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Authors:
Frank E. Mark
Dow Europe, fmark@dow.com
Theo Lehner
Boliden Mineral AB, theo.lehner@boliden.se
A technical
paper from :
TABLE OF CONTENTS
SUMMARY 2
1. INTRODUCTION 3
1.1 WASTE ELECTRICAL AND ELECTRONIC EQUIPMENT (WEEE) 3
1.2 PLASTICS INDUSTRY ISSUES 3
1.3 NON-FERROUS METALS INDUSTRY ISSUES 3
1.4 PROGRAMME OBJECTIVES 4
2. WEEE CHARACTERISTICS 5
2.1 ELECTRICAL AND ELECTRONIC (E+E) WASTE 5
2.2 FEED SUPPLIED TO NON-FERROUS METAL RECYCLING PLANTS 6
2.3 WEEE AS A SECONDARY RAW MATERIAL 6
6. RESULTS 14
6.1 METALS RECOVERY 14
6.2 COAL SUBSTITUTION: ENERGY BALANCE FOR THE ZINC FUMING PROCESS 14
6.3 METALLURGICAL ASPECTS: ZN PRODUCT QUALITY 15
6.4 EMISSIONS, MATERIAL AND MICRO-ORGANIC BALANCES 15
6.5 DESTRUCTION EFFICIENCY 16
7. ENVIRONMENTAL IMPACT 18
7.1 EMISSIONS TO AIR 18
7.2 EMISSIONS TO WATER 18
7.3 DISPOSAL OF SOLIDS 18
7.4 WORKPLACE SAFETY 18
8. CONCLUSIONS 19
9. RECOMMENDATIONS20
10. ACKNOWLEDGEMENTS 20
1
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
1. SUMMARY
A growing range of waste electrical and electronic equipment (WEEE) can now be
used as a feed stream in non-ferrous metal smelting plants. There are significant
environmental benefits, including the complete destruction of all micro-organic
compounds, and economic benefits both for the smelters in recovering valuable
metals, and for society in terms of reducing waste management costs.
The Association of Plastics Manufacturers in Europe (APME) and the Swedish
company Boliden Minerals AB carried out a joint project which demonstrates that the
use of scrap cable and printed circuit boards as secondary raw materials can be
extended to include other E+E equipment such as personal computers (PCs). Plant
performance and workplace safety standards are maintained, and emission levels are
unaffected. In the Boliden plant alone 15,000 tons per year of PC scrap could be
treated in this way.
Emerging requirements to reduce the volume of material going to landfill and
preserve valuable resources can be met more easily with this approach. Metal
recovery rates are high and the plastics content serves a dual function, both as a
reducing agent and as a source of energy for the smelting process.
Since the complete dismantling of WEEE is often neither ecologically nor
economically feasible, the more comprehensive approach of Integrated Waste
Management (IWM) is now preferred. Several different waste treatment methods,
including mechanical recycling, are combined in a way that achieves the optimum
balance of environmental, social and economic requirements. The report demonstrates
how the use of WEEE as a source of secondary raw materials in non-ferrous metals
smelting is a viable component of an IWM approach. It includes a review of
Bolidens long experience of processing scrap cable and printed circuit boards, and
describes trials conducted with PC scrap.
2
INTRODUCTION
3
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
INTRODUCTION
processing provides a combination of environmental and ensures that maximum recovery rates are achieved over a
economic benefits. For example, only one-sixth of the very wide range of metals.
energy is needed to produce copper from recycled material A third type of feed stream, WEEE, is becoming of
than from ores. increasing interest to the non-ferrous metals industry. It
Because of the large range and quantities of non-ferrous contains metals that are capable of extraction, and the
metals present in scrap, this waste stream is an attractive plastics content can play important roles in the smelting
source of secondary raw materials. A correspondingly process.
wide range of processes is needed to recover all of the As with plastics recycling there can be potential concerns
metal values present. The metals refining industry, which about emissions when WEEE is recycled. However,
has long experience of recycling and recovery, is Boliden Minerals already have considerable experience of
characterised by a small number of producers who recycling a range of E+E components, in particular printed
between them make use of a wide range of technologies. circuit boards and all types of cable.
