waste 4

Electronic-scrap recycling
Andreas Hornung and colleagues explain how pyrolysis neatly turns
brominated electronic scrap plastics into recyclable copper and methanol
feedstock while removing the halogens
PYROLYSIS the thermal decomposition
of a material in the absence of oxygen
is a process that can be applied to
a wide range of polymers, including
polymer mixtures, spilled mixtures and
mono fractions.
The problem is that if the feed contains
all kinds of materials, it is difficult to
develop a process that can handle the
breadth of materials. Moreover, the
output of the process can be just as
heterogeneous as what went into it, and
that tends to limit the options for reusing the materials. So the challenge is
to create new recycling technologies that
are versatile enough to handle a variety of
mixed plastic resins and additives typically
found in post-consumer waste streams,
economic to operate, and result in an end
product that is attractive for the industry
to re-use.
The Haloclean process, a rotary kiln
process developed by researchers at the
Forschungszentrum Karlsruhe, Germany
as part of a European project for recovery
of precious metals and materials from
electronic scrap, looks to fit the bill. Not
only does it turn the plastic components
of electronic scrap into gaseous or liquid
fuels that can be gasified and turned
into methanol, it also makes it possible
to recover copper and precious metals
from the scrap, ready for recycling. The
process has already demonstrated its
ability to recycle brominated electronic
scrap in extensive parametric studies. The
process will be scaled up at a plant due
to be commissioned later this year by Sea
Marconi, an Italian company specialising
in the decontamination of electrical
transformers.

the kiln

Figure 1: Haloclean
reactor

The Haloclean rotary kiln is specially

designed for the pyrolysis of high amounts
of inert and/or thermoset-containing
materials, eg electronic scrap. The
invention is based on the experience
with a vertical reactor system for the

spheres feed
scrap feed

oven
nitrogen

46

purge gas inlet by 200 sintered

metal plates on the screw shaft

tce july 2007

conversion of thermoplastics, the socalled cycled-spheres reactor. Hornung et

al invented a system that improves the
heat transfer to poorly heat transferring
materials like plastics, ensuring that
decomposition at laboratory scale can also
be described with micro kinetic analysis.
Using a reaction vessel filled with spheres
improves the heat conductivity by order of
magnitude of at least one. The system used
screw cycling metal spheres to keep the
polymer melt hot and to heat up entering
melt by mixing with metal spheres.
Obviously, the system was not suitable for
non-melting plastics. The idea of heatconducting metal spheres and a screw
which not only transports spheres but also
feed material was kept and incorporated
in an industrial reaction system, a rotary
kiln. To keep the performance in low rates
of consecutive reactions of the pyrolysis
gases as well as low residence times of the
pyrolysis gases in the system at all, the
hollow screw shaft has been equipped with
200 sintered metal plates. These plates
are permanently cleaned by the material
passing their surface, thus keeping the
inner core of the screw clean from pyrolysis
products and they introduce the purge gas
directly where the pyrolysis products are
evolved (see Figure 1).
The residence time control of the rotary
kiln is completely different to existing kiln
types. Feed and heat-transferring spheres
are transported in distinct volumes through
the kiln. By using the screw in forward and
backward movements the residence time
can be greatly extended, even keeping
the material permanently in motion and
mixing. The system is indirectly electrically
heated by an outer oven and by the screw.
The system has so far been at built pilot
scale (see Figure 2), and will be transferred
to technical scale in 2007 by Sea Marconi
in Turin, Italy.

Figure 2: The Haloclean plant.

dibenzodioxins and -furans if not treated
properly.
Existing technologies to treat these
fractions include co-combustion or use
in copper smelters, but because they
convert the plastic into energy rather
than recycling it, they do not contribute
to reaching the new European recycling
quotas for electronic goods.

the European dimension

Plastics in electrical devices contain

different additives like phosphates,
brominated compounds, chlorinated
substances or antimony oxides in order to
suppress the evolution of flames and the
development of heat in case of fire.
However, brominated flame retardants in
particular create problems when electronic
and electrical equipment reach the end of
their life. If landfilled, toxic brominated
flame retardants may slowly leach out
into the groundwater, where they persist
for several years, or they can be evolved
into the air. When incinerated, the flame
retardants can lead to the formation of
treatment of electronic scrap
toxic polybrominated dioxins and furans.
Treating electronic scrap is more
Although phosphates are replacing
complicated and delicate than treating
more and more brominated additives there
shredder residues or shredder light
is still a wide range of manufacturers
fractions. Electroscrap consists of a mixture around the world using them. So waste
of thermoplastics and thermosets which
will continue to contain these substances.
contain high amounts of bromine, precious The European directive for waste electrical
metals, non ferrous metals, and useful
and electronic equipment, which came
inerts. The material also has a tendency
into force in 2003, now requires that a
to react to high amounts of carbonaceous
large percentage of electronic scrap is
recycled (see Table 1 for the recommended
residue as well as forming brominated

waste 4

Figure 5: Television printed circuit boards,

pyrolysed at 350 and 450 C, 2 h at each
stage and the related remaining residues

Figure 6: Housing fractions, pyrolysed at

a too low temperature of about 350 C
for 2 h, the residues becoming sticky
quotas for 2006). This means that a new
innovative technology is needed to help
recycle electronic devices containing
bromine.

the Haloclean rotary kiln process

Since 2002, a European consortium
has been dealing with the transfer of a
pilot-scale Haloclean rotary kiln system
to technical scale. The technical scale
unit will have a capacity of 6000 t/y (or
685 kg/h) compared with the 40 kg/h
throughput rate of the pilot plant. The
Haloclean process, combined with its
post- treatment facilities, transforms
electronic scrap into three typical
fractions: residues containing metals,
precious metals, carbon, glass and inerts;
phenolic-based oils; and HBr.
The process helps the electronics
industry reach European recycling quotas
by delivering a residue that can be used
as a raw material in copper smelters, an

dehalogenation of pyrolysis oils

Finally we deal with the dehalogenation
of pyrolysis oils from electronic scrap. In
order to use those materials for feedstock
recycling, synthesis gas production or
fossil fuel substitution, a dehalogenation
step is needed. To make the oils suitable
for recycling, their halogen content must
not exceed 10 ppm. There are several
established ways of dehalogenating
pyrolysis oils.

