UNIT-5

RECYCLING
AKASH SINGH
OF RUBBER 1808026
SUBMISSION DATE:-
11/04/2020
INTRODUCTION
• Until world war-2, only natural rubber was
processed. This has the main reason behind it that
rubber plasticizer penetrated natural rubber
evenly and bond cleavage was uniform. Natural
rubber plasticizer does not penetrate synthetic
rubber particles as easily and synthetics harden
under heat and pressure.
• Less susceptible to oxidation than natural rubber.
So today’s tyre contain a mixture of synthetic and
natural rubber. Thus compared to natural rubber,
they must be grouped to a finer mesh for better
oil absorption and more active chemical
reclaiming agents must be used.
PROBLEMS RELATED TO RUBBER RECYCLING

• Pollution reduction is problem that has troubled

the industry. Cost of air pollution equipment
makes it worse.
• Water pollution had to be reduced by installation
of recycling system.
• Contamination has always been a problem.
• Discovery of plastics and oil-extended rubbers and
drop in crude oil prices have led to reduction in
rubber recycling.
 
WHY RUBBER RECYCLING IS NECESSARY?

 
• Disposal of rubber waste problems us because it can be
breeding place for mosquito.
• Petroleum scarcity in Europe and other parts of eastern
hemisphere have resulted in use of recycled rubber as
fuel.
• Recycled rubber is less expensive than virgin polymers
and costs less to process because it consists of a blend of
45-50% rubber hydrocarbon, sulphur, accelerators, oils
and fillers.
• In a compound using small amount of recycled rubber, it
performs like processing aid by reducing polymer
breakdown time.
• Addition of recycled rubber permits lower
calendaring temperature.
• Temperature range is broader for compounds with
recycled rubber. This also reduces shrinkage and
swelling, increasing processing rates and improves
fabric penetration.
• Extrusion compounds containing reclaim (recycled
rubber) are less thermoplastic and holds their shape.
• Reclaim acts as a mould releasing agent.
• Adhesives contain reclaim exhibit more uniform tack
over a wider temperature range.
RECLAIM RUBBER
• It is the product resulting from the treatment of
vulcanized scrap tyres, tubes and other waste
rubber articles by the application of heat and
chemical agents, permitting the product to be as
processed, compounded and vulcanized.
• Reclaiming is essentially depolymerisation.
• PROCESS OF RECLAIMING:-
 Fine grinding of waste.
 Separation of fibres and metals
 Incorporation of reclaiming chemicals and oils
 Heat treatment
 Mechanical process of straining and refining
BASIC PROCESSES USED IN RUBBER RECYCLING

• Digester- is a steam pressurized tank equipped with

horizontal mixing paddles. The blend (oil and processing
aids in crumb rubber) is mixed at steam pressure of 10-17
atm for 4-6 hrs. After that it is washed and dried.
Compounding ingredients like carbon black, clay, etc. are
added to modify and maintain certain physical and chemical
property. Metal and other contaminants are removed using
extruders.
• Heater/pan process- Scrap is mechanical ground, mixed with
reclaiming agents, loaded into pan or devulcanizing boats
and auto clave at steam pressures of 10-14 atm for 3-8 hrs.
• Reclaminator- is a high pressure extruder which
devulcanizes fibre-free rubber. High pressure and shear
between the rubber mixture and the extruder barrel walls.
Devulcanization occurs at 175-205⁰C in 1-3 min.
RECYCLING OF RUBBER

Devulcanization
Physical Breaking
method the three
(breaking of dimensional
rubber network
physical formed
into finer during
and smaller vulcanizatio
pieces) n
METHODS OF CHARACTERIZATION

• Gel content is a method to check the efficiency of

devulcanization occurred in the rubber molecule.
• Gel Content = 1 - weight of rubber dissolved
insolvents/Weight of pure rubber compound.

