Ministry of Higher Education and

Scientific Research
Al-Muthanna University
Engineering College
Chemical Engineering Department

Controlling of distillation in the

production of Vinyl acetate

Prepared by: Mahmoud Mohamed

Class: fourth
Subject: Processes control

Supervised by: Dr. Forat Yasir AlJaberi

 Vinyl acetate is an organic compound with the formula CH 3CO2CHCH2.vinyl
acetate is a colorless liquid with a low flash point, flammable that also has a
characteristic smell that can quickly become irritating. This monomer is used
principally in the production of polyvinyl acetate (PVAc) and other vinyl acetate co-
polymers. Polyvinyl acetate is a precursor of polyvinyl alcohol and polyvinyl acetate
resins (PVA) .vinyl acetate is also copolymerized as a minor raw material for vinyl
chloride and ethylene to form commercial polymers and acrylic fibers.

Vinyl acetate is completely soluble in organic liquids but not in water. At 20º C a
saturated solution of the monomer in water can contain between 2-2.4% of vinyl
acetate, while a saturated water solution in vinyl acetate contains 1% of water. At 50ºC
the solubility of the monomer in water increases in 0.1% in regards to 20ºC, while the
solubility of water in vinyl acetate doubles at 50ºC.

The most important reaction of vinyl acetate is the polymerization by free radicals
which is fast and exothermic. Due to the fact that the vinyl acetate is an Ester, it presents
the reactive properties of said group keeping in mind that the corresponding chain of
alcohols is unsaturated, the compound presents some differences in regards to the Ester
group.The speed of hydrolysis of the vinyl acetate is 1,000 times greater than its
saturated analogous in a alkaline medium, and it was researched that its speed of
hydrolysis is significantly lower at a pH of 4.4.

The production of vinyl acetate monomer (VAM) represents one of the largest
industries with a growth estimate of a near 2.7% per year starting in 2008. In recent
times, thanks to different studies and the importance of said product, one process has
been developed based on the reaction of ethylene -acetic acid, and oxygen using a
Pd/Au catalyst. In this work, a detailed study was made based on a simulation of the
process using the Aspen Plus v2006 program and establishing the correct operation
conditions. The simulated process involves, from the preparation of the raw materials
until the dehydration of the monomer. The restrictions set for the simulation
corresponds to the VAM composition restriction in the extractive distillation column
using glycerol.

Vinyl acetate is an organic compounds from the esters group which have the
general formula (CnH2nO2) with the structure (RCOOR) consists of a carbon double
bonded to oxygen single bonded to carbon and (R) (where R is refer to H or organic
groups).(11)

Figure (1:1)
 The Vinyl acetate is a colorless, flammable liquid at room temperature (20ºC).
As the monomer is an organic ester, it has a sweet smell in small quantities. Being an
organic ester, vinyl acetate monomer is soluble in many organic solvents of varying
solvent strength such as ethane, acetone and chloroform. In the presence of light, the
monomer will initiate self-polymerization.

Property Value

Chemical formula CH3COOCH=CH2

Structural formula

Molecular weight 86.09 g/mole

Melting point -93.2 C°

Boiling point 72.7 C°

Flash Point -9 C°

Freezing point -92.8 C°

Vapor Density 3.0 gm/cm3 (air = 1 gm/cm3)

83 mm Hg at 20C°
Vapor Pressure
And 115 mm Hg at 25C°
 And 140 mm Hg at 30C°

Density 0.932 g/cm3at 20/4 C° (water=1)

Specific Gravity 0.932 at 20/4 C°

Water Solubility 1 g/50 ml at 20 C°

Solubility Dissolved in ethyl acetate and ethanol

Henry's law constant 4.46 x 10-4 atm×m3/mole

Conversion Factor 1 ppm = 3.52 mg/m3

0.54 cp at 0 C°

Absolute Viscosity And 0.41cp at 20 C°

And 0.33 cp at 40 C°

Critical Temperature (Tc) 246 C°

Critical Pressure (Pc) 39.1 atm

Surface tension 23.8 mN/m at 20 C°

 Table (1-2): Thermodynamic properties of vinyl acetate

Property Value

Heat of formation −349.4 kJ/mol(liquid at 25 C°)

