Ministry of Higher Education and

Scientific Research
Al-Muthanna University
Engineering College
Chemical Engineering Department

Controlling of Absorber column in

the production of Nitric acid

Prepared By: Shakir Saad Isewid

Class: Fourth Stage

Subject: Process Control

Supervisor: Dr. Forat Yasir AlJaberi

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Table of Contents

1.0 INTRODUCTION 2

1.1 PROPERTIES 3

1.2 USES 4

1.3 METHODS OF MANUFACTURE 5

1.4 ABSORPTION OPERATION 13

1.5 PROCESS OPERATION 13

REFERENCES 22

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 NITRIC ACID

1.0 Introduction

Nitric acid (HNO3), also known as aqua fortis (strong water) and spirit of
niter, is a highly corrosive strong mineral acid. The pure compound is colourless,
but older samples are yellowish in colour due to the accumulation of oxides of
nitrogen. Commercially available nitric acid having concentration of 68% HNO3,
while the solution containing more than 86% HNO3, is referred to as fuming nitric
acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is
further characterized as white fuming nitric acid or red fuming nitric acid, at
concentrations above 95%.

First Nitric acid was mentioned in Pseudo-Geber's De Inventione Veritatis

which is prepared by calcining a mixture of saltpetre (Niter KNO3), alum and
sulfuric acid. Also, described by Albertus in the 13th century and by Ramon Lull,
who prepared it by heating niter and clay and called as "eau forte" (aqua fortis).

Glauber invent the process to obtain HNO3 by heating niter with strong
sulfuric acid. In 1776 Lavoisier showed that it contained oxygen, and in 1785
Henry Cavendish determined its precise composition and synthesized it by passing
a stream of electric sparks through moist air.

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1.1 PROPERTIES

Physical Properties

 Molecular formula: HNO3

 Molecular weight: 63.013gm/mole
 Appearance: Colorless liquid
 Odor: Pungent
 Boiling point: 121℃ (68% HNO3 solution)
 Melting point: -42 ℃
 Density: 1.5129gm/mL (liquid)
 Solubility: Miscible with water in all proportions
 The impure nitric acid is yellow due to dissolved oxides of nitrogen, mainly
NO2.
 It has a corrosive action on skin and causes painful blisters.

Chemical Properties

 Acidic properties: It is a strong monobasic acid and ionization in aqueous

solution.
 Oxidizing properties: It acts as a powerful oxidizing agent, due to the
formation of nascent oxygen.
 Action on metals: It reacts with almost all the metals, except noble metals,
like Pt and Au. The metals are oxidized to their corresponding positive metal
ions while HNO3 is reduced to NO, NO2. N2O, NH2OH or NH3, depending
upon the conditions such as temperature, nature of metal and concentration
of the acid.
 Nitric acid has ability to separate gold and silver.

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1.2 Uses
 As a starting material in the manufacture of nitrogen fertilizers such as
ammonium nitrate, ammonium phosphate and nitrophosphate. Large
amounts are reacted with ammonia to yield ammonium nitrate.
 Weak acid are used to digest crude phosphates.
 As a nitrating agent in the preparation of explosives such as TNT,
nitroglycerine, cellulose polynitrate, ammonium picrate.
 In manufacture of organic intermediates such as nitroalkanes and
nitroaromatics.
 Used in the production of adipic acid.
 Used in fibers, plastics and dyestuffs industries
 Used in metallurgy and in rocket fuel production
 As the replacement of sulfuric acid in acidulation of phosphate rock

1.3 Methods Of Manufacture

Nitric acid is manufactured by three methods.

1. From Chile saltpetre or nitrate
2. Arc process or Birkeland and eyde process
3. Ostwald's process or Ammonia oxidation process

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3. Ostwald's process or Ammonia oxidation process
Raw Materials
Basis: 1000kg nitric acid (100%)
Ammonia = 290kg
Air = 3000Nm3
Platinum = 0.001kg
Water = 120000kg
Steam credit 1000kg @ 200psig
Power = 10-30KWH

Reactions
Major Reactions:

Side reactions

Nitrous oxide oxidation and absorption

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Manufacture
Nitric acid is made by the oxidation of ammonia, using platinum or platinum- 10%
rhodium as catalyst, followed by the reaction of the resulting nitrogen oxides with
water.

The process involves four steps:

1. Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen
monoxide
2. Oxidation of the nitrogen monoxide product to nitrogen dioxide or dinitrogen
tetroxide
3. Absorption of the nitrogen oxides to yield nitric acid
4. Concentration of nitric acid

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 Compressed air is mixed with anhydrous ammonia, fed to a shell and tube
convertor designed so that the preheater and steam heat recovery boiler-super
heater are within the same reactor shell. The convertor section consists of 10-30
sheets of Pt-Rh alloy in the form of 60-80 mesh wire gauge packed in layers inside
the tube. Contact time and of the gas passes downward in the catalyst zone 2.5 X 10-
4
sec and are heated at 800 ℃.

