3

Recycling of Poly Vinyl Chloride (PVC)

Dr. M. Naseem Akhtar

Center for Refining & Advanced Chemicals
 PVC 3
Poly Vinyl Chloride (PVC) is produced by polymerisation of vinyl chloride monomer

• Vinyl Chloride is produced by reaction of ethylene with chlorine

Dehydrogenation

• Vinyl Chloride is also produced by reaction of acetylene with hydrochloric acid

 Recycling of PVC 3

• PVC is a versatile polymer and is ranked second behind polyethylene in terms of

consumption
• Recycling of PVC is not wide spread because PVC is mainly used in long term
applications
• Level of PVC in municipal waste is negligible 0.5-0.7 wt. %
• In hospital waste 1.4-3.7 wt. %
• PVC has good chemical resistance and can be fabricated by extrusion, calendaring,
moulding, film blowing and coatings
• PVC is being used in durable applications e.g. pipes, window profile, wire & cable
insulation & flooring
• PVC contains 57 wt. % chlorine & 43 wt. % ethylene
• Therefore PVC is effectively recycled to recover chlorine and then using it to
produce new vinyl chloride monomer
 PVC applications & Usage in idustries 3

Application Area of PVC Principal Industries using PVC

Building &
con-
sytruction
Flexible Footwear 53%
2% Others
tubes 5% Clothing & Domestic
4% Others
footwaer Applications 8%
Coatings Furniture 3% 1%
4% 3%
Pipes &
Flooring Fittings Transport
5% 28% 3%

Vottles Leisure
8% 4%

Wire &
Cables
9%

Rigid
Cable insu- Profile
lation 17%
9% Film & Sheet
18%
Packaging
16%
 3
Barriers to PVC recycling

• Contamination
• PVC bottles are not easily identifiable as PET drink
bottles or HDPE milk bottles.
• PVC bottles are available in wide range of styles &
capacity they can be clear or opaque, glossy or
frosty, handled or plain
• Many clear bottles appear similar to PVC such as
glycol modified PET (PETG), polycarbonate etc.
• It hamper recycling of post consumer containers,
sorting is laborious, expensive and lack reliability.
• However XRF equipment can be used for this
purpose
 Barriers to PVC recycling 3

• Thermal Instability of PVC

• Thermal degradation of PVC is well known due to defects in structure
• PVC needs thermal stabilizers during processing to capture HCl evolved during
degradation
• Since thermal stabilizer is consumed during processing therefore recycled PVC
have lower thermal stability than virgin PVC. Therefore recycled PVC is
restabilized using various additives.
• Multicomponent nature of PVC applications
• Many PVC applications e.g. wire insulation, PVC-clad dashboards, vinyl
upholstery etc. are comprised of PVC in combination with other polymers.
• Therefore it need extreme washing procedure including melt filtration
• Lower amount of PVC scrap
• Majority of PVC for recycling is not originated from post consumer sources but
from construction waste & cable insulations. Therefore collection volumes of
recoverable PVC are inadequate for economical recycling.
 Separation between PVC & PET 3
• A particular challenge in PVC bottle recycling is to remove PET
contaminations. A wide variety of separation techniques for PVC &
PET are available:
• Manual sorting 3
• Bottles can be sorted by number of recycling as 1 for PET & 3 for PVC
• PVC tends to have slightly blue tint while PET appears colourless
• Under UV light PVC bottles look different than PET
• Automatic Sorting
• Special methods for automated separation of PVC & PET have been
developed because their densities are comparable so sink/float method
doesn’t work
• Polarized light
s
• An optical light based on the polarized light can sort clear PVC bottles t o scillate
igh
ized l only
from PET Polar direction
e
in on
• PET tends to glow under polarized light whereas PVC is transparent.

Note: Polarized light waves are light waves in which the vibrations occur in a single plane. The process of transforming unpolarized light into polarized light is known as polarization
 Separation between PVC & PET 3
• Softening Point
• PVC (200C) & PET (260C) differs by 60C in their softening points
• The hot belt separator is physical method for sorting PVC flakes
from PET
• The PVC softens and stick to hot belt while PET does not and fall off
as belt turns upside down, while PVC is scrapped off