Heat of combustion −495.0 kcal/mol at 25C°

Heat of vaporization 87.6 cal/g (1atm)

Specific heat capacity (cp ) 0.64cal/g.C° at 20 ◦C (liquid)

Vinyl Acetate Monomer (VAM) is an ester organic compound with the formula
(CH3COOCH=CH2), is completely soluble in organic liquids but not in water. May
polymerize if heated or contaminated. If polymerization occurs inside a container, the
container may violently rupture. Highly flammable. VAM may undergo spontaneous
exothermic polymerization on exposure to light. Reacts with air or water to produces
peroxides that initiate explosively violent polymerization. Reacts with hydrogen
peroxide to form explosive peracetic acid. Reacts with oxygen to form explosive
peroxides Forms explosive vinyl acetate ozonide on contact with ozone. When heated
to decomposition, it burns and emits acrid fumes. Highly dangerous when exposed to
heat, flames or oxidizers; explosion hazard with strong acids and strong oxidizers.
Incompatible with alumina, oxidizing materials, 2-aminoethanol, chlorosulfonic acid;
ethyleneimine; 36% hydrochloric acid; 48.7% hydrofluoric acid; 70% nitric acid;
oleum; 96% sulfuric acid; ethylene diamine; peroxides and silica gel. Avoid light or
any polymerizing initiator. Hazardous polymerization can be initiated by organic and
inorganic peroxides; azo compounds; redox systems (including organometallic
components); light; and high energy radiation. Polymerization in toluene solution has
caused several large industrial explosions. It can be polymerized to give polyvinyl
acetate. With other monomers can be used to prepare copolymers such as ethylene-
vinyl acetate (EVA), vinyl acetate-acrylic acid (VA/AA), polyvinyl chloride acetate
(PVCA), and poly-vinyl-pyro lidone (Vp/Va Copolymer, used in hair gels).

Uses of Vinyl Acetate Monomer:-

Vinyl acetate monomer is mainly used in the production of polyvinyl acetate
(PVAc) and polyvinyl alcohol (PVOH or PVA). In fact, 80 % of all the VAM produced
in the world is used to make these two chemicals. Polyvinyl acetate is used in paints,
adhesives, paper coatings and textile treatments, while polyvinyl alcohol is used in the
production of adhesives, coatings, and water soluble packaging, and textile warp sizing
VAM is also used to make polyvinyl butyral (PVB) which is used in laminated safety
glass for cars and buildings. Ethylene-vinyl acetate (EVA) resin is also made from
VAM and is used in the manufacture of packaging film, heavy-duty bags, extrusion
coating, wire and cable jacketing, hot-melt adhesives and cross-linked foam. Other
products made from VAM are ethylene-vinyl alcohol (EVOH) resins which are used
as a gas barrier in multi-layered food and beverage packages, and as a barrier layer in
automobile tanks.
 Vinyl acetate monomer (VAM) is used as an intermediate in the manufacture of
various copolymers and homo polymers such as polyvinyl acetate, polyvinyl alcohol,
ethylene-vinyl acetate and ethylene-vinyl alcohol among others. Vinyl acetate
monomer (VAM) is one of the key ingredients used in the manufacture of furniture
glue and adhesives

Storage and Distribution:-

Vinyl acetate monomer is stored in mild steel storage tanks and/or new or
reconditioned steel drums and can be transported by bulk vessels or tank trucks. It has
a specific gravity of 0.933 and a flash point of -8° C (closed cup) and is highly
flammable. It should therefore be stored in a cool, dry, well-ventilated area that is free
from the risk of ignition. For transportation purposes, it is classified as packing group
II and hazard class 3 and it is an irritant.