Figure 1 depicts the various streams involved in the
recycling of metals.
E+E Products
Assemblies
Smelter
Components
Collect
& Sort
Component
Production
Metallurgical
Network
Au Fe Pb Sb
Ag Al Sn In
Pd Cu Zn Se
Cd Mg Ni Te
By-Products
4
WEEE CHARACTERISTICS
Cables
Brown Goods
Data Processing
Equipment
Plastics Content
Office Equipment
Other Materials
Telecommunications
0 5 10 15 20 25 30 35 40 45
% of total E+E waste
FIGURE 2: E+E WASTE SECTORS SHOWING PLASTICS CONTENT
5
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
WEEE CHARACTERISTICS
Keyboards Personal Printed Car Typical 2.2 Feed supplied to non-ferrous metal recycling
Computers Circuit Electronics Copper plants
Boards Ore
Non-ferrous metals feed streams have traditionally been of
High Value Extractable Metals
Ag (%) 0.05 0.009 0.3 0.12 0.00034 two main types: a) separated and concentrated ores and b)
Au (%) 0.005 0.001 0.008 0.007 0.00001 secondary raw materials or scrap. Depending on the
Cu (%) 13 7 25 20 0.8 process being used, the types of secondary feed used range
Zn (%) 3 1.2 1.5 1 0.12
Pd (%) 0.0020 0.0004 - - 0.04 quite broadly. Examples of traditional sources of secondary
AlTOT (%) 18 11 3 - - raw materials for the production of copper, lead, zinc and
Medium - Low Value Extractable Metals precious metals are shown in Table 2.
Ni (%) 0.6 0.2 0.5 0.3 -
Pb (%) 0.3 1.5 - 1 - Copper (Cu) Lead (Pb) Zinc (Zn) Precious Metals
Metals processed in other facilities Copper wire scrap Used batteries Zinc ashes/brass Printed circuit
Bi (%) <0.0003 <0.0004 0.17 0.01 - Electrical switchgear Solder residue boards
Fe (%)1 3 <0.1 5 5 - Printed circuit Cathode ray tubes EAF dust from steel Catalysts
Sb (%) 0.3 0.5 0.06 0.08 - boards (Pb glass) mills Jewellery
Machine shop Cable shielding Galvanising sludges Photographic film
TABLE 1: TYPICAL METAL COMPOSITIONAL production waste Dross
ANALYSIS OF FOUR E+E WASTE STREAMS
TABLE 2. SOURCES OF SECONDARY RAW
1
Fe remaining after magnetic separation
MATERIALS
6
NON-FERROUS METALS
PRODUCTION
Secondary
Copper Raw Drying Scrap
Materials
Precious
NiSO4 plant
Metals Plant
Zinc clinker
Zinc Fuming Crude Nickel
Selenium
Slag Gold Palladium Sulphate
Silver Slime
Lead production
Electronic Scrap Kaldo
Refining Lead
Lead Concentrates Furnace
This report assesses the opportunities to use PC waste Secondary Zinc Production
added to the feed stream of the Zinc Fuming Furnace and 3) Recovery of zinc from secondary sources via the
in a current routine process in which waste printed circuit production of zinc oxide, to be supplied to either of the
boards are recovered in the Kaldo furnace. The design and above processes.
operation of these two furnaces is described below. A major secondary source is steel-making dusts which arise
during re-melting e.g. of galvanised car scrap. The dust
3.1 Zinc Fuming Furnace may contain impurities. This upgrading is carried out in
Total annual Zinc production in Europe in 1999 was rotary furnaces, e.g.Waelz kilns, or in fuming furnaces.
approximately 2.7 Million tons. Of this total, Technologies of types 2 and 3 are also referred to as
approximately 30% is generated from recycled raw pyrometallurgy. The technology applied during this
materials. The potential treatment capacity is significantly investigation was No.3. The flow sheet of the Rnnskr
higher. site (Fig. 3) illustrates the many options for entering feed
7
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
NON-FERROUS METALS
PRODUCTION
materials to non-ferrous smelters. In this study, the zinc Rnnskr Smelter. The heat from the off gases is
fuming process was chosen for PC waste because it uses recovered in the boiler.
