Process Technologies Availability and Selection

Criteria
This chapter discusses the available technologies for VCM process
and the selected technology of Technik co. based on some criteria.
To produce VCM, several technologies were developed around the
world. Each technology differs from others by type of feed stocks,
numbers of units, and the reactors type. For instance, some
technologies use air as a feed to the oxy-chlorination reactor rather
than pure oxygen which Technik uses. Therefore, some technologies
have been eliminated like Ethyl integrated, PPG, B.F Goodrich,
Phone-Poulenc, and Monsanto technology. Technik co. passed
through other available technologies (MTC, Toyo Soda, Vinnolit, and
Stauffer) to select the best one based on some criteria such as
efficiency and economics.
1. Stauff er Technology
2. MTC technology
3. Toyo Soda Technology
4. Vinnolit Technology

Technik co. selected hybrid between both Toyo and Vinnolit

technologies, since there are many similarities between them.

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Objective
This chapter discusses the available technologies for VCM process
and the selected technology of Technik co. based on some criteria.

Introduction:
To produce VCM, several technologies were developed around the
world. Each technology differs from others by type of feed stocks,
numbers of units, and the reactors type. For instance, some
technologies use air as a feed to the oxy-chlorination reactor rather
than pure oxygen which Technik uses. Therefore, some technologies
have been eliminated like Ethyl integrated, PPG, B.F Goodrich,
Phone-Poulenc, and Monsanto technology. Technik co. passed
through other available technologies (MTC, Toyo Soda, Vinnolit, and
Stauffer) to select the best one based on some criteria such as
efficiency and economics.

Stauff er Technology:
In the direct chlorination process for Stauffer, ethylene and chlorine
are reacted in the liquid phase to produce a crude product which
contains 99.7% EDC. Then, the reactor product is combined with the
crude oxy EDC, washed and distilled to remove water, light ends
and heavy ends. Stauffer also offers an oxygen-based oxy process in
which the main reactor off-gas, following condensation of EDC, is

compressed and recycled to the first oxy reactor. An excess of

ethylene is used to maximize HCl conversion and minimize byproducts. A small slipstream from the ethylene-rich recycle is
purged to an ethylene recovery unit for control of inerts.

MTC technology:
For the direct chlorination reaction, MTC technology utilizes a
boiling liquid process. The heat of the reaction is dissipated with the
gaseous EDC exit stream which is condensed externally and sent to
purification. In the oxy-chlorination section, they use oxygen as a
fed in the fluidized bed reactor. The reactor effluent gases quench
cooled with circulating EDC followed by caustic neutralization. The
neutralized gas is cooled to condense EDC and water. For the EDC
purification, they split crude EDC into light ends, heavy ends, and
pure EDC which is cracked to yield VCM. The VCM purification is
similar to the Stauffer technology.

Toyo Soda Technology:

About Toyo Soda:
"Toyo Corporation is the parent company of a Japanese chemical
and specialty products and materials group that comprises 132
companies worldwide and a multiethnic workforce of more than
11,000 people." The parent company was established in 1935 and
it's named Toyo Soda. In 1987 the name of company changed to
Tosoh Corporation. One of the company products is Vinyl Chloride
Monomer (VCM) which developed by the oxy-chlorination process.

"This process allowed Tosoh to maintain the largest production

capacity of VCM in Japan."
Toyo Soda Process:
In the direct chlorination section, 100% pure ethylene and brine
electrolysis cell chlorine (97.25% v/v) containing by volume 2% O2,
0.5% N2, 0.15% CO2 and 0.1% H2 are reacted in the "boiling liquid"
reactor in the presence of FeCl3 catalyst, at 1 atm. The boiling
solvent is the product itself, EDC (at start-up, there is EDC and
catalyst in the reactor vessel). The conversion of Cl 2 is 100%. One
the Toyo technology advantages is

