbon ratio and a low catalyst activity.

• Carbon formation:
At the operating temperatures some of the reactant CHx-species may completely decompose and deposit a thick
layer of inactive carbon on the catalyst surface (coke).
Especially with nickel based catalysts, steam reforming involves the risk of carbon formation, which may cause
serious operational problems and catalyst deactivation.
Generally, higher hydrocarbons are more prone to carbon formation than methane.

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Secondary Reformer

Operating condition:Temperature-550°C-950°C
Pressure-32.2 kg/cm2G
Catalyst: Nickel

The reformer is a refractory-lined vessel, filled with nickel catalyst.

A controlled proportion of air is also introduced after pre heating into the reformer.
In the upper hollow space of the reformer, a highly exothermic reaction between hydrogen
and oxygen takes place which raising its temperature high enough to virtually complete the
conversion of the residual methane into additional hydrogen, carbon dioxide and carbon
monoxide.
Secondary reformer outlet gas at 950°C passed through waste heat boiler and super heater
and then reformed gas with 0.4-0.6% methane is exposed to shift reaction.

Reactions :
H2+ O2→ 2H2O
CH4 + O2→ 2H2O + CO2/CO
CH4+ H2O → CO + 3H2
CH4+ 2H2O → CO2+ 4H2

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 High Temperature Shift

Shift Reaction:

CO + H2O = CO2 + H2 + Heat

Process gas leaving SRF flows through exchangers to reach a temperature of about 360°C The
process gas is then introduced to HTS containing promoted iron oxide catalyst that reduces
CO content from 12.45 mol.% to 2.84 mol% (dry basis). As the reaction is exothermic, therefore,
the temperature rises across the catalyst bed. The equilibrium of the shift reaction is favored
by lower temperature and more water while the reaction rate will be higher at higher
temperature.

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Low Temperature Shift

The process gas at the exit of HTS is passed through exchangers in order to achieve
temperature about 210 °C at LTS inlet by heat transfer to the mentioned Exchangers. The
process gas is then introduced to LTS having two beds of catalyst containing oxides of Copper,
Zinc& Chromium on top and oxides Copper, Zinc & Aluminum on bottom that reduces CO
content about 0.28 mol.% (dry basis).

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET

 Shift Conversion Summary

HTS

Operating Condition: Temperature-350°C-420°C

Pressure-32.2 kg/cm2G
Reaction: CO + H2O = H2+ CO2
Catalyst: Iron oxide
CO content: 13% to 3%

LTS

Operating Condition: Temperature-220°C-260°C

Pressure-31.2 kg/cm2G
Catalyst: CuO+ ZnO
CO content: 3% to <0.3%

Md. Shihabuzzaman Apon, Lecturer, CFE Department, DUET