fossil fuel both as a reducing agent and as fuel to recover Finely ground coal and preheated air is injected into the
zinc from slags. liquid slag through submerged injection pipes (tuyeres)
situated along both long walls of the furnace. The injected
A fuming plant consists of three separate processes: coal and air react immediately to form CO gas which
reduces metal oxides such as magnetite (Fe3O4), lead
1) Fuming furnace oxide, and zinc oxide in the slag. Some of the useful resul-
2) Settling furnace ting metals are in the vapour state, which enables them to
3) Clinker furnace be stripped from the liquid slag. Nitrogen contained in the
injected air assists the stripping of zinc vapour from the
These are shown in detail in Figure 4. slag.
PCs
Revert Slag
EAF dust
Cooling Tower
Material Hoppers
Waste Heat Boiler Economizer
Slag
Fuming
Furnace ESP
Settling
Furnace Ash Hopper
Transfer of Slag
Emission Check Points
Mixed oxide to Clinker Plant Raw Fume
Hopper Gas Cooler
The fuming furnace is a water-cooled rectangular furnace. Directly above the foaming bath of liquid slag, the zinc
Water cooling is used to generate an autogenous lining of vapour is re-oxidised to zinc oxide. The reduction process
frozen slag. This prevents attack of the steel shell by the also recovers other metals such as lead and arsenic, and in
corrosive liquid slag. The heat is recovered in the boiler. addition extracts halogens from the slag. The resulting
Hot cooling water from the heat exchangers is fed into the mixture of oxides (mischoxide) is de-halogenated in the
Skelleftehamn district-heating network connected to the clinker furnace.
8
NON-FERROUS METALS
PRODUCTION
The cleaned slag is tapped from the fuming furnace into Table 4 indicates the products and their quantities
the settler furnace. Here the remaining copper alloy produced by the zinc fuming plant.
droplets and copper sulphide droplets in the liquid slag are Tons per day Zn (%) Pb (%) As (%) Se (%) Cu (%)
separated into liquid phases. These contain copper and Mixed Oxides: 120 65 10 0.15 0.02 0.2
Slag: 750 1 0.02 <0.005 <0.002 0.5
other precious metals and are either recycled to the copper
Clinker: 110 75 5 0.01 - 0.1
smelter or sold for further treatment in specialised
metallurgical plants belonging to the Metallurgical TABLE 4: PRODUCTS FROM THE ZINC FUMING
PLANT
Network highlighted in Figure 1. These two phases, rich
in copper and precious metals, allow for the almost
3.2. Kaldo Furnace
complete recovery of copper and precious metals
There are several similarities in the manufacturing
contained in the PC waste added to the furnace.
technologies used to recover non-ferrous metals in the
zinc fuming furnace and the Kaldo furnace. Plastics are
The geometry and operating parameters of the zinc
used as fuel, easily oxidisable impurities are dissolved in a
fuming plant can be seen in Table 3.
liquid slag and precious and base metals are collected as an
Length 8.1 m District heating: 4-8 MW alloy or Matte (liquid sulphides). Both processes make
Width 2.4 m Capacity: 105 t (batch)
use of the other plants on the site to extract the metals.
Nozzles: 52 Fuming agent: Coal + preheated air
Fuming cycle: 120 min Coal consumption: 1.5 kg/t Zn Residue streams, such as slags, dusts, sludges or matte, are
Off gas volume: 140-170,000 m3/h Steam generation: 55 tph (40 bar) usually recycled on-site or processed at other companies,
TABLE 3: OPERATING PARAMETERS OF making use of metallurgical networks (Fig. 1) when
THE ZINC FUMING PLANT in-house processing capacity is unavailable or trading is
economically more attractive. Through this highly
The total feed to the Zinc Fuming Furnace consists of: integrated industry set-up, which avoids the need for
landfilling, the non-ferrous metals industry contributes to
1. Liquid iron-silicate slag from the electric copper
sustainable development by assuring ecologically sound
smelting furnace
and economically viable treatment of the residues.