the better quality of EDC

produced and economy of energy since the heat of reaction is used

to boil-off EDC (at 1 atm and 85 C) and small amounts of byproducts. The EDC vapor (and by-products) is condensed completely
and the liquid stream containing some gases is sent to a knock out
drum where all gases disengage and are removed from the top
before being sent to gas treatment and disposal. The bottom
product of knock out drum is almost EDC with some by-products is
mixed with crude EDC produced from oxy-chlorination section,
before being sent to storage in large tanks.
In the oxy-chlorination section, pure ethylene (same source as for
direct chlorination), pure oxygen (from a neighboring air plant), and
the recycled HCl (coming from VCM purification section) are fed to
the fluidized bed reactor with CuCl2 catalyst supported on Alumina.
All feed streams are at 2.2 atm and preheated to 160 C. For safety

reason, ethylene and oxygen are not mixed outside the reactor. The
reaction takes place in the vapor phase at 250 C and 2 atm. The
conversion of HCl is 100%. The vapor product is quenched to 35 C
and the liquid is sent to a 3 phase separator phase separator where
95% v/v of water initially present and all gases are removed
(aqueous stream and gas stream of the 3-phase separator) and sent
to waste treatment. The organic stream containing EDC, by-products
and some water is sent to a dehydrator column (azeotropic
distillation) to remove water from the organic phase. Water is
removed from the top of the column (because of the azeotrope) and
EDC with by-products from the bottom. The bottom stream
containing crude EDC is mixed with EDC from the direct chlorination
section and recycled EDC from the VCM purification section before
being pumped to storage tanks at 35 C. stored crude EDC is then
pumped to the EDC purification section to obtain pure EDC suitable
for cracking. [16]
The EDC purification section consists of two distillation columns: a
"light ends" column to remove low boiling impurities and a "heavy
ends" column to remove higher boiling impurities. These impurities
take place as by-products in the 3 reaction sections. In the light
ends column, all low boiling components are removed as top
product at 20 C and sent to waste treatment (these are chlorinated
products and can be burnt to produce HCl which can be used to
produce low grade hydrochloric acid to adjust pH in water treatment

sections). The bottom product is pumped to the heavy ends column

at 115 C. In the heavy ends column, pure EDC is obtained as top
product at 70 C and the bottom product (at 120 C) is a mixture of
high boiling chlorinated components which can be mixed with the
low boiling by-products to produce hydrochloric acid. Pure EDC is
then pumped to the EDC cracking reactor (furnace heated with
natural gas fuel). It is assumed both columns are 100% efficient.
Pressure in the EDC purification train is maintained at 1 atm
throughout.
The EDC cracking section is made up of a tubular reactor, arranged
in serpentine vertically. Pure EDC is pumped to 10 atm and
preheated to 220 C before it enters the cracking tubes maintained
at 500 C, to undergo decomposition into VCM and HCl, and also to
some by-products. The EDC conversion is limited to 55% to avoid
coking of the tubes. The cracking reactor effluent emerges at 500 C
and 9 atm, and is quenched to 100 C. The pressure after the direct
contact heat exchanger is still 9 atm in order to keep the phase in a
liquid state.
In the VCM purification section, the cooled cracking product stream
is fed to a distillation column "HCl column" to recover 100% of HCl
at the top of the column at 5 atm and -30 C. HCl recycled to the
oxy-chlorination reactor after preheated to 160 C and 2.2 atm. The

bottom product of HCl column is pumped to the VCM column to

recover pure VCM from the top of the column at 10 C and 2 atm.
VCM is sent to storage (spherical tank). The VCM column bottom
product consists of EDC and by-products. These are recovered at
120 C and 6 atm. This stream is throttled down to 1 atm and cooled
in a heat exchanger to 35 C before being recycled and mixed with
EDC from the direct chlorination and oxy-chlorination reactors.
Columns in the VCM purification train are assumed to be 100%
efficient.

Vinnolit Technology:
About Vinnolit:
Vinnolit is one of the most common chemical companies in Europe and
worldwide producing EDC, VCM, and PVC. It is a technical leader in specialty
PVC. "Vinnolit was founded in 1993 as a joint venture of the PVC divisions of
Hoechst AG and Wacker Chemie GmbH."
Vinnolit Process:
The modern Vinnolit process for the production of VCM has many
distinctive features. One of these distinctive features is high
operational

reliability

(reliable

reaction

control).

