Ministry of Higher Education and

Scientific Research
Al-Muthanna University
Engineering College
Chemical Engineering Department

Controlling of Distillation column in

"The Production of Acrylic Acid via
"Propylene

Prepared By: Hussein Dhyaa Mohammed

Class: Fourth Stage

Subject: Process Control

Supervisor: Dr. Forat Yasir AlJaberi

Introduction
Acrylic acid is the simplest unsaturated carboxylic acid and is a building
block for thousands of consumer products. It is a commodity chemical
with a current market demand of nearly 10 billion pounds per year,
projected to surpass 13 billion pounds worth $14 billion by the end of
2018. Acrylic acid plays an integral role in and is the monomer for
polymerization used for super absorbent polymers (SAPs). Increasing
population, increasing lifespan, and improving lifestyle have all
significantly increased the demand and growth of super absorbent
polymers market in the developed and developing world which includes
disposable hygiene products such as baby diapers, and sanitary napkins.
The majority of the market growth is projected to occur in China and
India as these countries produce increasing amounts of products using
acrylic acid as intermediates with application including detergents,
coatings, adhesives, sealants, as well as personal care items. Currently,
the US accounts for 25% of global production. Generally, acrylic acid is
produced using propylene. Propylene is a byproduct of hydrocarbon
cracking and naphtha refining, and the price very closely follows that of
oil. Because of high refinery production rates in the US, propylene has
been sold at a slight discount to ethylene historically. However, the US
has seen a recent shale gas boom that has increased the supply of natural
gas and ethane and dropped their prices to the lowest ever seen. With the
announcement of large-scale ethane crackers such as the $6 billion
cracker ConocoPhillips plants to have operational by 2017, the price and
supply of ethylene may soon flood US markets. The purpose of this
report was to determine whether ethylene-based processes could
underscore and outcompete the propylene-based business . Acrylic acid
(AA) is used as a precursor for a wide variety of chemicals in the
polymers and textile industries. There are several chemical pathways to
produce AA, but the most common one is via the partial oxidation of
propylene

Physical and Chemical properties of Acrylic Acid

Acrylic acid is a federal hazardous air pollutant and was identified as a
toxic air contaminant in April 1993 under AB 2728.
CAS Registry Number: 79-10-7
Molecular Formula: C3H4O2
Description
Acrylic acid is a corrosive, colorless liquid with an acrid odor. It is
miscible with water, alcohol, ether, benzene, chloroform, and acetone. It
polymerizes readily in the presence of oxygen (Merck, 1989). Exothermic
polymerization at room temperature may cause acrylic acid to become
explosive if confined. It is also a fire hazard when exposed to heat or
flame (Sax, 1989).

Physical Properties of Acrylic Acid

Molecular Weight 72.06
Boiling Point 141.0 oC
Melting Point 14.0 oC
Flash Point 68 oC (155.0 oF) (open cup)
Vapor Density 2.45 (air = 1)
Density/Specific Gravity 1.0511 at 20/4 oC
Vapor Pressure 3.1 mm at 20 oC
Log Octanol/Water Partition 0.36
Coefficient
Conversion Factor 1 ppm = 2.95 mg/m3

CHEMICAL PROPERTIES
Acrylic acid undergoes reactions characteristics of both unsaturated acids
and aliphatic carbolic acids or esters. The high reactivity of these
compounds stems from the tow unsaturated centers situated in the
conjugated position. The β carbon atom, polarized by carbonyl group,
behaves as an electrophile; this fovours the addition of large variety of
nucleophiles and active hydrogen compounds to the vinyl group.
Moreover, the carbon-carbon double bond undergoes radical-initiated
addition reactions, Diels-Alder reactions with dienes, and polymerization
reactions. The carboxyl function is subject to the displacement reactions
typical of aliphatic acids and esters, such as esterification and
transesterification. The polymerization is catalyzed by heat, light, and
peroxides and inhibited by stabilizers, such as monomethyl ether of
hydroquinone or hydroquinone itself. These phenolic inhibiters are
effective only in the presence of oxygen. The highly exothermic,
.spontaneous polymerization of acrylic acid is extremely violent

Uses
1- plastic
2-paper manufacture and coating
3-exterior house paints for wood and masonry
4- coatings for compressed board and related building materials
5- flocculation of mineral ore fines and waste water, and treatment of
sewage
6- printing inks
7- interior wall paints
8- floor polishes
9- floor and wall coverings
10- industrial primers
11- textile sizing, treatment and finishing
12- leather impregnation and finishing
13- masonry sealers
14- lubricating and fuel oil additives
15- lacquers for automotive, appliance and furniture finish
16- pharmaceutical binders
hot metal coatings -17

Method of production
1- acrylic acid production by fermentation
2- Acrylic Acid from Ethylene
3- Catalytic hydro carboxylation of acetylene to acrylic acid using Ni2O3
and cupric bromide as combined catalysts
4- Highly Selective Production of Acrylic Acid from Glycerol via Two
Steps Using Au/CeO2 Catalysts
5- Acrylic Acid by Catalytic Partial Oxidation of Propylene.