2. Recycled reverts (solidified slag) e.g. from the transfer of The Kaldo furnace has been specially developed for the
the liquid iron-silicate slag (No. 1 above) by ladle recovery of metals from secondary raw materials. The total
amount of secondary raw materials and lead concentrate
3. Internally recycled dust from the fuming furnace (ash currently processed by Bolidens Kaldo furnace is
hopper - see Figure 4) approximately 100,000 tons per year. Most of the
large-scale plants at other major companies such as
4. Steel making dust (EAF dust) from electric arc furnaces
Norddeutsche Affinerie (Germany), Union Minire
re-melting galvanised steel scrap
(Belgium) and Noranda (Canada) have similar capacities.
5. E+E waste used for the test campaign
Kaldo technology has been practised for over 15 years to
recover cable scrap and printed circuit boards. Sound
ecological treatment is assured by means of stringent
emission regulations.
9
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
NON-FERROUS METALS
PRODUCTION
Process encapsulation
connected to bag house
Oil
Oxygen
Feed
The analysed material is blended in heaps to improve treatment. The sludge from the scrubber, and also the
integration with the melt and allow for maximum use of sulphide precipitate from the water treatment plant, are re-
energy and smelting capacities. The material is charged by circulated to the copper smelter to increase raw material
front-end loader into a skip hoist. The hoists are emptied recovery.
from above under a ventilated cover into the furnace The process produces a metallic copper alloy that is
vessel. The furnace is then tilted back into the operating transferred as liquid to the copper smelter for recovery of
position. Oxygen supply to the furnace via a lance is metals (Cu, Au, Ag, Pd, Ni, Se, Zn). Dusts (containing Pb,
started. If necessary, an oil-oxygen burner assists in Sb, In, Cd) are also generated and these are processed at
reaching the ignition temperature. Combustibles other smelters. Slag arising in the process is sent to the
contained in the charge supply heat for melting of the Boliden concentrator for extraction of any remaining
printed circuit board scrap, additional scrap and fluxes (slag metal value.
formers). Off-gases from the furnace are collected in a
water-cooled hood, where additional post-combustion air The role of plastics from cable insulation is to supply
also enters. Post-combustion takes place at around process heat for the smelting operation. PVC and
1200C. Residence time is estimated to exceed 2 seconds. crosslinked low-density polyethylene in the cable scrap, as
Steam is produced in the hood and the offtake and is fed well as the thermosetting resin in the printed circuit
into the smelters steam network for in-process use and boards, perform this very valuable function in the Cu
energy recovery. The process gases are then shock-cooled recovery process. Their high heat value provides most of
in a venturi scrubber, the dust particle loaded water being the process heat needed for secondary raw material
settled in a settler. Water is bled to the central water smelting to produce prime grade copper.
treatment plant for metal sulphide precipitation and lime
10
INTEGRATED WASTE
MANAGEMENT (IWM)
OF WEEE
4. INTEGRATED WASTE MANAGEMENT handling. For most of the articles or equipment the degree
(IWM) OF WEEE of dismantling needs to be evaluated further. Dismantling
adds significantly to the total cost of treatment and some of
Integrated Waste Management is a subject which is the products generated, such as old housings, have no
discussed widely both in society in general and in the material value.
development of European and national legislation. Within The use of secondary metals in the non-ferrous metals
the EU, several initiatives to describe the system in more industry requires all companies either to have shredding
detail exist such as (8). A proposed schematic overview of capabilities on site or to receive shredded materials. Partial
IWM, based on the one in Reference 8 (page 20), is dismantling has to be done at the recycling/recovery
shown in Figure 6.
Product
Waste
INSPECTION
Open loop MARKET
and eventual PROCESS
(Other use)
SORTING
END-USE-ENERGY
MARKET
PROCESS
RECOVERY
Waste for disposal
11
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
12
TRIALS WITH WEEE: PCs
fuming cycle in order to understand the effect of different their source or age has so far been identified. The average
feeding modes. PXDD/Fs content of all the samples of waste E+E plastics
Trial A B C D E so far investigated by APME have met the following two
Year 1996 1996 1996 1996 1999 German regulations: German Regulations for Hazardous
Type Base Medium High Prolonged Base Materials (6) and The German Chemical Banning
Feed slag (t) 85 85 85 85 85
WEEE (t) none 10 20 20 none Ordinance (7). A potentially high content of these
EAF dust (t) 5 5 5 5 15 organic compounds may well provide an extra reason for
large-scale handling, automatic fragmentation, Syngas
TABLE 7: EXPERIMENTAL PLAN FOR
PC RECOVERY IN ZINC FUMING PLANT production and post-combustion, thus minimising the
DURING SERIES II TO IV impact on the internal and external environment.