Also,

it's

specialize by high economic efficiency (High yield, low maintenance

cost).

Moreover,

extremely

low

pollution

levels

(low

VCM

emissions).
For Vinnolit process, in the direct chlorination section pure ethylene
and brine electrolysis cell chlorine (97.25% v/v) containing by

volume 2% O2, 0.5% N2, 0.15% CO2 and 0.1% H2 are reacted in a
conventional or in a boiling reactor at a temperature between 80120 C and pressure between 1-2.5 bars. The catalyst used in boiling
reactor is an organic compound to suppress the formation of byproducts and ensure higher selectivity to EDC. "Thus the Vinnolit
direct chlorination process combines the energy efficiency of high
temperature

chlorination

(HTC)

with

the

EDC

purity

of

low

temperature chlorination (LTC)."[10] The EDC produced by direct

chlorination is directly fed to the thermal cracking without any
farther purification.
In the oxy-chlorination section, the EDC produced in a fluidized bed
reactor by highly exothermic reaction at temperature >200 C
between ethylene, hydrogen chloride, oxygen and complicated
inorganic catalyst. "The excellent distribution in the fluidized-bed
makes it possible to maintain a constant temperature to ensure low
by-product formation and to achieve optimum process control."
Produced gases stream quenched and the EDC is condensed with
the aid of chilled water in a multi-stage condensation unit. The crud
EDC sent to the purification and then to the cracking.

For the EDC purification section, all EDC produced from oxychlorination and the recycled EDC from cracking enter the heads
column in order to remove the water and lo-boiling ends. The top
product (water with small quantities of chlorinated hydrocarbons

and sodium chloride) sent to the waste water treatment. The bottom
product pumped to the next distillation column "high-boil column" to
remove high-boil components and then to the vacuum column to
remove more high-boil ends. The bottom product of the vacuum
column sent to the incineration unit.
The EDC cracking takes place in a cracking furnace heated by fuel.
VCM, HCl and by-products are produced at a temperature >480 C.
"By incorporating a newly developed external EDC pre-evaporation
facility, the formation of coke in the cracking furnace is considerably
reduced."
The VCM purification section consists of three columns HCl column,
VCM column, and HCl stripper. In the HCl column, the hydrogen
chloride is recovered and recycled to the oxy-chlorination section.
The top product of the VCM column is pure VCM (HCl content <1
ppm). Any HCl traces removed from VCM in the HCl stripper.

Technologies Comparison:
The table below shows the comparison between Vinnolit, Toyo,
Stauffer, and MTC technologies based on some important criteria,
which are energy requirement, economics, safety, environmental
impact. In fact, number of columns affect energy requirement and
economics, safety and environmental. Vinnolit and Toyo have many
similarities in energy requirement, safety, and environmental
impact. Both of them have low energy consumption due to the
utilization of reaction and waste gas heat. Moreover, safety and

environment impact are very important criteria in the technology

selection. Toyo and Vinnolit consider high safety standard, O 2
content < 1%. Also, the pollution level is extremely low, where the
waste water quantities with EDC/VCM content < 1 ppm. The
difference between them was in the economics, since Vinnolit has
more columns than Toyo. In other hand, Stauffer and MTC have
number of columns more than others; therefore the required energy,
economics cost and safety, environmental impact will increase.

Table.2.1: Technologies comparison.

Criteria
Toyo

Technologies
Vinnolit Stauffer

MTC

Soda

/2

/2

/2

Energy

/2
2

1.5

Requirement
Economics
Safety
Environmental

2
2
2

1.5
2
2

1.5
1
1

1.5
1.5
1.5

Impact
Total /8

7.5

4.5

Based on these criteria, Technik co. selected hybrid between both

Toyo and Vinnolit technologies, since there are many similarities
between them.

2.8) Conclusion:

In conclusion, several technologies for VCM process verify around

the world. Some of these technologies are very common like Vinnolit
and Toyo. Technik co. studied all available technologies and
eliminated some of them, which didn't match with Technik feed
stocks. Finally, based on many criteria a hybrid between Toyo and
Vinnolit technologies selected to be use in Technik co.