Basic Unit Operations

Absorption
The removal of one or more selected components from
a mixture of gases into a suitable liquid. Examples:
 Removal of CO2 and H2S from natural gas or synthesis gas by absorption in
solutions of amines or alkaline salts.
 Washing of ammonia from a mixture of ammonia and air by means of liquid
water.
The solute is subsequently recovered from the liquid by
distillation, and the absorbing liquid can be either discarded
or reused.
*Sometimes a solute is removed from a liquid by
bringing the liquid into contact with an inert gas; such an
operation, the reverse of gas absorption, is desorption or
gas stripping.
Adsorption
The selective removal of components from a
gaseous or liquid mixture using small particles
of a porous solid.
In adsorption, the adsorbent is usually held in
a fixed bed, and fluid is passed continuously
through the bed until the solid is nearly
saturated. The flow is then switched to a
second bed, and the saturated bed is replaced
or regenerated.
Distillation:
 The separation of liquid mixtures into their several components.
 It is one of the major operations in the chemical and petroleum industries.
Evaporation:
  Evaporation is one of the main methods used for the concentration of aqueous
solutions. It refers to the removal of water from a solution by boiling the liquor in a
suitable vessel called the evaporator, and withdrawing the vapour.

 If the solution contains dissolved solids, the resulting strong liquor may become
saturated so that crystals are deposited.

Drying:
Drying refers to the final removal of water immediately prior to
packaging or dispatch. This operation often follows evaporation,
filtration, or crystallization. In most cases, drying is carried out for one or
more of the following reasons:
 To reduce the cost of transport.
 To make a material more suitable for handling, for example, soap powders,
dyestuffs, fertilizers.
 To provide definite properties, such as maintaining the free-flowing nature of salt.
 To remove moisture which may otherwise lead to corrosion, for example, the
drying of coal gas or of benzene prior to chlorination.