Furthermore, potentially significant amounts of these
In addition to the analysis for metals, heavy metals and impurities suggest that mechanical recycling of old plastics
precious metals shown in Table 1 (page 6), an extended from the WEEE should be looked at with great care. The
analysis was also performed during two of the above trials, process shown in Figure 4 has proven to be a sink for
B and C. The results are shown in Tables 8 and 9. dioxins and halogenated organic compounds, as
Organic Compounds Trial B Trial C demonstrated in section 6.5.
Ash (%) 9.2 7.2
Hu (MJ/kg) 31.2 24.4 The operators used their normal process mode to carry out
C (%) 65.4 62.7
H (%) 6.5 6.5 feeding to the furnace. The fuming process did not deviate
O (%) 12.0 14.1 from its usual performance. Operating capacity was limited
S (%) 0.2 0.2
during one of the campaigns by the capacity of the
TABLE 8: FEED STREAM ANALYSIS subsequent process. When feeding large amounts of PC
scrap, limitations in boiler capacity were experienced. In
Metals Trial B Trial C
Cd (mg/kg) 99 24 these cases the coal feed rate was reduced significantly
Tl (mg/kg) <1 <1 while charging the PC scrap/slag mix, indicating a
Hg (mg/kg) 9.5 0.9
Sb (mg/kg) 120 63 substantial substitution of coal by plastics.
As (mg/kg) 2 <1
Pb (mg/kg) 250 280 5.2 Printed circuit board and cable scrap recovery at
Cr (mg/kg) 41 13
Co (mg/kg) 1 1 the Kaldo furnace
Cu (mg/kg) 200 340 Processing of WEEE has been carried out in the Kaldo
Mn (mg/kg) 94 94
furnace for many years and is a regular commercial
Ni (mg/kg) 250 58
V (mg/kg) <2 <2 operation, conducted in campaigns between lead flash
Sn (mg/kg) 630 5,400 smelting campaigns. Similar plants are used for autogenous
Zn (mg/kg) 1,800 1,500
smelting of lead concentrates. The length of the
TABLE 9. METALS ANALYSIS OF PC PARTS campaigns, and hence the total annual capacity available
for WEEE, is thus determined mainly on economic
Analysis was carried out for halogen-containing organic considerations. Currently the split is about 50% of the
compounds: chlorinated PCDD/Fs, brominated available time running on lead and WEEE respectively.
PBDD/Fs and mixed brominated and chlorinated
PBCDD/Fs. The values found varied quite significantly. The Kaldo plant also makes use of an existing lead kettle
No correlation between the amount of PXDD/Fs and for the recovery of metals from lead sheeted complex
13
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
RESULTS
100%
In
WEEE
80%
Coal
60%
Out
40% Fume Gas
Cold Material (25 12000C)
20% Heat Losses
Chemical (Zn reduction)
0% Air
In Out In Out
FIGURE 8: INFLUENCE OF PLASTICS ON THE ENERGY BALANCE
IN THE FURNACE SEGMENT
14
RESULTS
The effects on batches with PC scrap are well within the in the aluminium content of the final slag would be
normal operational parameters with regard to fuming 0.7 - 0.9%, which in some cases may well lead to process
speed, despite a lowered coal feed rate of 1 ton per hour. problems.
The batches with PC scrap have an apparent lower unit
coal consumption per ton of zinc. From this we conclude 6.3 Metallurgical aspects: Zn product quality
that the plastics take part in the reduction of zinc oxide Zinc fuming rates during the trials were well within the
from the slag. The exact quantity is difficult to define at normal band of operation, in spite of a reduced coal feed
low substitution rates. rate. Figures 8 and 9 illustrate the performance of the trial
runs with regard to key parameters. From this we
The left side of Figure 9 illustrates the progressive conclude that a major part of the hydrocarbons contained
reduction in coal usage resulting from Bolidens efforts to in the plastic was used as a reducing agent, i.e. taking part
improve the operational efficiency of the Zinc furnace. in the chemical reaction. The standard chemistry
Each data point represents the average coal consumption describing this would be a formation reaction of hydrogen
rate for one month during a 3-year period. and carbon monoxide from the plastic, which then act as
reducing agents to form zinc metal in the melt.