• Crosslink density of the compound can estimated through

gel content. Higher the gel content higher is the crosslink
density.
• Crosslink density is measured through Flory Rehner
equation using equilibrium swelling method with toluene
as a solvent
• [X] = - [ln (1-Vrg) +Vrg + χV2rg ] / 2 V0 ѵ1/3rg 
• V0 = molar volume of the solvent
• Χ = rubber solvent interaction parameter
• SEM is mainly used in rubber to analyse the
particle characteristics, fracture analysis and
morphological analysis in the rubber compound
after the devulcanization.
• CURE CHARACTERISTICS Mooney viscosity and
other rheological properties are measured.
• FTIR is mainly used to analyse the structural and
functional changes especially changes in the main
backbone chain.
• Tensile strength and elongation at break upon
devulcanization.
• Thermal stability of the compound before and
after devulcanization using TGA.
 
DEVULCANIZATION METHODS
WITHOUT
USING SHEAR
FORCE.
CHEMICAL USE OF
SHEAR
FORCE.
• Various chemical reagents that help in the breakage of C-S
bonds (devulcanization of rubber).
• Many a time’s mechanically generated shear force is applied
with the chemicals for devulcanization.
• ADV; - can determine the various mono, di, polysulphidic
bonds broken down by measuring the crosslink density before
and after the treatment of chemicals.
• Devulcanizing agent; - diphenyl Sulphide, diarylsulphide,
thiosalicyclic acid, salts of lithium chloride, nitric acid.
 
Experimental method

• Vulcanized silicone rubber sheets containing fillers

were cut into pieces (about 2 * 3 * 4 mm3 in size).
• A mixture of 10 g of vulcanized rubber, 15 ml of
DEA, and 15 ml of hexane and 1.2 g of 25%
methanol solution of (CH3) 4NOH/KOH were
agitated under the solvent reflux for 5 h.
• When the silicone rubber was dissolved in the
solvent mixture, the mixed solution was filtered.
• After the fillers were separated by filtration, the
filtrate was transferred to a 100 ml flask, the
solution was heated to remove the solvent first
and then subjected to distillation at 170 8C/30
mm Hg for 3 h to obtain depolymerisation
PYROLYSIS OF NATURAL
RUBBER
• Pyrolysis of rubber wastes is an efficient thermo-
chemical means of generating high-value energy
and fuels. In this work, a variety of technological
tools were employed to characterise the pyrolysis
of natural and synthetic rubbers, which included
three tyres (natural rubber tyre, pneumatic tyre
and synthetic rubber tyre) and one natural rubber
mat. The composition of gas products was
determined by gas chromatography (GC). H2 and
CO were the major gases released from the
pyrolysis process although the evolution rates of
gas species differed for the four samples.
CHA
R
 
MICROWAVE

 
• A non-mechanical single stage process.
• Rubber containing polar groups such as EPDM,
Polychloroprene, Chlorinated polyethylene, Nitrile
rubber etc. can be devulcanized.
• ADV;- process has volumetric heating and promotes
uniformity in devulcanization in short span.
• On devulcanization rubber was made to blend with
the raw or virgin rubber which can act as filler.
• EG;- EPDM devulcanized by microwave treatment:
• ENERGY- 70-100 watt per hour
• FREQUENCY- 915-2240MHz.
• Small particle size so that it can pass through mesh.
 To check whether the rubber has devulcanized or not, it
was then blended with virgin EPDM rubber as:
10%DWR( dry weight rubber)+ 90% raw rubber.
• It results in:
 Tensile strength increased from 1115 psi-
11240psi.
 Slight improvement in shore A hardness from 58-
60.
• The major disadvantage comes during the
temperature control which is necessary as
exothermic reaction that takes place at 500˚F.
 
ULTRASONIC

• Use of high power ultrasonic waves for

devulcanization.
• Most efficient method.
• Almost every rubber can be devulcanized using the
ultrasonic process.
• The reactors are used which break the bond.
• Two types of reactors: 1. Coaxial reactor
• 2. Grooved barrel reactor
• Ultrasonic waves in the presence of pressure and heat
can break the rubber network while preventing the
main chain degradation.
• This makes the rubber soft which can be reprocessed
or can be blended with virgin polymers.
MICROBIAL

•  Enzymatic degradation of natural rubber and synthetic

natural rubber by the means of various enzymes-
Streptomyces, thermomonospora, xanthomonas, gordonia
enzymes.
• How do they break rubber network?
 They were allowed to cultivate on the rubber for several
weeks or months to analyse the efficiency of degradation.
 They are first swollen into an organic liquid and then the
microbes/enzymes are introduced to break the rubber
network.
 This is very slow process and absorption of sole carbon by
microbes adds to further increase in incubation (process of
developing) which is approximately up to 6 weeks and more.
 
