Jean M. Hoffman
Senior Editor
Consider the mix of materials that
go into household appliances and
automobiles. The good news, say
researchers at Argonne National
Laboratory (Argonne), is that over
95% of the over 50 million vehicles
scrapped globally each year enter a
comprehensive recycling infrastructure.
Nearly 75% of the weight of the
vehicles is metals and the metals are
profitably recycled through direct
reuse, component remanufacturing,
and scrap processing or shredding.
Other components such as batteries,
automotive fluids, some windshield
glass, starters, alternators, and other
dismantled parts are also recycled.
The percentage of recycled materials from vehicles is about
to go up. Argonne, working with
the Vehicle Recycling Partnership
(VRP) of the United States
Council for Automotive Research
(USCAR), a partnership between
General Motors, Ford Motor Co.,
and Chrysler, and the American
Chemistry Council-Plastics Div.
(ACC-PD), is developing technology
for recycling polymeric materials
from shredder residue.
Scrap processors use giant 3,000
to 8,000-hp hammer mills to shred
both vehicles and other obsolete
metal-containing products. Household
appliances, industrial scrap,
and demolition debris are all candidates for being turned into fist-sized
chunks as a means of liberating the
metals. Processing-unit operations
vary but the basic process involves
air classification of the “lights” fraction
followed by one or more stages
of magnetic separation to recover
the ferrous metals.
Trommels and screens are then
used to remove particles smaller
than about 5/8 in., followed by one
or more stages of eddy-current
separations to recover the nonferrous
metals.
Once the metals are gone, what’s
left is called shredder residue. It’s
typically a mix of polymers (plastics,
rubber, and polyurethane foam), a “fines” fraction that includes metal
oxides, glass, and dirt, as well as
residual amounts of ferrous and
nonferrous metals. For each ton of
metal a shredding facility recovers
there is roughly 500 lb of shredder
residue. Unfortunately, this byproduct
has historically ended up
in landfills. That’s because recycling
efforts were driven by the value
of the metal the single largest
source of recycled ferrous scrap for
the iron and steel industry is obsolete
automobiles.
In the last 15 years, however,
both automobiles and white goods
have increasingly used polymers
and composites. Existing separation
technologies for polymer recovery
rely on differences in density
to separate solid particles. These
methods will work on certain thermoplastics.
But shredder residue
content has overlapping densities
and shapes which make it difficult
to get enough material with the
right purity for scrap processors.
Bulk separation
Argonne’s new process is designed
to efficiently separate
polymers of equivalent densities.
Called froth flotation, it was originally developed to separate acrylonitrile-
butadiene-styrene (ABS)
from high-impact polystyrene
(HIPS); a mixture of plastics that
is typical of that recoverable from
obsolete appliances. A large-scale
(1,000 lb/hr) pilot plant was built
and operated at the Appliance Recycling
Center of America’s Minneapolis
facility to confirm process
economics and the effectiveness of
Argonne’s froth-flotation process.
The pilot plant recovered ABS
at purities in excess of 99% and at
yields of more than 80%, reports
Argonne’s Energy Systems Div. Director
Ed Daniels. ABS recovered
from this operation was successfully
used to injection mold automotive
parts, thus confirming the
feasibility of using obsolete postconsumer
plastics (in some cases,
plastics more than 15 years old)
to meet the performance requirements
of parts produced for this
industry today.
“Argonne has since adapted the
basic process to separate plastics
from other mixed-waste streams
including polyolefins, styrenics,
and rubber from the mixed plastics
found in consumer electronics and
auto-shredder residues,” says Energy
Systems Div.
Project Manager
Process Engineering
and Analysis
Group Bassam J.
Jody.
“The complexity
of shredder residue
makes it impractical
to recover recyclable
materials in a single
step. So Argonne
developed a mechanical-
separation
system that employs
commonly us e d
shredder equipment
to isolate polymers
and metals into preconcentrates
that are
more manageable.
The pilot plant processes
up to 2 tons
of shredder residue
hourly and can recover 90% of the polymers (pieces
larger than 2 mm) in the shredder
residue and over 90% of the residual
ferrous and nonferrous metals
(larger than 2 mm),” says Jody.
The plant can separate materials
in different sequences. But a
typical one starts with the manual
removal of large metallic and
polyurethane foams (PUFs), as
well as rocks. (Full-scale shredders
screen out large pieces by a
trommel and/or a destoner).
Breaking the PVC chain
PVC (or vinyl) recycling in the U.S. likely will continue to be based
on mechanical methods of grinding material into flakes and powder,
and then reusing it to manufacture products much like the originals
(pipes to pipes, for example). This method does not break the polymer
chain. The Vinyloop process developed by Solvay SA, Belgium,
is one recycling technology that does break the polymer chain.
Vinyloop makes possible separation of PVC from polyester fiber,
glass fiber, natural textiles, polyurethane foam, metals, rubber and
many other materials through selective dissolution.