3 Once this gaseous zinc leaves the molten bath
Tons of coal per ton of zinc fumed
2.8
it is oxidised to zinc oxide and is recoverable in
2.6
the electrostatic precipitator (ESP).
2.4
2.2
The composition of the product was
2 continuously monitored and fell well within
1.8 the normal range. No deviation in major
1.6
elements such as Zn, Pb, Sn, F and Cl, could
1.4
Monthly averages before the trials
Individual batch data be detected. The increased load of halogenides,
1.2
during the trial period
1
especially bromides, could be traced to the
Jan May Sep Jan May Sep Jan May Sep Jan 5 10 15
intermediate product called mixed oxides. The
1993 1994 1995 1996 Batch Number
15
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
RESULTS
6.4 Emissions, Material and Micro-Organic Balances lime precipitation, where fluorine is also precipitated
It is difficult to match mass and component balances on an (as NaF and CaF2), other salts (NaCl, CaCl2, NaBr and
industrial scale for elements at very low concentrations CaBr2 ) are discharged to the sea (Gulf of Bothnia). Of the
such as the volatile metals and halogens or for antimony added with the WEEE to the fuming process,
micro-organic components. The major uncertainties are over 65% leaves the plant with the raw fume. The overall
not with the analytical determination of concentrations potential recovery of Sb is about 40% under these
but rather with the difficulty of obtaining reliable conditions. The rest is stabilised in a glassy slag or
representative samples and making consistent mass flow contained in jarosite in mountain caverns. For mercury the
measurements. Additional problems arise from a corresponding figure was approximately 22%, but there
combination of sampling errors, analytical difficulties and was no special gas cleaning during the trial.
errors, scarcity of costly assays, and errors in determining
solid and gas flows. The material flow during the fuming The results of this study suggest that the following
tests was calculated for each batch and is illustrated in measures should be implemented to deal with WEEE
Figure 10, which contains typical compositions of the which contains potentially high amounts of Hg:
different streams around the fuming process. The
important elements, Hg, Br, Cl, F and Sb, were balanced. Tighter incoming WEEE control for Hg at the site and
Using this elemental analysis, data covering the entire Establishment of specifications which ensure low Hg
process, including the input and final output, can be levels or
calculated. Investment in effluent gas treatment (e.g. AC filter)
Hg Br Cl F Sb Hg Br Cl F Sb
(g) (Kg) (Kg) (Kg) (Kg) (g) (Kg) (Kg) (Kg) (Kg)
WEEE 70 <2.5 15 1.8 8.3 Raw Fume to
17 0.8 0.6 0.6 0.5
EAF Dust 20 <2.5 95 0.4 the Stack
Hg Br Cl F Sb
Furnace
Hg Br Cl F Sb
Hg Br Cl F Sb
(g) (Kg) (Kg) (Kg) (Kg)
Stack total out 22 3.2 0.9 1.3 0.01
In summary, less than 3% of the halogen content is emitted 6.5 Destruction efficiency
through the stack of the zinc refining plant in Norway. One of the objectives of this test programme is to support
The total halogen content is liberated in the fuming plant the general WEEE waste management strategy and to
and is neutralised in the gas cleaning section. Metal show that plastics are recyclable in the form of feedstock.
sulphide precipitates from the waste water plant are This has been the subject of many reviews and research
re-circulated to the copper smelter. After final polishing by studies because of the potential content of micro organic
16
RESULTS
halogenated substances, such as halogenated di-benzo clear destruction of all micro organic compounds from this
furans and dioxins (PXDD/Fs) in WEEE. Mechanical family with an efficiency of over 98%. From the total input
recycling of WEEE with increased detectable levels of of 6.4 g per batch only 0.104 g per batch leaves the fuming
PXDD/Fs will give rise to potential costs of handling and plant. This amount is almost evenly split between the
exposure to recyclates made from these WEEE plastics. gaseous emissions and the amount staying with the raw
The feedstock recycling technology as shown in this report fume. Since the raw fume is treated a second time at high
will not lead to these kinds of potential risk, if it can be temperature in the downstream kiln, which destroys
proven that no equivalent exposure to operators during residual PXDD/Fs on the solid, the destruction efficiency
feedstock recycling takes place. Equally important is the over both plants is more than 99%.