PHASE TRANSFER CATALYSIS

• Phase transfer catalysis is an attempt to devulcanize waste

tire rubber containing SBR.
• Benzyl Sulphide, butyl Sulphide, butyl disulphide were used to
analyse the scission of rubber network.
• Low cost process but requires harsh conditions.
• Used to transfer nucleophiles into rubber to break the rubber
network.
• PROCEURE:
• At first, mono sulphides are oxidized into sulphoxide via
tertbutylammoniumchloride as a catalyst with Sodium
hypochlorite as an oxidizing agent.
• Further oxidation is done followed by the formation of
sulphone from sulfoxide.
• Elimination reaction sulfone are further cleaved with
potassium tert-butoxide as base to form sulfinic acid and a
site for unsaturation.
 
Devulcanization using supercritical CO2

• Most efficient and practical ways to devulcanize the cured

rubber.
• Most efficient in a way that even carbon black and silica which
are used as reinforcing filler in rubber cannot prevent it from
devulcanization.
• Devulcanization using CO2 with the help of diphenyl
disulphide:-
• Supercritical Carbon dioxide selectively broke the cross-linked
network of IR by impregnating Diphenyl disulphide into rubber.
(Solubility of CO2 increases with increase in pressure, hence a
quite high pressure was required to solubilize CO2 into
Diphenyl disulphide).
• Once the CO2 gets solubilize into Diphenyl disulphide, it gets
transferred into rubber quickly cleaving the crosslink network.
Thermal Depolymerisation

• Ceiling Temperature
• Temperature at which rate of polymerization and
depolymerisation becomes equal
• Extent of depolymerisation depends on:-
• Reactivity of polymer chain radicals in chain
transfer reaction
• Activity of available chain transfer sites in
polymer.
 HEATING
WIRES

1. Rubber is fed
2. N2 is purged in evaporation tube
3. The cracking products were led into
electrical Cottrell precipitator
4. The distillate are carefully rectified in
the fraction below 60ᵒC
5. Isoprene content was measured by
Famer Warren procedure
• Isoprene Content Determination
 0.5g of crude isoprene fraction is heated with maleic anhydride in
benzene at 100ᵒC for 2h. Benzene is distilled off in vacuum to dryness
 Gain in weight by the maleic anhydride gives isoprene content 
• Chemical depolymerisation using phenylhydrazine-FeCl2system
Natural Rubber latex (60%) is stabilized by SDS and stirred until pH
reached the investigated values
Then Phenyl hydrazine and FeCl2 are added at 30⁰C
At every reaction period, a portion of sample is isolated, coagulated in
ethanol, washed several times with water, dried in a vacuum oven at
room temperature.
The degree of degradation was studied by intrinsic viscosity (measured
by Ostwald viscometer at 3O0C in toluene)
• Influence of FeCl2:- At pH = 7
• The degree of degradation was affected by the concentration of FeCl2<
0.045 mmol. But degree of depolymerisation is independent of FeCl2
above 0.045.
• At pH = 10 Initially slow rate of depolymerisation due to slower
decomposition of complex at high pH. This can be accelerated by using
high amount of FeCl2
FILLER EXTRACTION
• The fillers separated by filtration from the
treatment with tetramethylammonium
hydroxide were heated under atmospheric
pressure at 150⁰C for 5 h.
• (CH3)4NOH is easily decomposed at high
temperatures, the fillers containing this base
can be purified for re-use simply by a heating
treatment.
 