Product gases from the reactor which contain 10-12% NO, are sent through
heat recovery units consisting of heat recovery boiler, super heater and quenching
unit for rapid cooling to remove large fraction of product heat, and into the oxidizer
absorber system. Air is added to convert NO to NO2 at the more favourable
temperature (40-50 ℃) environment of the absorption system. The equipment in
the absorption train may be series of packed or sieve tray vertical towers or a series
of
horizontal cascade absorbers. The product from this water absorption system is 57-
60% HNO3 solution which can be sold as or concentrated as follows

Concentration by H2SO4

Rectification with 93% H 2SO4 (660Be) in silicon-iron or stoneware tower

produces concentrated nitric acid and 70% H2SO4 which can be re-evaporated to
93% H2SO4 or used as it is.

Concentration by Mg(NO3)2

Magnesium nitrate solution containing 70-75% Mg(NO3)2 is fed to

dehydrating tray along with dilute HNO3 from the absorption tower. The salt
solution acts as an extractive distillation agent, removing water at 1000C or higher,

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thus allowing rectification with azeotropic formation. The dilute Mg(NO3)2 solution
re-concentrated by evaporation.

Advantages
 Operating cost is half compare to H2SO4 process
 Acid quality and yield improved

Disadvantage
 Increase in 70% capital expenditure

Engineering aspects

Thermodynamics and kinetics

All the above exothermic reaction takes place in more or less extent. Reaction
12 and 13 occurs with decrease in enthalpy with increase in number of moles
followed by increase in entropy.

Ammonia oxidation reaction has an extremely favourable equilibrium

constant so that one step, high temperature converter design may be used.

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 Further, ammonia air mixture exhibit explosion limits. At STP it is 15.6%
ammonia, while temperature above 600 ℃and 1atm pressure, the limit is lowered
to 10.5%

The following condition should be fulfilled to convert NH3 into NO

 Explosion limit
The explosion limits are avoided by employing quantity of air such that the
amount of ammonia mixed with it is less than 10.5vol% of total volume.
 Thermodynamics
The thermodynamics of competing reactions (12) and (13) are rendered
unfavorable by working above 500 ℃, while the reaction (14) are not
favored if the process is carried out under 1200 ℃
 Kinetics
Kinetics of reaction (1) is speeded up by use of catalyst. This is also done by
preventing any reduction in the velocity of the reaction brought about by
presence of inert gas nitrogen in the reaction zone.

Reaction kinetics in ammonia oxidation stage

 Rate of reaction is directly proportional to system pressure.

 Alloying of platinum with rhodium improves yield at given set of conditions.
 Reaction to form NO is favoured by increasing temperature until an
optimum is reached which increases with higher velocities. This results from
the prevention of back diffusion of NO into higher NH3 concentration
region. If this occurs the following reaction is quite probable and should be
avoided for high NO yield.

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  Rate of NO formation very nearly corresponds to diffusional transport of
ammonia molecules to the catalyst surface.

There is slight equilibrium advantage to operation at atmospheric pressure.

This is more than offset by increased capacity in a given reactor volume with
subsequent catalyst and reactor savings when operating high pressures (3-8atm.)

Oxidation of nitrogen oxide does not have as large equilibrium constant.

There so, the reaction predominates in water and absorption portions of the
process, which operates at low temperature at 40-50 ℃. All the nitrogen oxide
liberated on absorption of NO2 must be reoxidized in absorption tower.

Absorption of nitrogen oxides into water

Following design criteria should be considered

 Rate of abortion depends on concentration of NO2 in gas phase. In absorber

where concentration of NO2 is greater than 5%, the controlling reaction is
solution of N2O4 accompanied by hydrolysis of HNO3 and HNO2.
 Low temperature is beneficial for absorber operation efficiency
 Increasing pressure favours physical absorption rate and shift chemical
equilibrium to produce higher acid strength.

Process design modification

Most plants operate at higher pressure (3-8atm) rather than complete

atmospheric pressure. Some operates at a combination of 1atm pressure oxidation
and high pressure absorption. Very high pressure is limited due to cost of pressure
vessel.

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Advantages and disadvantages of elevated pressure are as follows:
Advantages
 Higher acid strength
 Lower investment cost
 Higher reaction rate and lower volume in both oxidation and absorption
equipment
Disadvantages
 Lower oxidation yield
 Higher power require if recovery units are not specified
 Higher catalyst loss unless good catalyst recovery procedure are not used

Catalyst for oxidation of ammonia

Platinum/rhodium alloy containing 10% rhodium is the only industrially

viable
catalyst. Rhodium not only improves the catalytic properties of platinum but also
improves mechanical and anti-abrasive properties of material under the operating
condition such as to counter the severe corrosion and oxidation atmosphere.

