S-PVC Manufacturing

Technology
By
(Luqman Ahmad Shahid)
Nov 2012

Engro Polymer & Chemicals Limited

Outline

PVC Process & quality parameters

Kinetics of PVC polymerization

Suspending agents overview

Initiators Overview

PVC Process Chemicals

Productivity enhancement & new Technologies

PVC Process & Quality

Parameters

PVC plant PFD

RECOVERED

VCM

VCM RECOVERY
SECTION

VCM
PW, AGENTS, ADDITIVES
STRIPPING
COLUMN
POLYMERIZER

RECOVERY TANK
SLURRY SURGE TANK

PVC
SCREEN
CENTRIFUGE
SLURRY TANK

S
DRYER

SILOS

HOPPERS

PVC Quality Control

COA
QUALITY
LIMITS

OPS.

EPCL
LABORATORY

24 HOURS
SAMPLING
SCHEDULES
PM&S
Proce
ss
VCM RECOVERY
SECTION

PRODUCT
READY FOR
SHIPMENT

SABZ

POLYMERIZER
CENTRIFUGE

PVC
SABZ

SCREEN

SABZ

SABZ

HOPPERS
SLURRY TANK

DRYER

SILOS

PVC Quality Parameters

K Value

Bulk Density

Volatile Matter

Particle Size Distribution

Plasticizer Take Up ( PTU )

Plasticizers Absorption Time ( PAT )

VCM in product

Yellow Index ( YID )

Thermal Stability ( TS )

Foreign Particles

Fish Eye ( FE )

Volume Resistivity (VR)

6

Process Engineering Check Point

Lab Sampling Schedule. (routine & no routine sampling of product)

DCS Monitoring of critical parameters

Reaction temperature deviations

Reaction conversions monitoring

Grade change Matrix. (included equipment jetting, flushing & inspection)

Kinetics of PVC Polymerization

PVC Polymerization

Free radical polymerization of VCM will give PVC

n[C2H3Cl]

~C2H3Cl~n

An exothermic reaction with heat generation of 23 Kcal/mol.

For PVC-1, total heat of reaction of 18400 Mcal/batch(50 Met of VCM) & for 80%
conversion heat removal required is14700 Mcal/batch.

For PVC-2 total heat of reaction 9200 Mcal & heat removal of 7200 Mcal for 78%
conversion for 25 Met of VCM charged

PVC Polymerization Reactions

Initiation

Propagation

Chain Transfer

Termination

Copolymerization

10

Principles of Kinetics

Rate of reaction is directly proportional to Reaction temperature & pressure.

Rate of reaction is directly proportional to monomer concentration/ purity of

monomer.

Rate of reaction is directly proportional to catalyst concentration.

11

Effect of Temperature

In PVC grades AU 58 & 60 has highest reaction temperature of 64.5 C so highest

rate of reaction & less batch cycle time.

AU 72 has minimum reaction temperature i.e. 52 C and less reaction rate & lowest
productivity.

Control of reaction temperature is important to maintain the required K-value (MW

or solution viscosity) of PVC.

If reaction temperature is high K-value will be low & vice versa due to chain transfer
effect.

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Reactivity of VCM

Major impurities include acetylene, vinyl acetylene, Butadiene, chloroprene, methyl

chloride, Iron, Propylene, etc. have effect on reactivity, thermal stability & color of PVC.

Acetylene & vinyl acetylene are most damaging for polymerization reaction as it
consumes catalyst amount (1 mole acetylene consume 1 mole catalyst).

Acetylene & Vinyl Acetylene control of <3 ppm for normal reaction speed.

As polymerization reaction proceed, rate of reaction falls down due to monomer

starvation.

The ratio of fresh to recovered VCM is important in terms of reactivity of VCM, normally
it is 25% RVCM & 75% FVCM.

Moisture & foam carry over in RVCM reduce reactivity.

13

PVC Reaction Profile

Conversion[wt%]

Heat generation patten

(C26E/C29E)

Q[*10^2 Mcal/h]
Temperature[deg C]

100
95
90
85
80

Conversion, % / Heat

75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
0.00

0.50

1.00

1.50

2.00

2.50

3.00

3.50

4.00

4.50

5.00

5.50

Polymerization time [h]

6.00

6.50

7.00

7.50

8.00

8.50

9.00

9.50

10.00

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Optimum Reaction Conversion

Reactions are never taken to 100% Conversion.

Very slow rate of reaction in end phase of reaction because of monomer starvation.

Thermal stability becomes low at high conversion defect structures formed at high
conversion due to side reactions.

On the other hand, low reaction conversions leads to high variable cost, low bulk
density & more VCM emissions due to increase in RVCM.

Optimum reaction conversion is from 80 to 85%.