EXPERIMENTAL
 A flask was charged with FeCl3 ( 8 mmol),
poly(dimethylsiloxane) (160 mmol) and 1-decanol( 640
mmol).
 The reaction mixture was stirred at 200 °C for 24 hours.
 Afterwards, water (100 mL) and HCl ( 1.0 mL) were added
and the mixture was stirred for 12 h at ambient
temperature. To the two phase system, dichloromethane (50
mL) was added.
 The aqueous layer was extracted with dichloromethane (2 ×
25 mL) and the combined organic layers were dried with
Na2SO4.
 Afterwards, the fatty alcohol layer was easily separated from
the aqueous layer.
 The dichloromethane was removed in vacuum.
 The oligosiloxane was removed by distillation and isolated in
69% yield.
COMPACTING

• Mechanism used to reduce the size of material

such as waste material or bio mass and bundle it
with wire so it holds its shape, though some waste
baler machine rely on the post compaction
adhesion of the waste to hold the bale’s shape.

• Bailing
• Baling achieves a much higher density with an
additional one-third reduction in waste volume.
• Compaction-increases waste density 40 or 50 lbs.
per cubic foot.
• Baler-increases waste densities of 60 to 75 lbs.
per cubic foot.
Types of compactor
On basis of mobility of waste:- 
• Stationary equipment
• Moveable equipment
On basis of volume of waste:-
• Low-pressure (less than 7kg) compaction
• High-pressure (more than 7kg) compaction
 When wastes are compressed, their volume is
reduced:-
 Volume Reduction (%) = (Vi – V f \ Vi) 100
 Compaction ratio = Vi\ V f
 NOTE: Vi = volume of waste before compaction and
Vf = volume of waste after compaction.
Selection of compaction equipment

• Characteristics:- size, composition, moisture content,

amount of the waste to be compacted.
• Method of transferring and feeding wastes to the
compactor, and handling.
• Use of compacted waste materials.
• Design characteristics:- size of loading chamber,
compaction pressure, compaction ratio, etc.
• Operational characteristics:- energy requirements,
maintenance requirement, simplicity of operation,
reliability, noise output, air and water pollution
control requirement.
• Site consideration, including space and height,
access, noise and related environmental limitations.
TYPE MODE OF APPLICATION
ACTION

SMALL GRINDERS GRINDING, MESHING ORGANIC WASTE

CHIPPERS CUTTING,SLICING PAPER,CARDBOARD

LARGE GRINDERS GRINDING , MESHING BRITTLE , FIABLE MATERIAL

JAW CRUSHERS CRUSHING, BREAKING LARGE SOLID

RASP MILL SHREDDING, TEARING MOISTENED SOLID

WASTE

SHREDDERS BREAKING , TEARING MUNCIPAL SOLID

WASTE

CUTTERS SLICING,CUTTING MUNCIPAL SOLID WATE

  
Whole process…
• Trash collected for compacting and bailing
• Compacting( in COMPACTOR)
• Bailing of waste
• After bailing it transported to landfilling.
• Landfilling( in two ways given in pic. Below)
Working of compactor
 
TIRE RETREADING PROCESS

 Receiving Department: Worn tires are brought into

this designated area and visually inspected and
arranged in rows for retreading.
 Initial Inspection: Tires are mounted on inspection
spreaders allowing for a thorough examination of
the internal and external casing.
 Buffing:The worn tire is placed on a buffing machine
for removal of the original tire tread.
 Repairing: Determining the extent of injury, the
damaged area is filled-in with cushion gum or rope
rubber and aligned with the buffed surface using a
patch.
• Curing
• Cold Process Curing 
• The tires are loaded into a pre-cure curing chamber (3
meters inside diameter and can hold anywhere from 12”-
38” tires at one time).The chamber head is adjustable
from 210°F to 300°F.
• Cure times vary from 2-1/2 to 4 hours.
• Mold Curing Process
• Common curing temperature:-300°F.
• Heating of metal molds can be done either with steam or
electricity.
• Curing times will vary depending on tire size.
• Final Finish and Inspection
• Finished, cured tire is examined to ensure that the tire
meets customer and government regulations.
• The tire’s appearance is further enhanced.