Production

Advisors: of
Vinyl Acetate
Dr.Faheem
from Mr.Umair
Group Members:
Ethylene

Table of content

2013-CH-37
2013-CH-35
2013-CH-31
2013-CH-81
2013-CH-07

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Introduction:................................................................................................................. 2
Process selection:......................................................................................................... 2
Process flow diagram:.................................................................................................. 4
Process description:..................................................................................................... 5
Capacity:................................................................................................................... 6
References:................................................................................................................ 7

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Introduction:

Vinyl acetate monomer is a flammable, reactive, colorless liquid that is partly soluble in water. It
has a sweet, fruity smell in small quantities, but the odor may become sharp and irritating at
higher levels. It is usually shipped and stored in clearly marked bulk containers.
VAM is a versatile and economically important chemical with a wide variety of industrial and
commercial applications.
Vinyl acetate monomer is a chemical building block used to manufacture a wide variety of
polymers including: polyvinyl acetate, polyvinyl alcohol, polyvinyl acetate, ethylene vinyl
acetate copolymers, ethylene vinyl alcohol and several others.

Process selection:
Acetic acid and acetylene:
The first industrial manufacture of vinyl acetate involved addition of acetic acid to acetylene in
the gas phase over Zn(OAc)2 catalyst impregnated on charcoal at 170-250oC. The process is
based on the reaction:
CH =CH + CH 3 COOH H 2 C=CH O( CO ) CH 3

dH=-118kj/mole

It is a single step, heterogeneously catalyzed, very selective gas-phase reaction in fixed or

fluidized bed reactor. Per pass conversion is 60-70% with selectivity of 93% acetylene and 99%
acetic acid =for a time, Hg(OAc)2 and Zn silicate wer also used as catalysts. Although these
processes are distinguished by high selectivities, simple reaction control and insignificant
catalyst costs, the lower ethylene cost coupled with its storage and transport capability has
plagued the acetylene route. High acetylene cost and safety problems make this process less
competitive today.

Acetaldehyde and acetic anhydride:

The second traditional process takes place in two stages .firstly acet=aldehyde and acetic
anhydride form ethylidene diacetate in liquid phase at 120-140oC with FeCl3 as a catalyst:
(CH 3 CO)2O+CH 3CHO CH 3 CH ( OCOCH 3 ) 2

2nd reaction:
CH 3 CH ( OCOCH 3 ) 2 H 2C=CH O( CO ) CH 3
Note that this process may rely completely on renewable raw materials.

Acetic acid, ethylene and oxygen:

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This route dominates today and it will be adopted in this project. In older technologies reaction
was conducted in liquid phase at 110-130cC and 309-40 bars in presence of catalyst
PdCl2/CuCl2, but corrosion raised problems.
The palladium catalyzed oxidation of ethylene to acetaldehyde becomes an acetoxylatoin
reaction when conducted in a solution of acetic acid and in the presence of sodium acetate.
H 2 C=CH 2+ HO( CO ) CH 3+0.5 O2 H 2 C=CH O( CO ) CH 3+ H 20
The amount of heat that is released in that process is -176KJ/mole .Modern processes operate in
gas phase with Pd based catalysts. With modern Pd/Au catalysts the selectivity may reach 94%
based on ethylene and 98-995 based on acetic acid. The removal of CO2- usually done through a
wash with hot KOH solution negatively affects the overall economics. With respect to reaction
engineering a multi-tubular fixed-bed reactor is employed, where the operational difficulty is
metering the occurrence of excessive temperature rise (hot spot). Recently, fixed-bed reactor
technology was developed with better productivity and 30% lower investment.

Process Comparison:
Process
Acetic acid and Acetylene
Acetaldehyde and acidic
anhydride
Acetic acid, ethylene and
oxygen

Advantage
Single step process
Renewable raw materials
Better productivity and high
conversion per pass

Disadvantage
Lower conversion per pass
Corrosion problem due to
liquid phase reaction
By product CO2 is produced

We have selected the production of vinyl acetate by the acetic acid, ethylene and oxygen because
selectivity may reach 94%, based on ethylene and 98-99% based on acetic acid.

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Process flow diagram:

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Process description:

The basic unit operations proposed for the production of the vinyl acetate process, which is the
focus of this study and the plan we wish to design and opetate are:

Vaporizer
Reactor
Heat exchanger
Separator
Absorber
Distillation column

Vaporizer:
As our reaction occurs in gaseous form, fresh ethylene feed and acidic acid (fresh feed along
with recycle liquid from the distillation column)enters the vaporize; where steam is used to
vaporize the liquid. The gas stream from the vaporizer is further heated to the desired reactor
inlet temperature in a heater using steam. Fresh oxygen is added to the gas stream from the
vaporizer just prior to the reactor to keep oxygen composition in The gas recycle loop outside the
exclusivity region.