5- Acrylic Acid by Catalytic Partial Oxidation of Propylene

Acrylic acid (AA) is used as a precursor for a wide variety of chemicals
in the polymers and textile industries. There are several chemical
pathways to produce AA, but the most common one is via the partial
oxidation of propylene. The usual mechanism for producing AA utilizes a
two-step process in which propylene is first oxidized to acrolein and then
further oxidized to AA. Each reaction step usually takes place over a
separate catalyst and at different operating conditions.

Process Description
Figure is a preliminary process flow diagram (PFD) for the acrylic acid
production process. The raw materials are propylene and oxygen. Steam
in added to provide thermal ballast. The propylene feed may be assumed
pure vapor at 446 kPa. The air feed, which may be considered to contain
only oxygen, nitrogen, and water is also at 446 kPa. The steam is
saturated at 446 kPa. The feeds are mixed and sent to the reactor (R301)
in which acrylic acid is formed. The reactions which occur are shown
below. The reactor effluent is sent to a separation unit (S-301), in which
all light gases (oxygen, nitrogen, carbon dioxide, and propylene) are
separated as vapor in Stream 7. Stream 7 is split into Streams 8 and 9.
Stream 8 is a recycle stream containing propylene, oxygen, nitrogen, and
carbon dioxide. A pump is required in this stream which is not shown.
Stream 9 is incinerated. Stream 10,
containing water and acrylic acid is sent to a distillation column (T-301)
to produce purified acrylic acid. The desired acrylic acid production rate
.is 160,000 metric tons/yr
Distillation column
Distillation is a kind of separation technique of two or more volatile
liquid compounds by using the difference in boiling points and relative
volatility .The process takes place in a column, and two heat exchangers.
In the column two phases, liquid and gas, are distributed to enrich the
vapor in more volatile compounds and enrich the liquid phase on less
volatile compounds .Mass transfer is the key to a successful distillation.

Types of Distillation Columns

There are many types of distillation columns, each designed to perform
specific types of separations, and each design differs in terms of
complexity.

Batch Columns
The oldest operation used for separation of liquid mixtures.
•Feed is fed from bottom ,where includes reboiler, to be processed.
•Numbers of accumulator tanks are connected to collect the main and the
intermediate distillate fractions.

Continuous Columns
The mixture which is to be separated is fed to column at one or more
points.
Liquid mixture runs down the column while vapor goes up.
•Vapor is produced by partial vaporization of the mixture which is heated
in reboiler.
•Then vapor is partially condensed to earn back the less volatile
compounds to the column to separate as bottom product. (reflux)

Semi-batch Distillation
Semi-batch distillation is very similar to batch distillation.
•Feed is introduced to column in a continuous or semi-continuous mode.
•It is suitable for extractive and reactive distillations

Basic Operation and Terminology

The liquid mixture that is to be processed is known as the feed and this is
introduced usually somewhere near the middle of the column to a tray
known as the feed tray. The feed tray divides the column into a top
(enriching or rectification) section and a bottom (stripping) section. The
feed flows down the column where it is collected at the bottom in the
reboiler.

Heat is supplied to the reboiler to generate vapour. The source of heat

input can be any suitable fluid, although in most chemical plants this is
normally steam. In refineries, the heating source may be the output
streams of other columns. The vapour raised in the reboiler is re-
introduced into the unit at the bottom of the column. The liquid removed
from the reboiler is known as the bottoms product or simply, bottoms.

The vapor moves up the column, and as it exits the top of the unit, it is
cooled by a condenser. The condensed liquid is stored in a holding vessel
known as the reflux drum. Some of this liquid is recycled back to the top
of the column and this is called the reflux. The condensed liquid that is
removed from the system is known as the distillate or top product.
Control Distillation Column
The primary objective of distillation column control is to maintain the
specified composition of the top and bottom products, and any side
streams and To set stable conditions for column operation, To regulate
conditions in the column so that the product(s) always meet the required
specifications ,To achieve the above objective most efficiently, e.g. by
maximizing product yield, minimizing energy consumption, etc.;
correcting for the effects of disturbances in:
1. Feed flow-rate, composition and temperature.
2. Steam supply pressure.
3. Cooling water pressure and header temperature.
4. Ambient conditions, which cause changes in internal reflux
The compositions are controlled by regulating reflux flow and boil-up.
The column overall material balance must also be controlled; distillation
columns have little surge capacity (hold-up) and the flow of distillate and
bottom product (and side-streams) must match the feed flows.
Shinskey (1984) has shown that there are 120 ways of connecting the five
main parts of measured and controlled variables, in single loops. A
variety of control schemes has been devised for distillation column
control. Some typical schemes are shown in Figures 5.22a, b, c, d, e (see
pp. 234, 235); ancillary control loops and instruments are not shown.
Distillation column control is discussed in detail by Parkins (1959),
Bertrand and Jones (1961) and Shinskey (1984) Buckley et al. (1985).
.Column pressure is normally controlled at a constant value

