Production of Ethylene chloride:

Ethylene chloride (C2H4Cl2), also called ethylene dichloride or 1,2-dichloroethane, a

colorless, toxic, volatile liquid having an odor resembling that of chloroform. It is denser
than water, and it is practically insoluble in water.
Nearly 20 million tons of 1,2-dichloroethane are produced in the United States, Western Europe,
and Japan. Ethylene chloride is produced by the reaction of ethylene and chlorine. The annual
production of ethylene chloride exceeds that of all other organ halogen compounds and ranks
behind only that of ethylene and propylene among all organic compounds. Almost all ethylene
chloride is converted to vinyl chloride for the production of polyvinyl chloride,
Vinyl chloride is produced in a two step process from ethylene. Ethylene first reacts with
Chlorine to produce Ethylene dichloride. The purified Ethylene dichloride undergoes selective
cracking to form vinyl chloride. We first present the process technology associated to Ethylene
Chloride

C2H4 + Cl2 → C2H4Cl2

Undesired products: Propylene dichloride and Polychloroethanes.Reaction occurs in a liquid
phase reactor with ethylene dichloride serving as the liquid medium and reactants reacting the
liquid phase. Catalyst is FeCl3 or Ethylene dibromide

2 H2C=CH2 + 4 HCl + O2 → 2 ClCH2−CH2Cl + 2

H2O.
C2H4 and Cl2 are mixed and sent to the liquid phase reactor.

• Here, the feed mixture bubbles through the ethylene dichloride product medium.

• Reactor operating conditions are 50°C and 1.5 – 2 atms.

• The reaction is exothermic. Therefore, energy is removed using either cooling jacket or external
heat exchanger.

• To facilitate better conversion, circulating reactor designs are used.

• FeCl3 traces are also added to serve as catalyst.

• The vapor products are cooled to produce two products namely a vapor product and a liquid
product. The liquid product is partially recycled back to the reactor to maintain the liquid medium
concentration.

• The vapor product is sent to a refrigeration unit for further cooling which will further extract
ethylene dichloride to liquid phase and makes the vapor phase bereft of the product.

• The liquid product is crude ethylene dichloride with traces of HCl. Therefore, acid wash is carried
out first with dilute NaOH to obtain crude ethylene dichloride. A settling tank is allowed to separate
the spent NaOH solution and crude C2H4Cl2 (as well liquid).

• The crude ethylene dichloride eventually enters a distillation column that separates the ethylene
dichloride from the other heavy end products.

• The vapor phase stream is sent to a dilute NaOH solution to remove HCl and produce the spent
NaOH solution. The off gases consist of H2, CH4, C2H4 and C2H6
Production of vinyl chloride
The direct chlorination method of vinyl chloride production begins with its namesake: the direct
chlorination of ethylene to produce 1,2-dichloroethane. Ethylene and chlorine (streams 1 and 2) are
fed in stoichiometric amounts at 25°C and 1 atm to a 1.5 atm bubble column reactor (R-100) that
circulates the reactant gases via sparger dispersion through liquid 1,2-dichloroethane that is
maintained at 90°C by a cold water stream (E-100). The bubble column reactor design maximizes
ethylene mass transfer and its use in industry is well-characterized (Orejas, 2001). The product
stream exiting the direct chlorination reactor is a 97% pure 1,2-dichloroethane stream (stream 3)
with limited side reaction and unreacted feed compounds (see Appendix A for a thorough
description of process unit designs and a discussion of the various reactions and kinetics involved
with this system). R-100 also contains ferric chloride that acts as a Lewis acid catalyst, polarizing
chlorine to increase its electrophilic activity and encourage attack on ethylene’s double bond
(Wachi & Asai, Kinetics of 1,2-Dichloroethane Formation from Ethylene and Cupric Chloride, 1994).