Reactor:
Three raw materials, ethylene, oxygen and acetic acid, are concerted into the vinyl acetate and
water and carbon dioxide are the byproducts. We assume that an inlet component, ethane, enters
with the ethylene feed stream. We consider the following two reactions:
H 2 C=CH 2+ HO( CO ) CH 3+0.5 O2 H 2 C=CH O( CO ) CH 3+ H 20
C 2 H 4+3 O 2 2CO 2+ 2 H 2 O
The exothermic reactions occur in a reactor containing tubes packed with a precious metal
catalyst on a silica support. Heat is removed from the reactor by generating steam on the shell
side of the tubes. Water flows to the reactor from a steam drum, to which make up water is
supplied. The steam leaves the drum as saturated vapor. These reactions are irreversible.

Heat exchanger:
The reactor effluent flows through a process-to-process heat exchanger, where the cold steam is
the gas recycle. The reactor effluent is the n cooled with cooling water and sent to the separator.

Separator:
The vapor (oxygen, ethylene, carbon dioxide, ethane) and liquid (vinyl acetate, water, acetic
acid) are separated. The vapor stream from the separator goes to the compressor and the liquid
stream from the separator becomes a part of the feed to the azeotropic distillation column.

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CO2 removal system:

This could be one of the several standard industrial CO2 removal processes. here we simplify
this system by treating it as a component separator with a certain efficiency that is a function of
rate and composition. The gas stream minus carbon dioxide is split, with part going to the purge
for removal of the inert ethane from the process. The rest combines with the large recycle gas
stream and goes to the feed-effluent heat exchanger.

Distillation Column:
The distillation column separates the vinyl acetate and water from the unconverted acetic acid.
The overhead product is condensed with cooling water and the liquid goes to a decanter, where
the vinyl acetate and water phases separate. The organic and aqueous products are sent for
further refining to another distillation section. Here we ignore the additional separation steps
required to produce vinyl acetate of sufficient purity because there is no recycle from the reining
train back to the reaction loop. The bottom product from the distillation column contains acetic
acid, which recycles back to the vaporizer along with fresh make-up acetic acid. Part of this
bottoms stream is the wash acid used in the absorber after being cooled.

Capacity:
We selected the production capacity of vinyl acetate is 150 thousands metric tons per year. This
production capacity is selected on the base of the following reason:
The worldwide production capacity of vinyl acetate monomer (VAM) was estimated at
6,154,000tonnes/annum in 2007, with most capacity concentrated in the United States (1,585,000
all in Texas), China (1,261,000), Japan (725,000) and Taiwan (650,000). The average list price
for 2008 was $1600/tonne. Celanese is the largest producer (ca 25% of the worldwide capacity),
while other significant producers include China Petrochemical Corporation (7%), Chang Chun
Group (6%) and LyondellBasell (5%).

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On the basis of applications, the vinyl acetate monomer market is classified into polyvinyl
acetate (PVA), polyvinyl alcohol (PVOH), ethylene-vinyl acetate (EVA), ethylene-vinyl alcohol
(EVOH) and vinyl acetate ethylene (VAE), among others. Polyvinyl acetate accounted for the
highest demand market share for vinyl acetate monomer over the past few years. Polyvinyl
acetate is one of the major copolymers used in the adhesives industry. Polyvinyl alcohol was the
second-largest application for vinyl acetate monomer market in 2013.
Polyvinyl alcohol is used in manufacturing films and resins which further find applications in
packaging, molding and textile industries. With around 7% market share, ethylene-vinyl acetate
was the third-largest application for vinyl acetate monomer in 2013. Ethylene-vinyl alcohol is
anticipated to be the emerging application for vinyl acetate monomer and is anticipated to grow
at a healthy CAGR over the forecast period. Other applications such as vinyl acetate ethylene
and polyvinyl butyral (PVB) are likely to offer encouraging growth for the vinyl acetate
monomer market over the forecast period.
The global vinyl acetate monomer market is growing due to strong a outlook for adhesives from
end-user industries such as packaging, construction and furniture. Vinyl acetate monomer based
copolymers are commonly used in manufacturing adhesives in large amounts, thus driving the
demand for vinyl acetate monomer. Paints and coatings is another major end-user industry
driving the growth of vinyl acetate monomer market in the past years.

References:
https://www.amazon.com/Unit-Operations-Chemical-Engineering-McGraw/dp/0072848235
http://bocdoo.com/download/chemical-engineering-volume-1-coulson-and-richardson.pdf

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