Feed temperature is not normally controlled, unless a feed preheater is

used. Temperature is often used as an indication of composition. The
temperature sensor should be located at the position in the column where
the rate of change of temperature with change in composition of the key
component is a maximum; see Parkins (1959). Near the top and bottom of
the column the change is usually small. With multicomponent systems,
temperature is not a unique function of composition. Top temperatures
are usually controlled by varying the reflux ratio, and bottom
temperatures by varying the boil-up rate. If reliable on-line analyzers are
available they can be incorporated in the control loop, but more complex
control equipment will be needed. Differential pressure control is often
used on packed columns to ensure that the packing operates at the correct
loading; see Figure 5.22d (see p. 234). Additional temperature indicating
or recording points should be included up the column for monitoring
.column performance and for trouble shooting [7]
Figure 5.22. (a) Temperature pattern control. With this arrangement interaction can
occur between the top and bottom temperature controllers (b) Composition control.
Reflux ratio controlled by a ratio controller, or splitter box, and the bottom product as
a fixed ratio of the feed flow (c) Composition control. Top product take-off and boil-
up controlled by feed (d) Packed column, differential pressure control. Eckert (1964)
.discusses the control of packed columns
Figure 5.22. (e) Batch distillation, reflux flow cascaded with temperature to maintain
constant top composition

Represent the (Control Variable) where the process variable that )Xd(•
are control where the desired value of control variable is referred to as it's
.set point
Represent the (Manipulated Variable) where the process variable )R(•
that can be adjusted in order to keep the control variable ,at or near their
.set point

Represent the (Load Variable) )F(•

Control Temperature►
Temperature control is just one of many process variables in distillation
along with flow rate, and composition. Distillation is the action of
separating different components that are comingled in a base liquid. As
the quantity Reflux ratio increases, the temperature will decrease, and
vice versa. This separation is accomplished by carefully controlling the
temperature that is applied to a vessel that contains the base liquid so that
the desired “purified” component, which usually evaporates at a specific
and unique temperature, can be removed from the base liquid, whose
other elements evaporate at different temperatures than the desired
component .Column temperature control is perhaps the most popular way
of controlling product compositions. In this case, the control temperature
is used as a substitute to product composition analysis.
Ideally, both top and bottom compositions should be controlled to
maintain each within its specifications. In Distillation column It
separates the materials on the basis of the difference in boiling points and
the difference in volatility, as the materials enter the distillation tower at a
known pressure and temperature, where the materials descend at the
bottom of the distillation tower and enter the (reboiler) equipment, where
this equipment heats the materials and takes out some materials (waste)
Likewise, you return a part of the materials, where these returned
materials start to move upward, and whenever these materials move
upward, they will condense, decrease its temperature and enter the part
(condenser) where the temperature of these materials decreases and goes
to (Reflux Drum) and part of these materials separates and the rest part
Due to the increased stability and gradient of heat. The materials with a
low boiling point and high volatility will separate from the top, which
represents the light substance, while the materials with a high boiling
point and low volatility will be separated from the bottom, which
represents the heavy substance. In practice, simultaneous composition
control of both products suffer from serious "coupling" (interaction)
between the 2 controllers, resulting in column instability. In the system
shown, suppose that there are concentration changes in the feed
conditions that result in lower column temperature. The top and bottom
temperature controllers will respond by decreasing reflux and increasing
.boil-up respectively

If the actions of the 2 controllers are perfectly matched, and response is

instantaneous, both control temperatures will return to their set points
.without interaction

However, the 2 actions are rarely perfectly matched, and their dynamics
are dissimilar - usually the boil-up response is faster. The reflux and boil-
On-line analyzer can be used together with temperature control to control
product composition. The principal control action is rapidly performed by
the temperature controller, while the analyzer slowly adjusts the
temperature set point to prevent off-specification product purity In the
above set-up, delayed analyser response is acceptable, as its time lags
become a secondary consideration. The fast temperature controller action
renders this control method less sensitive to upsets and step changes in an
analyser-only control system. Another advantage is that, should the
analyser become inoperative, the temperature controller will maintain
automatic control of the process.
•Reboiler Control
This is required to provide good response to column disturbances, and to
protect the column from disturbances occurring in the heating medium.
The reboiler boil-up is regulated either: (1) to achieve desired product
purity, or (2) to maintain a constant boil-up rate. For inlet steam
controlled reboiler, the heat transfer rate is regulated by varying the steam
control valve opening, thereby changing the steam condensing pressure
and temperature.