The 1,2-dichloroethane stream is joined by a recycle (producing stream 4) and fed through a
centrifugal pump (P-100; stream 5) and a fired-heat evaporator (E-101; stream 6) to achieve
pressurization to 26 atm, complete vaporization, and a temperature increase to 500°C. This stream
is flown into a pyrolysis furnace at the same temperature and pressure, where it is primarily
converted to vinyl chloride. Although a catalytic pyrolysis method exists, similar conversion levels
can be reached without a catalyst, making the non-catalytic approach a simpler, less expensive, and
more favorable method (Dreher, Torkelson, & Beutel, 2012; Rus, 2013). The furnace contents are
transferred to a quench tank (V-100; stream 7), which is maintained at 6°C and 12 atm by
circulating the liquid condensate exiting the pyrolysis furnace through a refrigerant-cooled
condenser system (P-101, E-102). The quench tank is a vital component of this process: Without
rapid cooling the pyrolysis reaction will continue, degrading desirable vinyl chloride and producing
additional unwanted side products.
The quench contents are fed to a 7-stage distillation column above stage 2 at 12 atm (T-100; stream
8) where HCl is recovered at 97% purity in the distillate (stream 9) and the remainder of the
pyrolysis products are fed in the bottoms stream to a second, similar, 9-stage distillation column
above stage 3 at 4.8 atm (T-101; stream 10). This column yields a 97.6% pure vinyl chloride stream
in the distillate (stream 11) and the 1,2-dichloroethane-rich bottoms stream is recycled ahead of
the centrifugal pump (stream 12).
 Extrusion of Plastics
Extrusion
Extrusion is a high volume manufacturing process. The plastic material is melted with the
application of heat and extruded through die into a desired shape. A cylindrical rotating screw is
placed inside the barrel which forces out molten plastic material through a die. The extruded
material takes shape according to the cross-section of die. The schematic of extrusion process is
shown in figure 1.
Working Principle
In this process, plastic material in the form of pellets or granules is gravity fed from a top
mounted hopper into the barrel. Additives such as colorants and ultraviolet inhibitors (liquid or
pellet form) can be mixed in the hopper. The plastic material enters through the feed throat and
comes into contact with the rotating screw. The rotating screw pushes the plastic beads forward
into the barrel. The barrel is heated using the heating elements up to the melting temperature of
the plastic. The heating elements are used in such ways that gradually increase the temperature of
the barrel from the rear to the front.
There are three possible zones in a rotating screw i.e. feed zone, melting zone, and metering
zone. In the feed zone, the plastic beads melt gradually as they are pushed through the barrel.
The plastic material is completely melted in the melting zone. A thermostat is used to maintain
the inside temperature of the barrel. The overheating of plastics should be minimized which may
cause degradation in the material properties. A cooling fan or water cooling system is used to
maintain the temperature of the barrel during the process.
At the front of the barrel, the molten plastic leaves the screw and travels through a screen pack to
remove any contaminants in the molten plastic. The screens are reinforced by a breaker plate.
The breaker plate assembly also serves to create back pressure in the barrel. The back pressure
gives uniform melting and proper mixing of the molten plastic material into the barrel. After
passing through the breaker plate, molten plastic enters into die. The die gives the desired shape
of plastic product. An uneven flow of molten plastic would produce unwanted stresses in the
plastic product. These stresses can cause warping after solidification of molten plastic. Plastics
are very good thermal insulators and therefore it is very difficult to cool quickly. The plastic
product is cooled by pulling through a set of cooling rolls.
Figure 1 Extrusion process
Extrusion Process Parameters
There are five important process parameters to be considered before extrusion process:
Melting temperature of plastic
Speed of the screw
Extrusion pressure required
Types of die used
Cooling medium
Screw Design:
The design of screw is important for plastic processing. It has mainly three different functions:
namely, feeding mechanism; uniform melting and mixing of plastic and finally it generates the
pressure to push the molten material through die. A screw length (L) is referenced to its diameter
(D) as L/D ratio. Generally, L/D ratio is used as 24:1, but for more mixing and output, it may
increase up to 32:1. There are three possible zones in a screw length i.e. feed zone, melting zone,
and metering zone.
(a) Feed zone: In this zone, the resin is inserted from hopper into the barrel, and the channel
depth is constant.
(b) Melting zone: The plastic material is melted and the channel depth gets progressively
smaller. It is also called the transition or compression zone.
(c) Metering zone: The molten plastic is mixed at uniform temperature and pressure and