Health and Safety:-

Vinyl acetate is slightly or moderately toxic to humans and animals. The vapor
irritates the eyes starting with 20 ppm, while the detection threshold is reported to be
about 0.5 ppm. Released into the environment the vinyl acetate evaporates easily, being
degraded rapidly by photochemical reactions, as well as biodegraded by either
anaerobic or aerobic mechanisms. Therefore, the bioaccumulation of vinyl acetate in
the ecosphere is unlikely. Vinyl acetate is dangerous when exposed to heat, flame or
oxidizers, and as a consequence, it requires adhering to the safety measures when
stored or manipulated by operators. The same precaution is valid for the raw materials.
Ethylene is highly explosive in mixture with oxygen, the explosion limit being at 10%
vol. The acetic acid is a highly toxic and corrosive substance. Stainless steel of
Cr/Ni/Co type is employed for operations involving acetic - acid solutions in boiling
conditions , but normal stainless steel may be used for vapor - phase operations.

Vinyl acetate is primarily used as a monomer in the production of polyvinyl

acetate and polyvinyl alcohol. Acute (short-term) inhalation exposure of workers
to vinyl acetate has resulted in eye irritation and upper respiratory tract irritation.
Chronic (long-term) occupational exposure did not result in any severe adverse effects
in workers; some instances of upper respiratory tract irritation, cough, and/or
hoarseness were reported. Nasal epithelial lesions and irritation and inflammation of
the respiratory tract were observed in mice and rats chronically exposed by inhalation.
No information is available on the reproductive, developmental, or carcinogenic effects
of vinyl acetate in humans. An increased incidence of nasal cavity tumors has been
observed in rats exposed by inhalation. In one drinking water study, an increased
incidence of tumors was reported in rats. EPA has not classified vinyl acetate for
carcinogenicity.

1- Addition of acetic acid to acetylene:

a) In the liquid phase in the presence of homogeneous mercury salt catalysts.

b) In the gas phase in the presence of heterogeneous catalysts containing zinc salts.

2- Reaction of ethylene with acetic acid and oxygen:

 a) In the liquid phase in the presence of palladium/copper salts as homogeneous
catalysts.
C2H4 + PdCl2 + CH3CO2H → CH3CO2CH=CH2 + 2HCl + Pd

b) In the gas phase on heterogeneous catalysts containing palladium.

CH2=CH2 + CH3CO2H + 1/2O2 → CH3CO2CH=CH2 + H2O

3- Vinyl acetate can also be synthesized in high yields by reacting vinyl chloride with
sodium acetate in solution at 50°-75°C, using palladium chloride as a catalyst.

CH2=CHCl + CH3CO2Na → CH3CO2CH=CH2 + NaCl

4- Reaction of methyl acetate or dimethyl ether with carbon monoxide and hydrogen
in the liquid phase in the presence of homogeneous catalysts, e.g., rhodium salts or
noble metals of the platinum group, giving ethylene di acetate cleavage of the latter
giving acetic acid and vinyl acetate.

2CH3CO2CH3 + 2CO + H2 → (CH3CO2)2CHCH3 + CH3CO2H

(CH3CO2)2CHCH3 → CH3CO2CH=CH2 + CH3CO2H
2CH3OH + 2CH3CO2H → 2CH3CO2CH3 + 2H2O

5- Acetaldehyde and acetic anhydride:

The process takes place in two stages. Firstly acetaldehyde and acetic anhydride form
ethylene di acetate in liquid phase at 120 – 140 ° C with FeCl3 as a catalyst:
CH3CHO + (CH3CO) 2 O → CH3CH (OCOCH3)2

CH3CH (OCOCH3)2 → CH3CO2CH=CH2 + CH3CO2H

Figure (1:2):The flow sheet of the process
For continuous distillation, the primary process objective is to separate a feed mixture
into two (or more) product streams with specified compositions. Thus the product
compositions are the most important CVs.
For some distillation columns, one product composition is much more important than
the other. For example, consider a series of columns where the bottom stream of a
column serves as the feed stream to the next column.
The distillate composition for each column is more important because it is a product
stream (Guideline)
1. By contrast, the bottom stream for each column (except the last column in the
series) undergoes further separation, so the bottom compositions are of less
concern. Consequently, in these situations, the bottom compositions may not
have to be controlled. In addition to one or more product compositions, other
process variables need to be controlled. Consider the separation of a binary
mixture and the conventional tray-distillation column shown in Fig. 13.2.
Assume that the chief control objective is to control both product
compositions, xD and xB. However, the liquid levels in the reflux drum, hD,
and the column base (or sump), hB, must be kept between upper and lower
limits (Guideline
2. The column pressure, P, must also be controlled in order to avoid weeping or
flooding in the column and to control the vapor inventory in the column. Thus,
this column has a total of five CVs: xD, xB, hD, hB, and P. The MVs are
selected from among six input variables: feed flow rate F, product flow rates,
D and B, reflux flow rate R, and the heat duties for the condenser and reboiler,
qD and qB. If the feed stream comes from an upstream process, instead of from
a storage tank, itcannot be manipulated, and thus F is considered to be a DV. In
this situation, there are five MVs.