Physical processes including washing and cutting, grinding, milling
and a homogenization step turn the waste into a form that can
be fed into the Vinyloop. The need for these operations and their
sequence depend on the waste’s composition.
Dissolution takes place using a solvent that selectively dissolves
the PVC compound and not the secondary material. It is carried out
at a temperature which is adapted to the material and its composition,
always in the absence of air in a closed process.
Separation techniques are determined by the nature of the insolubles.
They include centrifuging,
decanting, or cycloning. This is
because the behavior of fibers from
coated fabric differs from that of rubber
in waste from cables, for instance.
After separation, the secondary material
is washed with pure hot solvent
to eliminate virtually all the dissolved
PVC compound, then stripped with
steam to recover all the solvent, and
then discharged.
Precipitation of the PVC begins
when additives are introduced. This is
a specific feature of this recycling process
and allows the properties of the
output to be adjusted. At Vinyloop
Ferrara SpA, in Italy, a plasticizer is
added to adjust the shore hardness.
Steam is injected to evaporate the solvent
completely.
The PVC compound formulation
is recovered as an aqueous slurry. All components of the original PVC
resin formulation are recovered in the regenerated compound, not
just PVC (except in special cases or in voluntarily designed separation).
The slurry from the precipitation (a mixture of process water
and regenerated PVC compound) is dried. The process water is
treated to reach the required purity before discharge. And the regenerated
PVC compound is packed and ready for use.
Solvents run in a closed loop. Over 99.9% of the solvent is recovered
and separated from the water in a multistep process using
condensation and density separation. A final gas effluent treatment
lowers the solvent concentration in the flue gas to meet legal
requirements.
The Ferrara Vinyloop handles five major categories of materials
(cables, automobile, flooring, tarpaulins, and rigid product). The process
can recycle PVC composites with any PVC concentration. |
The remaining material is shredded
to about 1-in. chunks and then
conveyed to a two-stage trommel.
The first stage removes fines. The
second removes thin planar and
semiplanar pieces through adjustable
slots. This portion is primarily plastics, rubber, and small amounts
of metal, foam, and fiber pieces.
This residue passes over a magnetic
pulley to recover the ferrous metals
and over an eddy-current separator
to sift out nonferrous metals.
Oversized material exits the
trommel and consists primarily of
PUF that gets squeezed down so it
exits the shredder as a larger piece.
Also in this stream are fabrics, fibers,
and plastics, as well as metals
that are too big to go through the
trommel slots. The oversized material
also passes over a magnetic
pulley and eddy-current separator
that extract metal alloys.
“About one-third of the shredder
residue the plastic-intensive
portion is recovered as a polymer
concentrate, says Jody. “This gets
granulated to an average particle
size of 1/4 to 3/8 in. It is processed on
a vibrating screen to remove fines
and an air stream removes residual
foam pieces, dust, and other light
materials. Next comes the froth flotation process. Here the plastic
concentrate goes into a solution
that selectively enhances or retards
the hydrophobicity (repelled by
water) or hydrophilicity (attraction
to water) one or more of the
targeted plastics so that they can be
separated from the mixture.”
Froth flotation
“The process uses a series of six
separation tanks,” explains Daniels.
“The chemistry of the solutions in
each tank controls the separation
effectiveness of the overall process.
So-called ‘light’ materials, including
polyolefins, float in the first
tank. At this stage the process can
also be set to force over 90% of the
wood to float so it can be dealt with
only once. The ‘light’ fraction also
contains appreciable amounts of
different rubber species. Any sinkers
at this stage become the ‘heavies’
and include metals, glass, rocks,
rubber, and glass-filled nylons.”
As the concentrate progresses from one tank to the next, Daniels
continues, the polyolefins are removed
from the “lights” followed
by targeted polymers such as ABS,
PC, ABS/PC, PS, and PVC. Final
processing includes polishing and
cleaning steps to remove dirt and
contaminants for better economics
and marketability.
PUF recovery
Though the PUF is only 5% of
shredder residue, it amounts to over
30% of its volume, says Jody. “The
market for recycled foam in North
America continues to grow. Foam
rebond industries import millions
of pounds of scrap foam from
Europe and Asia. The imported
scrap supplements the more than
1.75 billion pounds of virgin foam
used to produce such foam products
as residential and commercial
carpet padding, automotive carpet
padding and headliners, car-seat
cushions, and other consumer and
automotive products.”
But the viability of foam recovered
from shredder residue for the
foam-rebond market depends on
two key factors: Development of an
economical process for recovering
foam from shredder residue, and
confirmation that the recovered
foam meets quality requirements,
says Daniels. Unsurprisingly, Argonne
finds the highest-quality foam
comes from dismantling and then
washing the foam from seats. But
manual separation of the foam is not
economical.
Researchers from several of the
organizations involved developed
a continuous process for retrieving
flexible foam from shredder residue.
The continuous foam-washing
and drying system was pilot
tested at a shredder facility. Economic
analysis of the process indicates
a potential payback of less
than 2 years for a plant producing
about 1,000 tons/yr of foam.