fact that the overall destruction efficiency of the process is
guaranteed at a high enough level. Because of this The method used to calculate the destruction efficiency is
important issue, dioxin and furan balances have been based on a per-batch type of operation, as the long- and
carried out and the results of two calculations are shown short-term PXDD/F emission results are not very
here. different. From this it can be concluded that in
determining the dioxin balance, short-term sampling of
In the case of Boliden, the co-treatment of waste PC two hours for one batch is equally representative as
equipment and steel dust makes it important to understand long-term sampling.
the respective potential contribution of these two
In Figure 12 the equivalent balance for the same batch
materials. The following short analysis (Figure 11) is based
using toxic equivalent factors (ITE) is shown.
on the total amount of polyhalogenated dioxins and furans.
Input
Input
Feed Quantity (tons) m
ITE Concentration ( g/kg) I-TE Flux
m
( g/kg) (g/batch) Slag 86 - 0.0
Output
Output
Output Quantity ITE Concentration I-TE Flux
17
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
ENVIRONMENTAL IMPACT
7. ENVIRONMENTAL IMPACT The dusty materials are handled with care due to their
toxic nature and are kept well contained and sealed
7.1 Emissions to air according to Swedish government regulations. The Pb
Measurements of the environmental impact of this type of bearing dust was checked for the occurrence of dioxins,
feed have been carried out by both the Boliden using a combination of three-monthly samples. These
measurement team and by an independent certified samples represented normal operating practice with the
laboratory. The results from both laboratories agree within addition of EAF dust, but without the addition of PC
satisfactory limits. The average emissions for the more scrap.
important compounds: CO, NOX, SO2, TOC and O2
were as follows: From the balance of dioxins it may be concluded that
dioxins could occur in the lead bearing dust deposits, but
CO NOX TOC SO2 O2
mg/m3 mg/m3 mg/m3 mg/m3 vol % that their concentration is below the values of the German
A 10-15 100-160 2 600-1000 12-14 Chemical Banning Ordinance. No indications are
B 10-15 160-180 1 945 10-13
available that these values are increased by the input of PC
C 20-50 160-190 2 740 11-12
scrap.
TABLE 11. EMISSIONS DURING ZINC FUMING
TESTING
Insoluble elements or compounds at the zinc plant
The emissions of other compounds are not shown as they (Norway) end up in the jarosite precipitate and are
were not affected by the co-processing of PC scrap. The disposed in dry mountain caverns. As indicated above, the
concentrations of dust and ten heavy metals (sum of Sb, final product has been checked for the occurrence of
As, Pb, Cr, Co, Cu, Mn, Ni, V, Sn) were <11 mg/m3 and dioxins. The result shows values below detection limits.
approximately 0.4 mg/m3 respectively.
7.4 Workplace safety
7.2 Emissions to water Workplace safety was investigated and analysed. The
The run-off waters and the process water from the potential impact on operators of dioxins/furans was
subsequent scrubbing at the clinker plant, where the raw checked by means of a dust-emission sample. The value in
fume is dehalogenated, are treated jointly with the waters the fuming plant during recycling of PC scrap was found
from the rest of the smelter site in a central water to be 0.08-0.12 ng/m3, well below the recommended
treatment plant. Heavy metals are efficiently precipitated as 50 ng TE Eadon /m3 (8 hours working hygienic value).
sulphides. The sulphide sludge is returned to the fluidised
bed roaster of the copper plant. The water is further The potential impact of micro organic compounds during
treated with lime to precipitate fluorine as fluorspar feed preparation was further checked by personal
(CaF2). After treatment, the cleaned water is discharged to monitoring. The results from two different modes of
the sea (Gulf of Bothnia). operation of the fragmentation plant show values below
the proposed German workplace standard. No special
7.3 Disposal of solids precautions were taken during the handling of the PC
Deposits originating from the fuming treatment are minor scrap. The level of heavy metals was found to be well
amounts of slag and lead. Minor slag volumes are used for below the hygienic limit values. If necessary the practices
on-site construction and lead is concentrated into the for handling this type of material could be tightened.
clinker dust which is shipped for recycling to other non-
ferrous metals producers.