4–10 % of rhodium used in Pt/Rh supported catalyst. Higher efficiencies and

smaller platinum losses can be achieved by knitted gauzes.The metallic alloy
catalyst is prepared into very fine threads of diameter0.05mm which are woven into
meshes with more than 1000stiches/cm2. Two to four or even more of these
meshes are placed on top of one another inside the reactors when these are put into
operation. Catalyst threads are smooth, bright and less active at initial stage, as the
time progresses they becomes dull and wrinkled whereupon their activity rises to
the maximum. Finally they become spongy with activity falling off. When it is in
most active state, ammonia oxidation yields up to 98% of NO are obtained.

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 Ammonia conversion efficiency is a function of pressure and temperature.
As
the pressure increases, higher temperatures are needed to obtain the high
conversion efficiency. An increased flow rate and the presence of several layers of
the catalyst help to minimize undesirable side reactions. However, high flow rates
increase the catalyst loss which leads to search for non-platinum catalysts for
ammonia oxidation. The most prospective non-platinum catalysts are based on
oxides of Co, Fe or Cr.

Catalyst poison

Sulfates, H2S, chlorides, Arsenic and its oxide, Si, P, Pb, Sn and Bi are
permanently poisoning the catalyst. These elements lead to the formation of
inactive compounds in the wires resulting in decreasing of the catalytic activity.
Traces of acetylene, ethylene, Cr, Ni and Fe temporarily reduce the conversion
efficiency which can be restored by treatment with HCl. There so air should be
freed from all above impurities along with suspended particles of lubricants, fats,
fine dust and abrasive powder. Also, suspension of Fe2O3 from ammonia is
removed. For that efficient filtration system along with magnetic separators are
provided.

1.4 Absorption Operation

Absorption column is a unit operation where the solute of a gas are removed
by being placed in contact with a nonvolatile liquid solvent that removes the
components from the gas.

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1.5 Process Operation

Changing the conditions of the absorption column can influence the

effectiveness and efficiency of absorption. Some important controlled variables are
as follows:

 Pressure of the column.

 Temperature of entering liquid and gas streams.
 Humidity of the gas stream.
 Ratio of the liquid and gas stream rates.

Raising the total pressure of the column may increase the efficiency of the
separation because increasing the pressure decreases the liquid flowrate and
increases the concentration of the gas. The temperature of entering liquid affects
absorption in that it affects the flow rate of liquid required for the separation with a
given number of stages.

Example: Absorber-stripper

Figure 1.0 shows an absorber-stripper combination. The absorption liquid

circulates in a closed-loop system, consisting of absorber and stripper. Control of
one of the liquid levels also determines the other liquid level. It is therefore no
longer possible to control the latter liquid level. One of the intermediate flows can
be used for level control, for example, the flow from the stripper to the absorber.
This also determines the division of the liquid between the two towers. The other
intermediate flow can be used to determine the circulation speed of the liquid, for
example, the flow from the absorber to the stripper. This flow can be used for

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quality control. To compensate for liquid losses, a separate supply flow can be
used, handled by the process operator.

Figure 1.0 Absorber-stripper combination.

• Controlled qualities: Qualities of intermediate, final and waste products usually

have to be controlled near desired values. Often there is a sharp boundary beyond
which the value of the product decreases. Some qualities can be measured using
robust and affordable measuring devices, which can be installed in the process.
(Table 1.0).
Table 1.0 On-line measuring devices.

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 The reliability depends strongly on the presence of solid particles (rust, catalyst
particles, etc.) in the sample. Sample conditioning is therefore a critical step in the
entire measuring system.

One could also try to estimate the quality (“inferential control”) by using a
suitable algorithm that uses conventional measured values of for example
temperature, pressure, etc. A simple example is the pressure compensation of
temperature measurements on the tray of a distillation column. For binary mixtures
this yields a measure of the composition, for a multi-component system it is an
approximate measure of the composition.

Often the process operators are responsible for the final control of product
quality, based on “off-line” analysis of quality via the laboratory.

(v) Throughput/load and recycle flows: Choose a process variable (or several
process variables) which determine the load of the process. It is not required to use
the feed as the variable, which determines the throughput. Especially, in case of
high load, can the production be maximized by keeping the variable, which is the
limiting factor, at its maximum. In case of a distillation column this could be the
reboiler, which should then be operated with the steam supply fully open. If one

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process acts as a supply to other processes, for example a central steam boiler, then
the throughput is usually determined by the consumer(s).

Recycle flows can best be kept at constant flow or flow ratio, this reduces the
propagation of disturbances. Disturbance propagation is more difficult to control if
the recycle flow includes multiple process units.