Crystallization:
Crystallization is the formation of solid
particles within a homogeneous phase. It may
occur as the formation of solid particles in a
vapor, as in snow; as solidification from a liquid
melt, as in the manufacture of large single
crystals; or as crystallization from liquid
solution. Crystallization from solution is
important industrially because of the variety of
materials that are marketed in the crystalline
form.
Introduction to Chemical Fertilizers:
Plants require nutrients for growth and
development. C, H, O are provided by air
and water while the remaining elements
are provided by the soil. N, P, K are called the
primary nutrients.
When soil nutrients are missing or present in
short supply (e.g. due to excessive farming),
plants suffer from nutrient deficiency.
Substances which must be added to the soil in
order to remove the deficiency of essential
elements required for plant growth are called
fertilizers.
Need for Fertilizers:
 To supplement what has been eaten up by the plants
 To supply them an additional tonic and good food, so that they may grow more
health and produce a better yield.
 To maintain the pH of the soil in the vicinity of 7-8 and thereby facilitate optimum
growth and health.
Chief Requisites of a Fertilizer:
 The element present in the compound must be easily available to the plant.
 The substance must be soluble in water.
 It should be stable, so that it may be made available to the plant for a long time.
 It should not be very costly.
 It should maintain the pH of the soil in the vicinity of 7 to 8.
 It should not be a poison for plant.
Nitrogenous Fertilizer:
Soil takes up the nitrogen in the form of ammonium or nitrate ions and forms
amino acids and carbon compounds in the complex chemical system in the plant.
These amino acids are then converted into proteins and enzymes.
Important commercial nitrogenous fertilizers are nitrates of sodium, calcium and
potassium, ammonium sulphate, calcium cyanamide, ammonium nitrate and
urea.
Based on the form of nitrogen, nitrogenous fertilizers are divided into ammonia
(containing nitrogen as NH4+ ion), nitrate (containing nitrogen as NO3- ion),
ammonia-nitrate (containing both NH4+ and NO3- ions), and amide
(containing nitrogen as NH2) fertilizers.
Properties of Ammonia:
 Chemical Formula: NH3
 Molar Mass: 17.031 g/mol
 Appearance: Colorless Gas
 Odor: Strong Pungent Odor
 Melting Point: -77.73°C
 Boiling Point: -33.34°C
Ammonia Production:
The manufacture of ammonia is carried out by passing a
mixture of pure hydrogen and nitrogen in the proportion of
3:1 by volume under pressure over a catalyst heated to
an optimum temperature.
This method was first developed by Haber and Bosch and is
therefore known as the Haber and Bosch process.
N2 + 3 H2 ⇌ 2 NH3 (ΔH° =−45.8 kJ·mol−1)
This reaction is reversible, exothermic and
proceeds forward with a decrease in volume.
Raw materials:
Nitrogen necessary for producing the
nitrogen-hydrogen mixture is derived from
the air by:
 Physical separation of air into nitrogen and oxygen – Liquefaction of air.
 Obtaining the nitrogen together with the necessary amount of hydrogen through
combining all the oxygen of the air into CO2 and then separating the CO2 from the
nitrogen-hydrogen mixture.
Hydrogen required for commercial
ammonia synthesis can be obtained by:
 Reforming of methane in natural gas, or its homologues, followed by conversion
of the CO formed.
CH4+2H2O ⇌ CO + 4H2
 Conversion of carbon monoxide in water gas or semi-water gas, obtained by
gasifying solid or liquid fuels.
 Separation of coke-oven gas by liquefying in succession all the components of
the gas mixture, except hydrogen.
 Electrolysis of water and sodium chloride solutions.
The process of ammonia synthesis is most frequently performed from a
nitrogen-hydrogen mixture that is usually prepared by the conversion of CH4
and CO with steam and the oxygen of the air.
Ammonia Synthesis:
Step 1:
Gas Purification/Desulfurization:
The catalysts used in the conversion of CH4, the
conversion of CO and the synthesis of ammonia are
poisoned by the impurities usually present in the gas
mixture. H2S and organic Sulphur compounds are
especially strong poisons for catalysts. Thus,
purification is highly required.
Note: In natural gas being fed to the catalyst for
CH4 reforming, the Sulphur content should not
exceed 2.0 milligrams per cu. m.
  Conversion of organic sulfur into
inorganic form by hydrogenation over a
cobalt-molybdenum catalyst at 350-
450°C:
RSH+H2→ H2S+RH
 The H2S formed can be
removed using adsorbents
such as Zinc Oxide, Activated Charcoal,
Ferrous Hydroxide:
ZnO + H2S → ZnS + H2O
Step 2:
Hydrogen Production in Primary Reformer
:
Natural gas from the desulfurizer goes to the primary
reformer for steam reforming. Super-heated steam is
fed into the reformer with the methane. The gas
mixture is heated with natural gas to around 770°C in
the presence of a nickel catalyst:
CH4 + H2O ⇌ 3H2 + CO
CH4 + 2H2O ⇌ 4H2 + CO2
CO + H2O ⇌ H2 + CO2
This gaseous mixture is
known as synthesis gas.
Step 3:
Nitrogen Addition in Secondary Reformer
The synthesis gas flows to the secondary
reformer where it is mixed with a calculated
amount of air. The highly exothermic reaction
between oxygen and methane produces
more hydrogen:
CO + H2O ⇌ CO2 + H2
O2 + 2CH4 ⇌ 2CO + 4H2
O2 + CH4 ⇌ CO2 + 2H2
2O2 + CH4 ⇌ 2H2O + CO2
Step 4:
Removal of Carbon Monoxide in Shift Converter:
Here the carbon monoxide is converted to
carbon dioxide (which is used later in the
Synthesis of urea) in a reaction known as
the water gas shift reaction:
CO + H2O ⇌ CO2 + H2
Removal of CO is achieved in two steps:
 HTS (High Temperature Shift Conversion)
Firstly, conversion of CO to CO2 in presence
of iron based catalyst at 360°C.
 LTS (Low Temperature Shift Conversion)
Later on, the conversion continues over a
copper based catalyst at 210°C.
The same reaction occurs in both steps,
but using the two steps maximizes conversion.
Step 5:
Removal of Carbon Dioxide by Absorption and Stripping:
After conversion, the gas mixture is passed
to the CO2 recovery section. CO2 is absorbed in the
absorber through a counter-current solution of
liquid sorbents such as ethanolamines, alkaline
solutions, etc. Benfield solution is one of the
well known absorbent solutions containing:
K2CO3 → 29~30% (K2CO3 +CO2 +H2O →2KHCO3,
V2O5 →0.7% (Corrosion Inhibitor),
DEA →2~3% (Promoter),
H20