18
CONCLUSIONS
19
TECHNICAL REPORT Plastics Recovery from Waste Electrical & Electronic Equipment in Non-Ferrous Metal Processes.
RECOMMENDATIONS
Current proposals from national environmental protection The authors would like to acknowledge the valuable
agencies call for dismantling of WEEE into separate contribution to the success of their work made by a
components to achieve better environmental performance. number of individuals and organisations:
The depth and extent of dismantling is sometimes very
vaguely defined and there is a great lack of sound data, Project Sponsors
both socio-economic and scientific. The joint efforts at Boliden Minerals AB
Boliden have shown that total dismantling of PCs is not Association of Plastics Manufacturers Europe (APME)
required. A low content of potentially harmful chemical American Plastics Council (APC)
elements in the feed, such as Hg or Cd, should be achieved
by selective dismantling. Investment in known and Companies
demonstrated gas cleaning technology may be appropriate. AB Arv. Andersson, Skellefte, Sweden
It is recommended that certain used E+E equipment,
which is known to contain substantial amounts of precious Individuals
metals and plastics, be handled in smelting processes of the M.Fisher American Plastics Council
types described.
APME E+E Sector Task Force
M. Frankenhaeuser - Borealis Polymers Oy
P.Peuch BP/Amoco
20
REFERENCES
AND WEBSITES
References: Websites:
(1) Lehner T. & Vikdahl A. (Boliden) Trim, slim and American Plastics Council:
quality. Paper presented at Copper 95, www.plastics.org
Santiago de Chile, November 1995 APME:
(2) Willbrandt, P. Operational Results of Norddeutsche www.apme.org
Affinerie Copper Smelter in Queneau. P (Ed.) Boliden (Sweden):
Symposium: Extractive Metallurgy of Cu,Ni,Co www.boliden.ca
Las Vegas, 1993. Bureau of International Recycling:
(3) Moulins, L.J. & Picard, D. Precious Metals Recycling www.bir.org
at Noranda Horne - a logical choice. Paper presented Institute of Scrap Recycling Industries:
at Precious Metals 1994, Vancouver BC. www.isri.org
(4) Vehlow, J. & Mark, Frank E. Electrical and Dow Europe:
Electronic plastics waste co-combustion with www.dow.com
Municipal Solid Waste for energy recovery. APME Noranda (Canada):
Technical Report No. 8020, February 1997. www.noranda.advancedmaterials.com
(5) Bureau of International Recycling (BIR) Plastic Norddeutsche Affinerie (Germany):
Coated Cable Scrap. Article on website www.affinerie-hamburg.com
http://www.bir.org/ Outokumpu (Finland):
(6) Hazardous Substances Ordinance: Gefahrstoffrecht, www.outokumpu.fi
Recht-und Verwaltungsvorschriften ber gefaehrliche Union Minire (Belgium):
Stoffe im Arbeits- und Vebraucherschutz, vom 26 www.um.be
Oktober 1993, zuletzt gendert 27 Januar 1999.
(7) Chemicals Banning Ordinance: Verordnung ber
Verbote und Beschrnkungen des Inverkehrbringens
gefhrlicher Stoffe, Zubereitungen und Erzeugnisse
nach dem Chemikaliengesetz (Chemikalien-
Verbotsverordnung - ChemVerbots V) 18 Juli 1996.
(8) Krajenbrink, G.W., Temmink, H.M.G., Zeevalkink,
J.A. & Frankenhaeuser, M. Fuel and Energy
Recovery. Consortium Report TNO-MEP -
R 98/220 for European Commission Directorate-
General XVII Energy. January 1999
(9) Lehner T. & Vikdahl A. Integrated recycling of
non-ferrous metals at Boliden Ltd.Rnnskr Smelter.
Paper presented at Sulfide Smelting 98,
San Antonio, Texas 1998.
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