(vi) Correcting variables: For total control, all process flows should be adjustable,
hence in principle every process flow is a candidate for a correcting variable. This
only holds under the condition that the accumulations are automatically controlled:
every form of self-regulation decreases the number of correcting variables.

Investigate whether it is economically feasible to adjust the correcting

variables by control valves. Control valves for pipelines with large diameter are
very expensive and consume large amounts of mechanical energy. They can be
omitted unless the controllability of the process is negatively affected.

An alternate for control valves are speed controllers of pumps, compressors

and turbines. This is especially interesting because of the high cost of energy.
Already interesting options exist for asynchronous motors.

A simple rule of thumb for the selection of adjustable process variables is:

Every incoming flow that has not been determined externally, should be
controlled, except when the flow is established as a result of self-regulation of the
adjustable mass- or energy accumulation.

The positioning of a valve, which creates an extra accumulation that has to be

controlled, is not allowed. Similarly, two valves in a pipeline (without creating a
meaningful accumulation) is not allowed either. If a flow is separated into two
other flows, only two of the three flows may contain a control valve.

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Examples of flows that do not have to be controlled or should not be controlled are:

• no valve should be positioned in the discharge line of a thermo syphon reboiler,

since free circulation is required.

• no valve should be positioned in a multiphase flow of vapor and liquid between a

condenser and accumulator, since the liquid flow into the accumulator as a result of
gravity should be unobstructed.

• no valve should be positioned in a supply or discharge line of an evaporator or

condenser, since the amount of liquid that evaporates or vapor that condenses, is
directly determined by the energy supply or removal.

• no valve should be positioned between pressure vessels if the pressure drop is

relatively small, since otherwise an undesired pressure drop is created, one of the
pressures will follow the other one which is controlled and is therefore more or less
self-regulating.

• valves should not be present in fluidized flows, the gas and solids flows have to
be adjusted separately.

(vii) Interaction table and count of degrees of freedom: From this point on, the
procedure for the development of the control scheme deviates from the procedure
for the development of an environmental model. The controlled variables now have
to be arranged in a table versus the correcting variables. The table is used to
represent power and speed of control for each combination of variables.

(viii) Power of control and speed of control: For each combination of the
controlled and correcting variables in the Table, the power and speed of control
have to be established. An example is shown in Table 1.1, which will be discussed
in the sequel. The quality of control that can be expected for an automatic control

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loop, is characterized by the power of control and speed of control. The power of
control is a measure for the static impact of the correcting variable on the
controlled variable. If this impact is small or negligible, then the corresponding
control loop will not function properly. The speed of control is a measure for the
dynamic impact. This can be expressed by the oscillation frequency for
proportional control close to the limit of stability. The higher the frequency, the
better disturbances can be eliminated. The speed of control is limited by the
apparent dead time in the control loop, which is the cumulative dead time of
correcting device, process and measurement device together. The overall system
response has usually one of the following shapes:

• “dead-time like” (see Fig. 1.1a)

• “first-order like” (see Fig. 1.1b)

• “second-order like” (see Fig. 1.1c)

“Dead-time like” responses are dominated by an apparent or real propagation time

Td. The most important control action that should be used is integral action.

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 Figure 1.1 Step responses of a closed loop control system.

Sometimes a weighting between power of control and speed of control is

necessary. An example of such a situation is shown in Fig. 1.2.

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 Figure 1.2 Difference in process dynamics leading to difference in power and
speed of control.

When the temperature sensor is located in the top of the column, the speed of
control for the reflux is high. However, owing to small temperature fluctuations,
often within 0.1 ℃, the power of control is limited. If the temperature sensor is
located in the middle of the column, the power of control is at its maximum and the
speed of control is lower.

(ix) Selection of basic control schemes: Avoid fields that have an indication of the
power of control “none” or “small”. At this level, a third criterion in addition to
power and speed of control should be considered, namely, control loop interaction.
When control loop interaction cannot be avoided, one might have to resort to
decoupling or multivariable control If more than one control scheme has been
found, a proper selection can only be made after the extension of the control
schemes have been reviewed.

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References
1- Dale E. Seborg, Thomas F. Edgar, Duncan A. Mellichamp, Francis J. Doyle
III, ‘’ Process Dynamics and Control ‘’ edition 4th 2017.
2- Blevins, T., W. Wojsznis, and M. Nixon, Advanced Control Foundation:
Tools, Techniques, and Applications, ISA, Research Triangle Park, NC,
2013.

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3- Nichols, G. D., On-Line Process Analyzers, John Wiley and Sons,
Hoboken, NJ, 2010.
4- Strothman, J., More Than a Century of Measuring and Controlling Industrial
Processes, InTech, 42 (6), 52 (1995).
5- Dr. N. K. Patel, ‘’ Heavy and Fine Chemicals’’

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