Benfield/UCARSOL solutions are the names

used in industry for absorbent solutions in
CO2 removal. UCARSOL is an MDEA (Methyl
Diethanolamine) solution while Benfield, as
we know, is a solution of K2CO3. The CO2 is
first absorbed into the absorbents and
then stripped from the absorbent solution
to be used in urea manufacture.
(Industrial Chemistry – pg 738 reactions)
Step 6:
Methanation:
 In order to prevent catalyst poisoning in the reactor, any remaining CO and CO2
in the gaseous mixture are reduced further catalytically in the Methanator using a
Ni/Al2O3 catalyst at 200-400°C.
CO + 3H2 ⇌ CH4 + H2O
CO2 + 4H2 ⇌ CH4 + 2H2O
Step 7:
Compression and Cooling:
 The outlet stream from methanator contains mainly N2,H2 and trace amounts of
H2O(g), CH4, Ar. The gas mixture is now cooled, compressed and fed into the
ammonia synthesis loop. Cooling enables the water to become liquid that can be
easily removed.
Step 8:
Ammonia Synthesis:
 The incoming gas stream is mixed with unreacted gases which have already
been around the loop and cooled to 5°C.
 The ammonia present is removed and the unreacted gases heated to 400°C at a
pressure of 330 barg and passed over an iron catalyst.
 Under these conditions 26% of the hydrogen and nitrogen are converted to
ammonia. The outlet gas from the ammonia converter is cooled to 30°C. This
cooling process condenses more than half the ammonia, which is then separated
out.
Step 9:
Decompression:
 The ammonia is rapidly decompressed to 24 barg. At this pressure, impurities
such as methane and hydrogen become gases. The gas mixture above the liquid
ammonia (which also contains significant levels of ammonia) is removed and
sent to the ammonia recovery unit. This is an absorber-stripper system using
water as solvent. The remaining gas (purge gas) is used as fuel for the heating of
the primary reformer.
Basic conditions for high productivity and stable operation of ammonia synthesis
units are:
 Effective purification of nitrogen-hydrogen mixture to remove catalyst poison and
inert admixtures.
 Maintaining the N2:H2 ratio close to 1:3.
 Optimum temperature conditions over the length of the catalyst zone.
  A low ammonia content at the inlet to the catalyst reactor.
 A well designed converter or synthesis tower.
Design considerations:
 Objective of development in design: Aim is to lower consumption of energy,
materials and capital investments, and to attain a low cost product and high
labour productivity. For example: Utilization of heat from the gas-combustion
products and gases from the converters used to produce steam that drives the
turbine that powers the compressors.
 STEAM/ CARBON SENSITIVITY
 Primary reformer inlet steam-to-carbon (s/c) ratio is an important factor in
reformer design. The literature advises the maintenance of a relatively high s/c
ratio to prevent mechanical as well as economic problems during the life of the
plant. Higher s/c ratios are more effective for a number of reasons:
First, because a high s/c ratio favors the products in the reforming reaction equilibrium,
it lowers the amount of unreacted methane, or methane slip, out of the secondary
reformer and increases the production of hydrogen.
Second, a high s/c ratio inhibits the occurence of carbon-forming side reactions in the
primary reformer that result in carbon deposits on the catalyst. Carbon deposition
increases the resistance to gas flow in the primary reformer tubes and may impair
catalyst activity. This impairment lowers the rate of the reforming reaction and can
cause local overheating or "hot bands" in reformer tubes that result in premature tube
wall failure.
Finally, a high s/c ratio provides the necessary steam for the shift conversion of carbon
monoxide and reduces the risk of carburization damage to the tube material.