1. There can be significant interaction between process variables. One important

example is that changing a single MV can have significant effects on many CVs.
For example, increasing heat duty qB by increasing the steam flow rate causes
more liquid to be boiled and thus increases the vapor flow in the column.
Consequently, the qB increase causes sump level hB, pressure P, and bottom
composition xB to change rather quickly (Guideline 7). However, the increase in
qB also affects reflux drum level hD and distillate composition xD more slowly,
after the increased vapor flow reaches the top of the column (Guideline 8).
Similarly, changes in R or D affect hD and xD rather quickly and hB and xB more
slowly. Other interactions arise when the hot bottom stream from the column is
used to heat the cold feed stream in a bottom-feed heat exchanger, in order to
reduce energy consumption.
2. The column behavior can be very nonlinear, especially for high-purity
separations. For example, the amount of effort required to reduce an impurity
level in a product composition from 5% to 4% is typically much less than the
effort required to reduce it from 1.5% to 0.5%. The nonlinear behavior is largely
due to the nonlinear vapor–liquid equilibrium relationships (Skogestad, 1997).

3. Distillation columns often have very slow dynamics.

The dominant time constants can be several hours, or even longer, and long time
delays are also common. Because slow dynamics result in long response times with
feedback control, the addition of feedforward control can be very advantageous.

3. Process constraints are important.

The most profitable operating conditions typically occur when some MVs and
CVs are at upper or lower limits. For example, maximum separation, or maximum
recovery of a valuable feed component, often Occurs for maximum reboiler
heating or condenser cooling.

5. Product compositions are often not measured.

Although product compositions are the primary CVs, their on-line measurement is
often difficult, expensive, and costly to maintain. Consequently, tray or product
stream temperatures are commonly measured and controlled as proxies for product
compositions. This strategy is easier to implement but makes tight composition
control more difficult. Another major complication is that there are many different
column configurations, especially for reboilers and condensers, and many alternative
process and control objectives. Consequently, each column control application tends
to be different and to require individual analysis. Fortunately, there is an extensive
literature available on both the practical and theoretical aspects of distillation column
control (Shinskey, 1984; Luyben,1992; Skogestad, 1997, 2007).

The loss of the coolant to a process vessel can produce an unacceptably high pressure
in the vessel. As a result, a pressure relief valve is used to reduce the pressure by
releasing the vapor mixture to the atmosphere. But if the mixture is toxic or
flammable, the release can be hazardous. For the distillation column in Fig. E10.4,
which operates at above ambient temperature, propose an alarm/SIS system that will
reduce the number of releases to the environment, even though the occasional loss of
coolant flow to the condenser is unavoidable.
A temperature control system for a distillation column is shown in Fig. The
temperature T of a tray near the top of the column is controlled by adjusting the
reflux flow rate R.
1. Alain, C., Gilles, L., Pierre, L., Petrochemical Processes: Technical and
Economic Characteristics, 2th edition, 1986.
2. Alexandre, C., Costin, S., Chemical Process Design: Computer-Aided Case
Studies, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim, 2008.
3. Chen,R., Dave,K.,, Mc Avoy,T.,A Nonlinear Dynamic Model of a Vinyl Acetate
Process.
4. Vinyl acetate safety handling guide, April 2010.
5. www.Alibaba.com
6. www.dow.com
7. www.solventis.net/other/vinyl-acetate-monomer
8. Process Dynamics and Control Fourth Edition
9. Chemical Process Engineering Design and Economics - H.Silla