Remarketing
and
recycling

1 White goods

80%

75%

2 Brown goods
3 Lamps
4 Tools, electronic/electric
5 Toys, electronic/electric
6 System control and
measurement

70%
70%
70%
70%
70%

50%
50%
50%
50%
50%

7 IT and Telecomms
8 Entertainment

75%
75%

65%
65%

10

12

14

16

20

Phenol, 2, 4,6-tribromo-

Phenol, 2, 4-dibromo-

18

Phenol, 2, 6-dibromo-

Phenol, 4-bromo-

Phenol, 4-isopropyl-

(a)

Phenol, 2-bromo-4-methyl-

Phenol

Phenol, 2-bromo-

Table 1: Recycling quotas of the European Union

Detector response

22

1
3

10

12

14

Phenol, 4-propyl-

Phenol, 4-isopropyl-

Phenol, 2-ethylPhenol, 4-ethyl-

Phenol

(b)

Phenol, 4-methyl-

Retention time (min)

Phenol, 2-methyl-

Figure 4: Populated computer circuit

boards, pyrolysed at 350 and 450 C, 2 h
at each stage and the related remaining
residues

Total quota
inc. thermal
treatment

Category

Detector response

Figure 3: Non populated computer circuit

boards, pyrolysed at 350 and 450 C, 2 h
at each stage and the remaining residues;
if necessary these residues can be sieved
in fractions for accumulation of metals or
used in total.

oil low in bromine suitable for gasifiers

with combined methanol synthesis, and
HBr obtained through post-treatment
reactions.
Pilot-scale trials allowed us to
optimise several process parameters such
as temperature, residence time, rotation
speed and modes. The temperature has
been varied between 250C and 550C,
while residence time in the trials varied
from one hour and four hours.
In all cases, the bromine content
of the residue fractions was carefully
measured, especially the amount of
brominated dibenzodioxins and furans,
and correlated with temperature.
Different fractions of electronic scrap
were tested and pyrolysed. Figures 36
show feed materials and their related
residues. In the cases of populated and
non-populated computer circuit boards
and television boards, a non-sticky
residue results.
The trials show that different
materials, for example populated and nonpopulated circuit boards from computers
or television sets, as well as computers
and monitor casings, are best processed
in a two-stage process at 350 C and
450 C, with a residence time of 2 h at
each stage. The residue amount under
these conditions can be specified to 65
wt% for non-populated printed circuit
boards up to 88wt% for television
printed circuit boards or computer chips.
In the case of housing fractions, the
entire feed fraction has been converted
in oils and gases. This result is strongly
dependent on the composition of
the feed.
The chosen reaction conditions ensure
that all residue fractions consisting of
brominated dibenzodioxins or furans are
well below the German limits of 1 g/kg
for 2,3,7,8-tetrabromodibenzo-p-dioxin,
1,2,3,7,8-pentrabromodibenzo-p-dioxin,
2,3,7,8-tetrabromodibenzofuran and
2,3,4,7,8-pentabromodibenzofuran and
lower than 5 g/kg for 1,2,3,6,7,8hexabromodibenzo-p-dioxin, 1,2,3,7,8,9hexabromodibenzo-p-dioxin and
1,2,3,7,8-pentabromodibenzofuran
(limits set by the Deutsche Chemikalien
Verbotsverordnung for free transportation
of goods).

56

16

18

20

22

Retention time (min)

Figure 7: Dehalogenation of pyrolysis product from

tetrabromobisphenol A (a) and by copyrolysis with PP in a
closed ampoule (b), at 350 C for 15 minutes
A very different solution, which
is even suitable for the selective
production of HBr in the presence of
chlorine (without any catalyst use) is
the treatment of the pyrolysis oils with
molten polypropylene. In a temperature
range of 310 C 350 C polypropylene
acts as a hydrogen donor. HBr is
evolving from the brominated phenols
and substituted phenols are formed in
the case of the decomposition of flame
retardants such as tetrabromobisphenol
A (see Figure 7).
This treatment is offering the
possibility to use the gas and liquid
fraction from pyrolysis of electronic
scrap as fossil fuel substitute in copper
smelter processes or as feedstock for
methanol production via gasification.
The technical-scale prototype of the socalled polypropylene-reactor has been
recently finalised by Brabender of Duirg,
Germany. tce
Andreas Hornung (andreas.hornung@itc-tab.fzk.de) is
head of the pyrolysis/gas treatment department at the
Institute for Technical Chemistry, Forschungszentrum
Karlsruhe, Germany. Jochen Schner is researcher at
the same Institute and Helmut Seifert is head of the
Institute. Vander Tumiatti is managing director of Sea
Marconi Technologies, Italy. For references and further
reading, please contact the lead author.

july 2007

tce 47