15

Suspending Agents

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Purpose of Suspending Agents

VCM & water are almost insoluble with each other & their dispersion is
achieved by using suspending agents

Suspending agents reduces surface tension & forms a protective layer

around VCM droplets.

PVC suspending agents are Poly vinyl alcohols (PVA) & Hydroxyl Propyl
Methyl Cellulose (HPMC).

They influence PVC particles, imparting consistency in shape/ size,

distribution of pores, and control Bulk Density and number of Fish Eyes
produced by forming a protective layer around VCM droplet.

Change in concentration of agents, their amount or ratio with other

agents all effect the physical properties of resin.
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How PVA works

18

How PVA works

19

Formation of PVC Particles

20

Types of Suspending Agents

Primary suspending agents (PVAs)

Secondary suspending agents (PVAs)

Cellulosic agents (HMPC)

21

Initiators

22

Function of Initiators

Initiators are the organic peroxides which provide free radicals to start
PVC polymerization reaction.

Organic peroxide have low bond energy and breaks itself quickly to
give free radicals. Their energy of activation is only 25 to 40 Kcal/ mol at
25 C.

Initiator decomposition rate, radical energy levels, byproducts formed ,

shipping, storage and handling are the important factors which must be
considered for their use.

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Initiators Basics
Storage Temperature (Ts)
Maximum allowable temperature to store a catalyst at which negligible
decomposition in it.

Self accelerated decomposition temperature (SADT )

The lowest ambient temperature at which uncontrolled decomposition
of a catalyst starts. At this temperature, heat generated by catalyst is
greater than heat dissipated in the environment i.e. runaway condition
for catalyst.

Half Life Temperature (T10)

The temperature at which 50% catalyst amount is decomposed in 10 hrs.
It is a measure of catalyst free radical generation rate.

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Initiators Impact on PQ

Fish eye

Scale formation in the reactor causes the lowering of heat conductivity and
the formation of fish eyes. Initiators may be one of the factors for scale
formation.
The volatility of peroxides influences scale formation. Initiator with high
vapor pressure have low MW & cause high scaling & FE.

Initial color (YID) & thermal stability

Per-esters are excellent for Initial coloring due to their low free radical
production efficiency in PVC and low hydrogen abstraction ability. They
exhibit good thermal stability as compared to dicarbonates.

25

Selection of Initiators

When a single peroxide is used, the peak reaction rate increases rapidly.

To lower the peak heat load and use more of the heat removal
capacity, it is required to use two peroxides in combination.

One of the peroxides decomposes rapidly(low T10) at the beginning of

the reaction while the other decomposes slowly(high T10).

The faster decomposing peroxide is referred to as the front end peroxide

and the slower is referred to as the back end.

26

Selection of Initiators

Using a faster front end peroxide results in faster initial reactor rates, a
more constant rate of reaction and minimal heat kick.

The exact ratio of front and back end peroxides must be changed to
specific situations, conditions & reaction profiles.

At lower CW temperatures, the amount of front end peroxide to be

increased and back end peroxide to be decreased to gain a steady
reaction rate & profile.

Monomer impurities, reactor fouling, fluctuations in cooling water

temperature and changes in market demand are the reasons for
changing the ratio of front to back end peroxide.
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Process Chemicals

28

Presences of O2 in Reaction

VCM easily copolymerize with O2 forming Vinyl Chloride Polyperoxide (VCPP).

The VCPP tend to decompose at polymerization condition giving HCL, CO &

formaldehyde.

With HCl generation, acidity during reaction increase. (pH <4)

Thermal stability of PVC decreased with O2 content increase due to branch reactions
of VCPP.

Growing polymer chain tend to react with O2 much easily as compared to VCM. This
results in inhibition time during reaction.

Final MW or K-value of PVC decreases in the presence of O2.

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Acidic Slurry pH

Hydrolysis of VCM during reaction produce HCL (Acidity) i.e. pH value
b/w 2.5 to 4.

Residual O2 during reaction increase acidity

Following are the influence of acidity during reaction
1. Walls scaling increases as AFA efficiency affected
2. Agents efficiency may reduce
3. VCM recovery will be highly corrosive, problems for compressors
4. Very fine particles formation & foam carry over
5. Final color & thermal stability have effect

Use of Buffer agent during polymerization ( optimum pH range is 6.7 to 6.9)
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Basic slurry pH

At high pH, the droplet suspension formed are highly unstable and
the PVC consist of very large, coarse grains.

Basicity during polymerization reaction can only caused by caustic

carry over in reactor.

Sodium ions have adverse effects on agents performance.

PVA amount will be scarce due to high sodium ion.

Agglomeration and beads formation observed due to excess

caustic presence in charging VCM.

Two incidents of caustic carry over into reactor caused bead

formation at PVC-1.
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