• Electrostatics
• PET & PVC can be separated by differential triboelectrification
• The exchange of electrostatic charge between two surfaces when
they are brought into contact within each other is called
triboelectrification
 3
Separation between PVC & PET
X-Ray Fluorescence (XRF)
• Whenever a sample is bombarded with X-rays,
it causes ejection of an electron from the
inner shell of an atom
• Once an electron is ejected from inner shell
another electron from outer shell drop-in to
fill the space.
• This phenomenal result into emission of
fluorescence radiation.
• Kα & Kb are fluorescence radiation generated,
which is characteristic of each element
 Separation between PVC & PET 3
X-Ray Fluorescence (XRF)
• Cl atom present in PVC emit a characteristic X-ray
signature which is easily detectable by X-Ray analyzer.
• Whereas, PET having atoms with lower atomic wt. emit
lower back scattering that barely register any response
on X-Ray analyzer.
• XRF based system can detect PVC bottles in a stream of
PET bottles at rate of 10 bottles per second
Limitations
• This system is quite expensive
• Plastic flakes can’t be used for separation on this system
• Bottles need to pass within 6mm of XRF detector
• PVC bottles with thick paper-label can not be detected,
because low energy X-rays can’t pass through thick paper
 Size Reduction 3

• The ambient grinding of PVC produces high amount of fines

relative to PET. Therefore by simple sieving PET carse
particles can be separated from PVC fine particles. Cryogenic tunnel

• Cryogenic Grinding
• This process uses liquid nitrogen (-196C)to embrittle the
polymer before grinding.
• This process is well suited for PVC and result into uniform
particles as compared to that of mechanical grinding
• This method help in avoiding thermal degradation of PVC Grinding Mill

• This method is specifically used for PVC cable insulation.

Granulated cable is fed into cryogenic tunnel sprayed with
liquid N2. The cooled material is finely ground in grinding mill.
Liquid N2 vapours are fed to hopper to precool the material.
• The ground material is passed over electrostatic separator to
separate copper metal from PVC.
 Melt Filtration 3

• Several contaminants e.g. particulate matter, paper, metals, PET etc.

can cause moulding imperfections in recycling of PVC. Therefore
melt filtration of recycled PVC is required to produce high quality

Back Pressure (PSI)

Back Pressure (PSI)
PVC extrudates.
• Melt filtration is generally performed just before the die, where melt
is well plasticized. The non-melt impurities are removed by fine
mesh screens.
• The major problem in melt filtration is level of contaminant as above Area of filter screen blocked (%)
Time (min.)
certain threshold value these screens are blocked and result into
pressure build-up leading to excessive back flow in the extruder.
• Back pressure builds up quickly as effective screening area of filter is
blocked
• Level of contaminants play crucial role in pressure build up. The
impurity level must be about 0.1 vol. % or less to get optimum
filtration.
• The continuous screen changers are most suitable for PVC melt
filtration
 Mechanical Recycling of PVC-Bottles 3
• PVC bottles are widely used because of
their high clarity, easy moldability & cost
advantage over PET
PVC Paper,
• There are two major bottle recycling PVC
Bale Sorting Station
Granulator
Dynamic Spin
dryer
film,
Breaker dirt
process for PVC bottles Bale

1. Solvay Process
PE, PET
• PET bottles are separated from PVC using
either manually with help of UV lamp or by
automatic XRF system.
Static Spin
• The bottles are then granulated Purified
PVC
Buffer dryer
Density
Densitywith
Separation Density Silo
PVC
• The contaminant are removed using Extruder melt filter Separation
Separation

centrifugal separators, metals are removed

by electrostatic separators and PE & PP are PE, PP
separated sink/float separator.
• PVC is then passed through extruder and
contaminants are removed through melt Solvay Process
filtration
 Mechanical Recycling of PVC-Bottles 3
2. GEON Process
Granulator

• This process has been developed by GEON company for

purification of post consumer PVC bottles.
ASPIRATION Fines, Paper, film
• This process uses series of density baths.
• PVC bottles after granulation are passed through
aspirators to remove fine, paper & films
PE, PP, Paper
Density
• The ground flakes are then washed by water at 80C; Separation
Water Bath (80C)
PE, PP & paper are separated by float/sink method
• Then flakes are passed through aqueous solution of PVC, PET, PC
calcium nitrate (d=1.35 g/cm3) to remove Al, PET & dirt PVC, PET copolymer,
PC
by sinking. Density
Calcium nitrate
PET copolymer, Density
Calcium nitrate
Separation
Separation PC solution (d= 1.30)
solution (d= 1.35)
• The flakes are then passed through another bath having
calcium nitrate (d=1.30 g/cm3). Pure PVC sinks in this
Pure PVC
bath and separated. PET, Al, Dirt

GEON Process
 Mechanical Recycling of PVC-Cables 3

• Wire & cable insulation is a

major application area of PVC.
• Previously cable scrap was finely Lighter components
Accept Stream
shredded (fluff) and disposed off Shredder
Grinder Magnets
Gravity
Separator
Vibratory
separator

by landfilling.
Fe metal Cu metal Fines & Overs
• However with introduction of PE PE
High Attrition
stringent guidelines regarding washer

leachate of toxic material it is Cu, Dirt & Grease

considered as hazardous Hydro cyclone
Salt solution
Hydro cyclone
Salt solution
Hydro cyclone
Salt solution

material and is not allowed to (d=1.0 g/cm3) (d=1.2 g/cm3) (d=1.4 g/cm3)

discard by land fill.