When an additional boil-up is required, the valve opens and raises the
reboiler pressure, which increase the temperature, and in turn increases
the boil-up rate. This scheme has the disadvantage of non-linear
relationship between pressure and boil-up, and is affected by fouling in
the reboiler.

Condenser Control•
Temperature control is unlikely to be effective for condensers, unless the
liquid stream is sub-cooled. Pressure control is often used ,or control can
.be based on the outlet coolant temperature
Controlling Level►
When there is more than one substance, it is difficult to separate the
materials, especially if they have close boiling points, as well as if the
flow contains high impurities and creates side effects, it will face
difficulty in the separation process. for distillation columns level control
refers, in most cases, to overhead condenser receivers (reflux
accumulators), column bases, surge or feed tanks, and sometimes steam
condensate receivers Level controllers are used to maintain the level in
the accumulator, the reboiler and the intermediate accumulator of a
stacked column (i.e., a distillation column composed of two separate
columns when there are too many trays for one column). Loose level
control on the accumulator and reboiler has been shown to worsen the
composition control problem for material balance control configurations
(when either D or B is used as a MV for composition control). When D or
B is adjusted, the internal vapor/liquid traffic changes only after the
corresponding level controller acts as a result of the change in D or B. On
the other hand, if a level controller is tuned too aggressively, it can result
in oscillations passed back to the column and contribute to erratic
operation. When the reboiler duty is set by the level controller on the
reboiler, a level controller that causes oscillation in the reboiler can also
cause cycling in the column pressure.. For most of these applications, the
chief function is not that of holding level constant, but rather of achieving
the smoothest possible transitions in manipulated flows in response to
disturbances. This is “averaging” level control.’
As stated in Chapter 1, the actions of averaging level control are:
1. Balancing inflows against outflows at a point in a process.
2. Providing for smooth and gradual changes in manipulated flows to
avoid
upsetting process equipment.
3. Maintaining inventory or accumulation between an upper and a lower
limit (not at a fixed value).
On new projects the engineer is confronted with two alternatives: (1) the
tank or holdup size is already specified and the problem is to get
maximum flow smoothing, or (2) the tank is to be sized and the level
control system designed to achieve flow smoothing adequate for
downstream composition controls.

►Feed Preheat Control

Feed preheat is usually practiced for heat recovery or to attain the desired
vapor and liquid traffic above and below the feed tray. The objective of
the preheat control system is to supply the column with a feed of
consistent specific enthalpy. With a single-phase feed, this becomes a
constant feed temperature control; with a partially vaporized feed, a
constant fractional vaporization is required.

►Controlling Tops Composition in Distillation

the other parameter most likely to be controlled is the composition of the
tops product. The reason is that the final product will most probably come
from the top of the column and it is important to know its composition.
Again, as with pressure, there are many different ways of controlling the
tops composition. Three methods are described below.

 Reflux Rate
 Reflux Ratio
 Distillate Rate

•Reflux Rate: In this first example the reflux rate is adjusted to control
the composition of the tops product.(Figure-Reflux Rate)
As the amount of reflux is changed so the temperature profile in the
column changes and hence the composition.

•Reflux Ratio: The second example uses the reflux ratio as the control
parameter.

Figure-Reflux Ratio

When designing a distillation column it is usually the reflux ratio that is

determined. This can be kept constant throughout operation by using two
.flow indicators and a ratio controller

•Distillate Rate:The third example is for high purity tops. It uses the
distillate flowrate to control the distillate composition.
 Figure- Distillate Rate

It can be shown that for a high purity column i.e. one with a large reflux,
that the composition of the distillate is sensitive to the distillate flow but
insensitive to the reflux rate. Therefore for a high purity column the
control scheme outlined above is used. It should be noted that tight
.control on the level in the reflux drum is required using the reflux rate

References
Volume 6•
•Plant design and Operations(Second Edition),2017

•James G. Speight, in The Refinery of the Future, 2011

Editors: Jacqueline I. Kroschwitz and Arza Seidel (2004). Kirk-•

Othmer Encyclopedia of Chemical Technology (5th ed.). Hoboken,
.New Jersey: Wiley-Interscience

McCabe, W., Smith, J. and Harriott, P. (2004). Unit Operations of •

.Chemical Engineering (7th ed.). McGraw Hill