forwarded through the die. The channel depth is constant throughout this zone.
Types of Extrusion Process
The extrusion process is broadly classified into seven different types depending upon the specific
applications.
(a) Sheet/Film Extrusion
In this extrusion process, the molten plastic material is extruded through a flat die. The cooling
rolls are used to determine the thickness of sheet/film and its surface texture. The thickness of
sheet can be obtained in the range of 0.2 to 15 mm. The thin flat sheet or film of plastic material
can be made. Generally, polystyrene plastic is used as a raw material in the sheet extrusion
process.
(b) Blown Film Extrusion
In the blown film process, the die is like a vertical cylinder with a circular profile. The molten
plastic is pulled upwards from the die by a pair of nip rollers. The compressed air is used to
inflating the tube. Around the die, an air-ring is fitted. The purpose of an air-ring is to cool the
film as it travel upwards. In the center of the die, there is an air inlet from which compressed air
can be forced into the centre of the circular profile, and creating a bubble. The extruded circular
cross section may be increased 2-3 times of the die diameter. The bubbles are collapsed with the
help of collapsing plate. The nip rolls flatten the bubble into double layer of film which is called
layflat. The wall thickness of the film can be controlled by changing the speed of the nip rollers.
The layflat can be spooled in the form of roll or cut into desired shapes. Bottom side of the
layflat is sealed with the application of heat, and cut across further up to form opening; hence it
can be used to make a plastic bag. The die diameter may vary from 1 to 300 centimeters.
Generally, polyurethane plastic is used in this process. The schematic of blown film extrusion is
shown in figure 2.
Figure 2 Blown film extrusion
(c) Over Jacketing Extrusion
This is also called wire coating process. In this process, a bare wire is pulled through the center
of a die. There are two different types of extrusion tooling used for coating over a wire i.e.
pressure or jacketing tooling as shown in figure 3. If intimate contact or adhesion is required
between the wire and coating, pressure tooling is used. If adhesion is not desired, jacketing
tooling is used. For pressure tooling, the wire is retracted inside the die, where it comes in
contact with the molten plastic at a much higher pressure. For jacketing tooling, the wire will
extend and molten plastic will make a cover on the wire after die. The bare wire is fed through
the die and it does not come in direct contact with the molten plastic until it leaves the die. The
main difference between the jacketing and pressure tooling is the position of the wire with
respect to the die.
Jacketing coating Pressure coating
Figure 3 Over jacketing extrusion process
(d) Tubing Extrusion
In this process, the molten plastic is extruded through a die and hollow cross sections are formed
by placing a mandrel inside the die. Tube with multiple holes can also be made for specific
applications, by placing a number of mandrels in the center of the die.
(e) Coextrusion
Coextrusion is the extrusion process of making multiple layers of material simultaneously. It is
used to apply one or more layers on top of base material to obtain specific properties such as
ultraviolet absorption, grip, matte surface, and energy reflection, while base material is more
suitable for other applications, e.g. impact resistance and structural performance. It may be used
on any of the processes such as blown film, overjacketing, tubing, sheet/film extrusion. In this
process, two or more extruders are used to deliver materials which are combined into a single die
that extrudes the materials in the desired shape. The layer thickness is controlled by the speed
and size of the individual extruders delivering the materials.
(f) Extrusion Coating
Extrusion coating is used to make an additional layer onto an existing rollstock of paper, foil or
film. For example, to improve the water resistant of paper polyethylene coating is used. The
applications of extrusion coating are liquid packaging, photographic paper, envelopes, sacks
lining for fertilizers packaging and medical packaging. Generally, polyethylene and
polypropylene are used.
Materials Used
The different types of plastic materials that can be used in extrusion process are Polyethylene,
Polypropylene (PP), Acetal, Acrylic, Nylon (Polyamides), Polystyrene, Polyvinyl Chloride
(PVC), Acrylonitrile Butadiene Styrene (ABS) and Polycarbonate.
Applications
The extrusion process is used for manufacturing rods, plates and tubes, wire and cable coating,
hose liners, hose mandrels, filaments, sheet, multilayer film, medical packaging and food
packaging, etc.
Advantages
High production volumes
Relatively low cost as compared with other molding process
Design flexibility
Short lead times
Coating of wire can be done to achieves desired properties
Continuous part can be produced
Disadvantages:
Limited complexity of parts
Uniform cross section can only be produced