• Three hydro cyclones with salt Heavy components Heavy fraction,
Purified PVC
solution having densities 1.4, 1.2 PTFE, PVDF etc.

& 1.0 g/cm3 are used to separate Hydro cyclone

PVC from other contaminants
 Mechanical Recycling of PVC-Cables 3
• PVC cables can also be recycled using cryogenic method (i.e. liquid
N2).
• The copper is separated from PVC insulation by electrostatic
separator
• Applications of PVC from wire & cables
• Floor mats
• Garden hose
• Floor tiles
• Close-loop recycling by cable jacketing with 30% recycled PVC is also
used. PVC recycled is suitable for this purpose because it is already
lead-stabilized a requirement of cable industry
• Close-loop recycling need high grade purity of recycled PVC which can
be achieved by melt filtration. The critical property in this application is
dielectric strength. Presence of traces of conductors (copper fines) can
have drastic effect on dielectric strength of the insulator.
 Recycling of –PVC Pipes 3
• PVC pipes are widely used in
water & sewerage system.
PVC shreds 30 cm long
• Used PVC pipes can be recycled Vibratory
PVC Sand
using Solvay recycling process
Crusher Sieving Grinder Sieving & dirt

involving size reduction &

purification. PE Sand & dirt

• This is a dry process therefore

no problem of disposal of waste Accept PVC
(1.5-15mm)
water. Grinder
Shaking Sieving
Overband
Magnets
Al & Sand Sieving Screen
(< 8 mm)

Reject PVC Fe metal

Al & Glass (<1.5mm>15mm)

Micronizer

Purified PVC powder (~800 mm)

PE, PP
 Recycling of –PVC Window Frames 3
PVC shreds 15-45 mm
Eddy current separator
• PVC window frames can be Repelled

recycled into PVC powder to be Shredder

Magnetic
Separator
Sieving
metals

reused for production of new Magnetic Rotor

window frames.
Fines Non
Fe metal
• An eddy current
Nonferrous
(<4 mm) metals metals

separator uses a powerful
magnetic field to separate non- Used PVC window frames Hot Air H2O

ferrous metals ( Al, Zn, Cu etc.)

from non metallic material. Colour
Dry PVC
Dryer Air Tables Air Tables
Sorting Wet Mill

White PVC
H2O Glass Wood
Non-White PVC Dirt

Applications of recycled PVC window frames

• The recycled PVC is used in production of new window profiles usingcoextrusion method
• The coextruded profile have inner layer of recycled PVC while outer layer of virgin PVC
• The new frames incorporate 80 wt. % of recycled PVC and exhibit properties comparable to virgin PVC frames
 Applications of mechanically recycled PVC 3
Virgin PVC

• Coextruded PVC pipes

• Post consumer PVC recycle from scrap bottles &
pipes can be used to produce new pipes by
incorporating recycled material as middle layer
using coextrusion process. These pipes meet
technical specifications for building sewerage pipes Recycled PVC
& building discharge pipes.
• The middle layer of recycled PVC can be foamed by
the addition of blowing agent to improve the
strength properties of the pipes.
 Applications of mechanically recycled PVC 3

• Co-extruded Cladding
• Recycled PVC is used to make coextruded vinyl cladding
material for house siding
• The cladding has a low-density foam core (recycled PVC) and a
coextruded solid skin of virgin PVC to provide good finishing
• Rigid foamed profile application is well suited to use recycled
PVC bottle material because the cellular structure of foamed
material is relatively insensitive to the presence of
contaminant.
• Mechanical properties are maintained despite the presence of
particulate contamination
 Applications of mechanically recycled PVC 3

Coextruded Window frames

• PVC window frames are being produced by coextruding inner layer of
recycled PVC (80 %) and an outer layer of virgin PVC
Conduit for Cables
• Recycled PVC is being used to make conduit for use in telephone networks and for
TV cables
Pipe Fittings
• Injection moulded pipe fittings produced from cryogenically ground PVC
bottles are in ideal applications for recycled PVC

Floor Coverings
• PVC floor coverings are shredded and cryogenically ground to produce
new floor coverings from recycled PVC

Fibres
• PVC fibres produced from post consumer bottles are being used in
pullovers, scarves & socks